JPS6324028B2 - - Google Patents
Info
- Publication number
- JPS6324028B2 JPS6324028B2 JP8593980A JP8593980A JPS6324028B2 JP S6324028 B2 JPS6324028 B2 JP S6324028B2 JP 8593980 A JP8593980 A JP 8593980A JP 8593980 A JP8593980 A JP 8593980A JP S6324028 B2 JPS6324028 B2 JP S6324028B2
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- coating
- paint
- resin
- modified polyolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000098 polyolefin Polymers 0.000 claims description 71
- 239000003973 paint Substances 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 31
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 150000002736 metal compounds Chemical class 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 42
- 239000011248 coating agent Substances 0.000 description 36
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- -1 ethylene, propylene Chemical group 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- XFNGYPLLARFULH-UHFFFAOYSA-N 1,2,4-oxadiazetidin-3-one Chemical compound O=C1NON1 XFNGYPLLARFULH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000005007 epoxy-phenolic resin Substances 0.000 description 5
- 239000000796 flavoring agent Substances 0.000 description 5
- 235000019634 flavors Nutrition 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 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
- 239000004711 α-olefin Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-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
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004826 seaming Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】
本発明は缶内面用塗料、更に詳しくは金属容器
内面用の分散型塗料に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a paint for the inside of a can, and more particularly to a dispersion type paint for the inside of a metal container.
従来から食品および飲料缶として鉄、ブリキ、
アルミニウムなどの材料からなる容器が使用され
てきた。これらの容器に詰める内容物を容器、つ
まり金属による汚染から守るために、該容器の内
部を、内容物に本質的に不活性で、かつ容器と内
容物間に効果的な障害となる有機塗料で被覆する
必要がある。現在この種の目的には有機溶媒に溶
解させたエポキシ−フエノール樹脂、エポキシ−
尿素樹脂などの有機塗料が保護塗膜として使用さ
れている。これらの樹脂は金属素材に対して優れ
た密着性を示すとともに、容器と内容物間に効果
的な障害となり、水、その他内容物に対するバリ
ヤー性が高いものである。この意味では金属容器
用内面塗料（以下缶内面塗料とよぶ）として好適
である。しかしながら、実際には製缶工程におい
て種々の外的な力が加わるので、塗料のベースと
なる樹脂は上記の性質以外にかなり可撓性に富ん
だものでなければならない。エポキシフエノール
樹脂やエポキシ−尿素樹脂などの熱硬化性樹脂を
金属板上で加熱すると加熱条件により、内容物に
対するバリヤー性、密着性、樹脂の可撓性などの
性質が大きく変化する。加熱処理の条件を調節す
るだけでこれらの性質を全て適切なレベルに維持
することはむつかしい。事実、製缶工程において
缶ブタのプレス成形、缶胴のフランジ加工、巻き
締めなどの成形加工を行なつた際に、塗膜の損傷
や部分的な剥離が認められる。この場合、塗膜の
加工性は充分とは言えず、わずかな損傷によつて
も密着不良の部分が発生し、露出金属の腐蝕が進
行する。この結果内容物の風味や新鮮さを損ない
食品を長期に亘つて保護するという食品包装材本
来の機能が充分果されないことになる。 Food and beverage cans have traditionally been made of iron, tin,
Containers made of materials such as aluminum have been used. In order to protect the contents packed in these containers from contamination by the container, i.e. metal, the interior of the container is coated with an organic paint that is essentially inert to the contents and provides an effective barrier between the container and the contents. It needs to be covered with. Currently, epoxy-phenolic resins dissolved in organic solvents, epoxy-phenolic resins, and
Organic paints such as urea resins are used as protective coatings. These resins exhibit excellent adhesion to metal materials, act as an effective barrier between the container and the contents, and have high barrier properties against water and other contents. In this sense, it is suitable as an inner surface coating for metal containers (hereinafter referred to as can inner surface coating). However, in reality, various external forces are applied during the can manufacturing process, so the resin that serves as the base of the paint must be highly flexible in addition to the above-mentioned properties. When a thermosetting resin such as an epoxy phenol resin or an epoxy-urea resin is heated on a metal plate, its properties such as barrier properties, adhesion to contents, and flexibility of the resin change greatly depending on the heating conditions. It is difficult to maintain all of these properties at appropriate levels simply by adjusting the heat treatment conditions. In fact, during the can manufacturing process, when forming processes such as press molding of can lids, flanging of can bodies, and seaming are performed, damage to the paint film and partial peeling are observed. In this case, the workability of the coating film is not sufficient, and even the slightest damage causes areas with poor adhesion, and corrosion of the exposed metal progresses. As a result, the flavor and freshness of the contents are impaired, and the original function of the food packaging material, which is to protect the food over a long period of time, is not fully fulfilled.
そこで、実際の製缶工程においては前記エポキ
シ−フエノール樹脂又はエポキシ−尿素樹脂を下
塗り塗料として金属に塗装した上に、更に別の塗
料を重ね塗りしてこれら熱硬化性樹脂単一塗膜の
欠点を補なつているのが現状である。この場合表
面塗装に使用される樹脂は塩化ビニル−酢酸ビニ
ル共重合体、塩化ビニル−酢酸ビニル−無水マレ
イン酸共重合体などである。また、これら塩化ビ
ニル系の樹脂の単一塗膜ではバリヤー性、加工性
が優れているが、金属素材に対する密着性が劣る
という欠点がある。 Therefore, in the actual can manufacturing process, the epoxy-phenolic resin or epoxy-urea resin is applied to the metal as an undercoat, and then another coating is applied over it to avoid the drawbacks of these thermosetting resin single coatings. The current situation is that they are making up for it. In this case, the resin used for surface coating is vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, etc. Further, although a single coating film of these vinyl chloride resins has excellent barrier properties and processability, it has a drawback of poor adhesion to metal materials.
以上の結果から熱硬化型樹脂、熱可塑性樹脂何
れを使用するにしても内容物に対するバリヤー
性、密着性、加工性、衛生性、フレーバー、耐煮
沸性など缶内面塗料として必要とされる巾広い性
質を高いレベルで維持できる樹脂はほとんど見あ
たらないと言える。この意味で缶内面塗料として
使用できる樹脂の種類は非常に限定されてしまう
が、現在上記適性のある樹脂の出現が強く望まれ
ている。 From the above results, regardless of whether thermosetting resin or thermoplastic resin is used, it has a wide range of properties required for can interior coatings, including barrier properties against contents, adhesion, processability, hygiene, flavor, and boiling resistance. It can be said that there are almost no resins that can maintain properties at a high level. In this sense, the types of resins that can be used as paints for the inside of cans are extremely limited, but there is currently a strong desire for the emergence of resins with the above-mentioned suitability.
従来から、缶内面塗料用として種々の樹脂が検
討されている。その１つとしてポリオレフインも
検討対象とされており、ポリオレフインは衛生
性、フレーバー等が非常に優れており、缶内面塗
料として単独もしくはエポキシ−フエノール樹脂
等の熱硬化性樹脂の下塗りと組合せることによ
り、巾広い用途に適用が可能であるとされている
が、金属もしくは熱硬化性樹脂との密着性に劣
り、更に塗料化適性が必ずしも良好でないため、
実用化が困難であつた。密着性については、ポリ
オレフインは結晶性が高く、無極性のため他の基
材との接着性に乏しいものとなつている。 Conventionally, various resins have been studied as paints for the inner surface of cans. Polyolefins are also being considered as one of them.Polyolefins have excellent hygiene and flavor, and can be used alone or in combination with an undercoat of thermosetting resin such as epoxy-phenolic resin as a coating for the inside of cans. Although it is said that it can be applied to a wide range of applications, it has poor adhesion to metals or thermosetting resins, and is not necessarily suitable for coating.
It was difficult to put it into practical use. Regarding adhesion, polyolefin has high crystallinity and is nonpolar, so it has poor adhesion to other base materials.
また、塗料化適性については、ポリオレフイン
は常温で溶解させる溶剤はほとんどなく、溶液型
塗料は一般に困難である。なお、変性ポリオレフ
インについても、変性の種類、度合にもよるが、
常温で溶剤に溶解する程度に変性したポリオレフ
インでは、未変性ポリオレフインが有している利
点、例えば衛生性、フレーバー等が劣化するとい
う問題が生じるため、溶液型塗料は通常では難か
しいとされている。更に、分散型塗料について言
えば、ポリオレフインを溶剤中に分散させるには
界面活性剤を使用するのが普通であるが、界面活
性剤が塗膜に残存することの問題が生じる。 Regarding suitability for forming into paints, there are almost no solvents that can dissolve polyolefins at room temperature, and it is generally difficult to form them into solution-type paints. Regarding modified polyolefins, it also depends on the type and degree of modification, but
Polyolefins that have been modified to the extent that they dissolve in solvents at room temperature have the problem of deteriorating the advantages that unmodified polyolefins have, such as hygiene and flavor, so it is generally considered difficult to use solution-based paints. . Furthermore, in the case of dispersion-type paints, surfactants are commonly used to disperse polyolefins in solvents, but a problem arises in that the surfactants remain in the paint film.
ポリオレフインを粉体塗装法によつて缶内面に
塗装するということも一応考えられ得ることであ
る。しかし、この方法では缶の隅の部分において
粉体が付き難く、従つてその部分の塗膜が薄くな
り内容物保護機能を十分に果たすことができず、
更に通常のベースコートを施こされた金属缶には
この粉体塗装法を適用することができないといつ
た重大な欠陥がある。また、必要以上の樹脂塗膜
が形成されるため省資源の立場からも望ましい方
法とは言えず、従来からの塗装設備を利用するこ
とができず、大規模な設備投資を必要とするため
現状においては工業上非常に不利である。 It is also conceivable to apply polyolefin to the inner surface of the can using a powder coating method. However, with this method, it is difficult for powder to adhere to the corners of the can, and the coating film in those areas becomes thinner and cannot adequately protect the contents.
Additionally, metal cans coated with conventional base coats have serious drawbacks, such as the inability to apply this powder coating method. In addition, since more resin coating is formed than necessary, it is not a desirable method from the standpoint of resource conservation, and conventional coating equipment cannot be used, requiring large-scale equipment investment, which is the current situation. It is very disadvantageous industrially.
また、ポリオレフインを熔融して塗装し塗膜の
冷却によつて固化するといういわゆるホツトメル
ト方式と云われるものがある。しかし、この方法
に於ても塗膜は非常に厚くなるという問題は解消
されないばかりでなく、ポリオレフインは金属面
およびエポキシ系ベースコートに接着せずしかも
融点が高いために通常はエチレン−酢酸ビニル共
重合体（略称EVA）を添加して用いる。この
EVAの量が増すと接着性は良くなるが内容物の
味が悪くなるという問題があり実用されていな
い。 There is also a so-called hot-melt method in which polyolefin is melted and applied, and the coating is solidified by cooling. However, this method does not solve the problem of creating a very thick coating film, and because polyolefins do not adhere to metal surfaces or epoxy base coats and have a high melting point, they are usually made using ethylene-vinyl acetate copolymer. It is used by adding a combination (abbreviated as EVA). this
Increasing the amount of EVA improves adhesion, but the problem is that the taste of the contents deteriorates, so it has not been put to practical use.
本発明は上記問題点のない缶内面塗料を目的と
して研究され発明されたものであつて、製缶用内
面塗料組成物に関するものである。 The present invention was researched and invented with the aim of creating a paint for the inner surface of cans that does not have the above-mentioned problems, and relates to an inner surface paint composition for manufacturing cans.
本発明の缶内面塗料は、界面活性剤を使用する
ことなく保存安定性の優れたものが得られ、かつ
缶の内面に均一、平滑な塗膜を形成することがで
き、在来からの塗装システムを活性することがで
きる。また、粉体塗装法を適用するとした場合に
比較して樹脂量を大巾に減少すること等工業上大
きな利点がある。 The can interior paint of the present invention has excellent storage stability without the use of surfactants, and can form a uniform and smooth coating film on the interior surface of cans, making it possible to achieve better storage stability without using surfactants. The system can be activated. Furthermore, there are great industrial advantages, such as the fact that the amount of resin can be greatly reduced compared to when a powder coating method is applied.
カルボキシル基含有ポリオレフインに金属化合
物を配合した変性ポリオレフインにつき、以下に
説明する。カルボキシル基含有ポリオレフインと
してはエチレン、プロピレンあるいはブテンなど
のオレフイン系単量体とアクリル酸、メタクリル
酸、イタコン酸、フマル酸、マレイン酸、無水マ
レイン酸などのエチレン性不飽和カルボン酸を共
重合せしめたもの、ポリエチレン、ポリプロピレ
ンあるいはポリブテンなどのポリオレフインにエ
チレン性不飽和カルボン酸をグラフト重合せしめ
たものである。あるいはエチレン性不飽和カルボ
ン酸のエステルを用いて、共重合もしくはグラフ
ト重合せしめた後、エステル基をケン化してカル
ボキシル基に変えたものであつてもよい。缶体が
レトルト殺菌用等のため耐熱性を要求される場合
には、ポリオレフインとして高密度ポリエチレ
ン、ポリプロピレン等が好ましい。エチレン性不
飽和カルボン酸の量はオレフイン成分100重量部
に対して0.01〜50重量部が好ましい。0.01重量部
以下では接着に関する効果が弱く、逆に50重量部
以上では接着に関する効果の向上が認められな
い。なお、エチレン性不飽和カルボン酸の変性度
合は0.01〜10重量％程度である。金属化合物とし
てはナトリウム、カリウム、マグネシウム、カル
シウム、亜鉛、アルミニウム、銅、ニツケル等の
炭酸塩、硫酸塩、酢酸塩、酸化物、水酸化物およ
び有機化合物等が用いられる。なお、薬品、食品
関連分野にはナトリウム、マグネシウム、カルシ
ウム、亜鉛、アルミニウムの金属化合物が好まし
い。金属化合物はカルボキシル基含有ポリオレフ
イン100重量部に対して0.05〜10重量部配合され
る。この範囲の使用で高い接着力を示す。0.05重
量部未満の使用では高い接着力を得ることはむず
かしく、逆に10重量部を超える添加は接着強度の
向上は認められない。 A modified polyolefin prepared by blending a metal compound into a carboxyl group-containing polyolefin will be described below. Carboxyl group-containing polyolefins are copolymerized with olefin monomers such as ethylene, propylene, or butene, and ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and maleic anhydride. It is obtained by graft polymerizing ethylenically unsaturated carboxylic acid to polyolefin such as polyethylene, polypropylene, or polybutene. Alternatively, it may be copolymerized or graft polymerized using an ester of ethylenically unsaturated carboxylic acid, and then the ester group is saponified to convert it into a carboxyl group. When heat resistance is required for the can body for retort sterilization, etc., high-density polyethylene, polypropylene, etc. are preferable as the polyolefin. The amount of ethylenically unsaturated carboxylic acid is preferably 0.01 to 50 parts by weight per 100 parts by weight of the olefin component. If the amount is less than 0.01 parts by weight, the adhesion effect will be weak, and if it is more than 50 parts by weight, no improvement in the adhesion effect will be observed. Note that the degree of modification of the ethylenically unsaturated carboxylic acid is about 0.01 to 10% by weight. As the metal compound, carbonates, sulfates, acetates, oxides, hydroxides, and organic compounds of sodium, potassium, magnesium, calcium, zinc, aluminum, copper, nickel, etc. are used. Note that metal compounds of sodium, magnesium, calcium, zinc, and aluminum are preferable for the pharmaceutical and food related fields. The metal compound is blended in an amount of 0.05 to 10 parts by weight per 100 parts by weight of the carboxyl group-containing polyolefin. It shows high adhesive strength when used within this range. If less than 0.05 parts by weight is used, it is difficult to obtain high adhesive strength, and conversely, if more than 10 parts by weight is added, no improvement in adhesive strength is observed.
なお、金属化合物はカルボキシル基含有ポリオ
レフインに混合分散されている場合のほか、金属
イオンが配位して塩を形成したり、金属イオン架
橋を形成している場合も含み得る。 In addition to the case where the metal compound is mixed and dispersed in the carboxyl group-containing polyolefin, the metal compound may also include cases where metal ions are coordinated to form a salt or metal ion crosslinks are formed.
変性ポリオレフインを合成するに際し、ポリブ
タジエン等の第３成分を併用することも可能であ
る。ただし、接着性等に悪影響を及ぼさない第３
成分を選ばなければならない。 When synthesizing the modified polyolefin, it is also possible to use a third component such as polybutadiene. However, a third layer that does not adversely affect adhesion, etc.
You have to choose the ingredients.
変性ポリオレフインはいくつかの方法で作るこ
とができ、以下に示すように加熱操作等と共に混
合する方法がある。前述のようなカルボキシル基
含有ポリオレフインと金属化合物とを約120〜220
℃の温度に加熱し、５〜120分間程度均一に混合
する。別法としてポリオレフイン、エチレン性不
飽和カルボン酸および金属化合物を同時に加熱混
合し、グラフト重合を行わせることも可能であ
る。場合によつては、未変性のポリオレフインも
しくは衛生性の優れた樹脂を配合して使用するこ
とも可能である。 Modified polyolefin can be produced by several methods, including a method of mixing together with a heating operation, etc., as shown below. The carboxyl group-containing polyolefin and the metal compound as described above are mixed at about 120 to 220
Heat to a temperature of °C and mix uniformly for about 5 to 120 minutes. Alternatively, it is also possible to heat and mix the polyolefin, ethylenically unsaturated carboxylic acid, and metal compound simultaneously to carry out graft polymerization. In some cases, it is also possible to use unmodified polyolefin or a resin with excellent hygiene.
カルボキシル基含有ポリオレフインもしくは金
属化合物を配合したカルボキシル基含有ポリオレ
フインは接着性は勿論、食品用においては厳しい
衛生性が要求される。従つて、合成途中または合
成後の段階で、アセトン、メチルエチルケトン、
酢酸エチルなどで十分洗滌することが望ましく、
洗滌処理を行つて得られたものは接着性において
格段に優れた性質を示すものである。洗滌の終了
は、GPCによつて低分子単量体もしくは単独重
合体の存在を確認することによつてチエツクする
ことができる。 Carboxyl group-containing polyolefins or carboxyl group-containing polyolefins blended with metal compounds are required not only to have adhesive properties but also to have strict hygienic properties when used for food. Therefore, acetone, methyl ethyl ketone,
It is recommended to wash thoroughly with ethyl acetate etc.
The products obtained after the washing treatment exhibit significantly superior adhesive properties. Completion of washing can be checked by confirming the presence of low molecular weight monomers or homopolymers by GPC.
本発明では以上のような変性ポリオレフイン単
独は勿論、未変性のポリオレフインと共に塗料化
することも出来る。変性ポリオレフインと未変性
ポリオレフインとの混合物を塗料化することによ
り、変性ポリオレフイン中の微量の残留物は、未
変性ポリオレフインで希釈され、全体に占める残
留物の割合は極端に減少する。従つて、残留物に
よる接着性への影響が小さくなり、更に洗滌作業
も比較的容易となる。また、変性ポリオレフイン
に対し、用途に応じた諸物性を出す為、広い範囲
の未変性ポリオレフインから適宜選択して混合す
ることにより、種々の要求に対処することも可能
である。 In the present invention, not only the modified polyolefin described above can be used alone, but also an unmodified polyolefin can be used to form a coating material. By forming a mixture of a modified polyolefin and an unmodified polyolefin into a paint, a trace amount of residue in the modified polyolefin is diluted with the unmodified polyolefin, and the proportion of the residue in the whole is extremely reduced. Therefore, the influence of the residue on the adhesion is reduced, and cleaning work is also relatively easy. Furthermore, in order to provide the modified polyolefin with various physical properties depending on the intended use, it is possible to meet various demands by appropriately selecting and mixing a wide range of unmodified polyolefins.
変性ポリオレフインと未変性ポリオレフインの
混合の割合は、変性ポリオレフインの変性率及び
用途により異なるが、エチレン性不飽和カルボン
酸量は変性ポリオレフインおよび未変性ポリオレ
フインのオレフイン成分に対して0.01〜６重量％
になるような割合で混合することが望ましい。従
つて、エチレン性不飽和カルボン酸による変性度
合の高い変性ポリオレフインでは多量の未変性ポ
リオレフインが混合できる。 The mixing ratio of modified polyolefin and unmodified polyolefin varies depending on the modification rate of modified polyolefin and the intended use, but the amount of ethylenically unsaturated carboxylic acid is 0.01 to 6% by weight based on the olefin component of modified polyolefin and unmodified polyolefin.
It is desirable to mix in proportions such that Therefore, a modified polyolefin having a high degree of modification with ethylenically unsaturated carboxylic acid can be mixed with a large amount of unmodified polyolefin.
変性ポリオレフインと混合される未変性ポリオ
レフインとしては変性ポリオレフインのベース樹
脂として使用されているポリオレフインと同一も
しくは別種のポリオレフインである。未変性ポリ
オレフインの例としては、高密度ポリエチレン、
中密度ポリエチレン、低密度ポリエチレン、ポリ
プロピレン、エチレン−プロピレン共重合体、ポ
リブテン、その他のエチレン−α−オレフイン共
重合体等である。 The unmodified polyolefin to be mixed with the modified polyolefin is the same as or different from the polyolefin used as the base resin of the modified polyolefin. Examples of unmodified polyolefins include high density polyethylene,
These include medium density polyethylene, low density polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, and other ethylene-α-olefin copolymers.
本発明に使用される親溶媒の一つとしては炭化
水素系の溶剤であり、沸点は用いられる変性ポリ
オレフインの軟化点以上のものが好ましいが、焼
付け時の温度よりもあまりに高い沸点を有する炭
化水素系溶剤を用いると形成塗膜中に溶剤が残留
する恐れがあつて好ましくない。具体的には、ト
ルエン、キシレンのような芳香族炭化水素、イソ
オクタン、ノナン、デカンのような脂肪族炭化水
素、メチルシクロヘキサン、エチルシクロヘキサ
ン、デカハイドロナフタリンのような脂環式炭化
水素、あるいはソルベントナフサ等の１種もしく
は２種以上の混合物を挙げることができる。 One of the parent solvents used in the present invention is a hydrocarbon solvent, and preferably has a boiling point higher than the softening point of the modified polyolefin used, but hydrocarbons with a boiling point that is too high than the baking temperature If a solvent-based solvent is used, the solvent may remain in the formed coating film, which is not preferable. Specifically, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as isooctane, nonane, and decane, alicyclic hydrocarbons such as methylcyclohexane, ethylcyclohexane, decahydronaphthalene, or solvent naphtha. One type or a mixture of two or more types can be mentioned.
また、本発明の他の溶剤としては、変性ポリオ
レフインの軟化点以上の沸点を有する炭化水素系
溶剤を除けば特に制限は受けず、ベンゼン、ヘキ
サン、ヘプタン、ミネラルスピリツト等の、変性
ポリオレフインの軟化点以下の沸点を有する炭化
水素系溶剤等の親溶媒が用いられる。また貧溶媒
としては、エタノール、メタノール、プロパノー
ル、イソプロパノール、ブタノール、オクタノー
ル、セチルアルコール、ダイアセトンアルコール
等のアルコール系溶剤、酢酸エチル、酢酸ブチ
ル、セロソルブアセテート等のエステル系溶剤、
メチルエチルケトン、メチルイソブチルケトン、
シクロヘキサノン、イソホロン等のケトン系溶
剤、エチルエーテル、エチレングリコールモノメ
チルエーテル、エチレングリコールモノエチルエ
ーテル、エチレングリコールモノブチルエーテ
ル、ジエチレングリコールモノメチルエーテル、
ジエチレングリコールモノエチルエーテル、ジエ
チレングリコールモノブチルエーテル等のエーテ
ル系溶剤、四塩化炭素、トリクロルエチレン等の
ハロゲン化炭化水素系溶剤、などを示すことがで
き、これらの１種もしくは２種以上を使用するこ
とができる。 Further, other solvents used in the present invention are not particularly limited except for hydrocarbon solvents having a boiling point higher than the softening point of the modified polyolefin, such as benzene, hexane, heptane, mineral spirits, etc. A parent solvent such as a hydrocarbon solvent having a boiling point below this point is used. Examples of poor solvents include alcohol solvents such as ethanol, methanol, propanol, isopropanol, butanol, octanol, cetyl alcohol, and diacetone alcohol; ester solvents such as ethyl acetate, butyl acetate, and cellosolve acetate;
Methyl ethyl ketone, methyl isobutyl ketone,
Ketone solvents such as cyclohexanone and isophorone, ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,
Examples include ether solvents such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether, and halogenated hydrocarbon solvents such as carbon tetrachloride and trichlorethylene, and one or more of these may be used. .
本発明において、変性ポリオレフインの軟化点
以上の沸点を有する炭化水素系溶剤のみでは保存
安定性に若干問題を生ずることがあり、貧溶媒の
みの使用では塗装直後もしくは焼付けの初期の段
階における樹脂粒子の軟化前に樹脂の析出による
白化現象が観察される。この白化現象の生じたま
まで焼付けをすると均一で平滑な塗膜を形成させ
ることはできない。本発明では両者の溶剤を混合
使用することにより、変性ポリオレフインの膨潤
を完全に防止することができ、タレ、レベリング
の面においてもより改良される。両者の溶剤の比
率は大略５／95〜95／５（重量）、望ましくは30／
70〜70／30程度から、それぞれの溶剤の種類、変
性ポリオレフインの種類等によつて適宜選択す
る。 In the present invention, using only a hydrocarbon solvent with a boiling point higher than the softening point of the modified polyolefin may cause some problems in storage stability, and using only a poor solvent may cause damage to the resin particles immediately after coating or in the early stages of baking. A whitening phenomenon due to resin precipitation is observed before softening. If baking is performed with this whitening phenomenon occurring, a uniform and smooth coating film cannot be formed. In the present invention, by using a mixture of both solvents, swelling of the modified polyolefin can be completely prevented, and sagging and leveling are further improved. The ratio of both solvents is approximately 5/95 to 95/5 (by weight), preferably 30/5.
It is appropriately selected from about 70 to 70/30 depending on the type of solvent, the type of modified polyolefin, etc.
本発明において、溶剤中に変性ポリオレフイン
を固体状態で分散せしめる方法としては、溶剤中
に変性ポリオレフインを加熱溶解し、これを***
剤中に撹拌しながら滴下して分散する方法、ある
いはボールミル、サンドグラインダー等の分散機
を用いて分散する方法などを採用することができ
る。変性ポリオレフインは溶剤中に固体状態で分
散しているため、比較的低粘度、高固形分となり
作業性および溶剤回収の面で有利である。この目
的に反しない程度に一部膨潤、溶解していてもよ
い。 In the present invention, the method of dispersing the modified polyolefin in a solid state in a solvent includes a method of dissolving the modified polyolefin in a solvent by heating and dispersing it by dropping it into a cold solvent while stirring, or using a ball mill or sand grinder. A method of dispersing using a dispersing machine such as the above can be adopted. Since the modified polyolefin is dispersed in a solvent in a solid state, it has a relatively low viscosity and a high solid content, which is advantageous in terms of workability and solvent recovery. It may be partially swollen or dissolved to the extent that this purpose is not violated.
また、本発明の缶内面塗料には、目的に反しな
い限り、顔料その他の充てん剤、分散性改良剤等
の添加物を加えることもできる。 Furthermore, additives such as pigments, other fillers, and dispersibility improvers can also be added to the can inner surface coating of the present invention, as long as they do not contradict the purpose.
本発明の塗料を適用する缶用素材としては、ア
ルミニウム板、鉄鋼板の表面に亜鉛、スズ、クロ
ム等をメツキしたメツキ鋼板、或いは鉄鋼板等の
広範な缶用金属素材が使用される。更に、本発明
によれば缶用素材として、ポリオレフイン等の樹
脂や紙ボード等の有機質基質の表面に、アルミニ
ウム箔のような金属箔を接着積層して成る複合
（コンボジツト）金属素材を使用することも可能
である。 As can materials to which the paint of the present invention is applied, a wide range of metal materials for cans can be used, such as aluminum plates, plated steel plates whose surfaces are plated with zinc, tin, chromium, etc., and steel plates. Furthermore, according to the present invention, a composite metal material is used as the material for the can, which is made by adhering and laminating metal foil such as aluminum foil on the surface of a resin such as polyolefin or an organic substrate such as paper board. is also possible.
上記の様な金属素材を、必要に応じトリクレレ
ン等の脱脂用溶剤で洗浄した後、フエノール樹
脂、エポキシ樹脂、エポキシ−フエノール樹脂、
エポキシ−尿素樹脂、ポリアミドを用いて、ハケ
塗り、スプレー塗装、浸漬塗料、ロールコーテイ
ング、静電塗装、電気泳動塗装、ラミネート被覆
等により皮膜形成する。なお、皮膜形成１層だけ
に限らず、異なる樹脂を用いた２層以上でもよ
い。また、皮膜形成に際し、ブライマー等を用い
てもよい。このように皮膜形成された上に、本発
明の塗料を適用することも出来る。 After cleaning the above-mentioned metal materials with a degreasing solvent such as triclelene as necessary, phenol resin, epoxy resin, epoxy-phenol resin, etc.
A film is formed using epoxy-urea resin or polyamide by brush coating, spray coating, dip coating, roll coating, electrostatic coating, electrophoretic coating, laminate coating, etc. Note that the film formation is not limited to one layer, but may be two or more layers using different resins. Furthermore, a brimer or the like may be used when forming the film. The paint of the present invention can also be applied to the film formed in this way.
本発明に係わる分散型塗料は外観上乳白色を呈
し、不揮発分５〜60重量％の濃度であり、40℃で
保存しても樹脂分の分離、沈降などが全く生じな
い非常に安定な塗料である。 The dispersion type paint according to the present invention has a milky white appearance, has a non-volatile content of 5 to 60% by weight, and is an extremely stable paint that does not cause any separation or sedimentation of the resin even when stored at 40°C. be.
本発明の分散型塗料を缶内面塗料として使用す
る場合、金属容器素材の表面に直接塗装すること
もできるが、従来のエポキシ−フエノール樹脂、
エポキシ−尿素樹脂、メラミン−エポキシ樹脂、
アクリル−エポキシ樹脂などの上にトツプコーテ
イング剤として使用することもできる。これら何
れの場合にも、造膜性、透明性、密着性、耐煮沸
性、過マンガン酸カリウム消費量、加工性などの
性質は良好である。本発明の分散型塗料を金属素
材または各種プラスチツクス上に塗装する方法と
してスプレー塗装、ロールコート塗装、ナイフコ
ート塗装、エアーナイフコート塗装など何れの方
法でもよいが、金属素材を完全に保護し、容器と
内容物間に効果的な障害となる保護塗料本来の機
能が発揮される塗装法でなければならない。この
意味では樹脂の塗膜厚を重要な役割も果たすこと
になる。どうしても避けられないピンホールなど
を考えた場合、実用的には前記熱硬化性樹脂と併
用することが望ましい。 When the dispersion type paint of the present invention is used as a can inner surface paint, it can be applied directly to the surface of the metal container material, but conventional epoxy-phenolic resin,
Epoxy-urea resin, melamine-epoxy resin,
It can also be used as a top coating over acrylic-epoxy resins and the like. In any of these cases, properties such as film-forming properties, transparency, adhesion, boiling resistance, consumption of potassium permanganate, and processability are good. Any method such as spray painting, roll coating, knife coating, or air knife coating may be used to apply the dispersion type coating of the present invention onto metal materials or various plastics, but it is possible to completely protect the metal materials. The coating method must enable the protective coating to function as an effective barrier between the container and its contents. In this sense, the resin coating thickness also plays an important role. Considering unavoidable pinholes, it is practically desirable to use the thermosetting resin in combination with the thermosetting resin.
本発明の有機溶媒分散型塗料を缶内面塗料とし
て使用すれば、ポリオレフインに起因した特徴が
生かされるのみならず、常温では有機溶媒に溶解
は勿論、分散させることが難かしいポリオレフイ
ンでも安定に溶媒中に分散させることができる。
しかも分散型塗料であるため、高い樹脂濃度で、
低い粘度の塗料を合成することも可能となる。一
般に缶内面塗料として塗膜にバリヤー性、内容物
保護機能を付与するためには一定塗膜厚が必要で
あるが、低い樹脂濃度の塗料をこの目的に使用す
ると塗料のタレが生じたり、缶の底部分が厚塗り
になるなどの問題が生じる。同時に缶底部にブリ
ツジなどが生じる原因となる。本発明の分散型塗
料では高い樹脂濃度で、かつ低粘度塗料の調整が
でき、目的とする塗装物が得やすいばかりでな
く、作業上の安全性、大気汚染、経済性に優れる
という点で非常に有利である。 When the organic solvent-dispersed paint of the present invention is used as a paint for the inside of a can, not only can the characteristics of polyolefin be utilized, but even polyolefin, which is difficult to dissolve or disperse in organic solvents at room temperature, can be stably dissolved in the solvent. can be dispersed into
Moreover, since it is a dispersion type paint, it has a high resin concentration,
It also becomes possible to synthesize paints with low viscosity. Generally speaking, a certain coating thickness is required to impart barrier properties and contents protection functions to the coating for the inside of a can, but if a coating with a low resin concentration is used for this purpose, the coating may sag or the coating may sag. Problems arise, such as thick coating on the bottom. At the same time, this may cause brittleness to occur at the bottom of the can. The dispersion type paint of the present invention has a high resin concentration and a low viscosity paint, making it easy to obtain the desired coated product, as well as being extremely safe in terms of work safety, air pollution, and economic efficiency. advantageous to
以下実施例によつて本発明を具体的に説明す
る。例中、部および％とは重量部および重量％で
ある。 The present invention will be specifically explained below using Examples. In the examples, parts and % are by weight.
実施例 １
ポリプロピレン（MI値10）100部に無水マレイ
ン酸20部およびキシレン375部を窒素吹込口、温
度計、撹拌棒を備えた１の３つ口フラスコに仕
込み、窒素ガス雰囲気中で撹拌しながら130℃に
加熱する。0.1部の過酸化ベンゾイルを40部のキ
シレンに溶解し、90分間で滴下する。滴下終了後
130℃で60分間加熱および撹拌を続ける。60分後
室温まで冷却する。得られた懸濁物をロ過し、キ
シレンを除去した後、メチルエチルケトンで洗浄
を２−３回繰り返し、メチルエチルケトン中に無
水マレイン酸および無水マレイン酸単独反応物が
液体クロマトグラフイーによつてほとんど認めら
れなくなるまで洗浄を続ける。得られたポリプロ
ピレン−無水マレイン酸共重合体樹脂（無水マレ
イン酸グラフト率0.6％）100部、水酸化アルミニ
ウム１部、ソルベツソ100（芳香族系炭化水素溶
剤、シユル化学剤）320部、メチルイソブチルケ
トン80部とを窒素ガス雰囲気下で130℃に加熱し、
完全に溶解する。これを下部を水冷したバツトに
注いで急冷する。平均粒径10μの乳白色分散件を
得た。この塗料は作製直後は勿論、３ケ月間経時
後でも安定であり、塗装時のガンのつまり（スプ
レー時）はない。Example 1 100 parts of polypropylene (MI value 10), 20 parts of maleic anhydride and 375 parts of xylene were charged into a three-necked flask equipped with a nitrogen inlet, a thermometer, and a stirring bar, and stirred in a nitrogen gas atmosphere. While heating, heat to 130℃. 0.1 part of benzoyl peroxide is dissolved in 40 parts of xylene and added dropwise over 90 minutes. After dripping
Continue heating and stirring at 130 °C for 60 minutes. After 60 minutes, cool to room temperature. The obtained suspension was filtered to remove xylene, and then washed with methyl ethyl ketone 2-3 times, and almost all maleic anhydride and maleic anhydride reactant alone were detected in the methyl ethyl ketone by liquid chromatography. Continue washing until it disappears. 100 parts of the obtained polypropylene-maleic anhydride copolymer resin (maleic anhydride grafting rate 0.6%), 1 part of aluminum hydroxide, 320 parts of Solbetsuso 100 (aromatic hydrocarbon solvent, Schul chemical agent), methyl isobutyl ketone 80 parts and heated to 130℃ under nitrogen gas atmosphere,
Dissolve completely. Pour this into a vat with a water-cooled bottom to cool it quickly. A milky white dispersion with an average particle size of 10μ was obtained. This paint is stable not only immediately after preparation but also after three months of aging, and there is no clogging of the gun during painting (spraying).
成形したアルミニウム缶の内面に、上記塗料を
エアレススプレーガンにより、100mg／100cm2の割
合で施し、190℃、５分間焼付けた。 The above paint was applied to the inner surface of the formed aluminum can using an airless spray gun at a rate of 100 mg/100 cm 2 and baked at 190° C. for 5 minutes.
この塗装物は平滑であり、下記の方法により通
電性を測定すると、電流の流れは検出されず、ア
イホール、ピンホールのないことが証明される。
また、レトルト試験（125℃−30分）によつても
白化およびプリスターの発生はなく、実用に耐え
るものであつた。また、焼付け塗膜には臭気はな
かつた。更に、１ベントでの折り曲げ（折り曲げ
条件は50cmの高さから３Kgの荷重を落下させて行
う）において、クラツク、白化等はみられず、良
好な加工性を示した。 This coated product was smooth, and when its conductivity was measured using the method described below, no current flow was detected, proving that there were no eyeholes or pinholes.
In addition, there was no whitening or pristal formation in the retort test (125° C. for 30 minutes), and the product was suitable for practical use. Moreover, the baked coating film had no odor. Furthermore, no cracks, whitening, etc. were observed during bending in one bend (the bending conditions were to drop a load of 3 kg from a height of 50 cm), indicating good workability.
第１図は、通電試験に供する装置の断面図であ
り、缶の金属部分１に施された塗膜２の上に食塩
水溶液３を入れ、アンメーター４により電流を検
知するものである。 FIG. 1 is a sectional view of a device used for the current test, in which a saline solution 3 is poured onto a coating 2 applied to a metal part 1 of a can, and an ammeter 4 detects the current.
実施例 ２
実施例１において、メチルイソブチルケトンに
代えてトルエンを用いても塗料作製時にはほとん
ど問題はなく、通電性を測定すると電流の流れは
検出されず、アイホール、ピンホールのないこと
が証明された。また、レトルト性、耐屈屈曲性等
は十分実用に耐えるものであつた。Example 2 Even if toluene was used instead of methyl isobutyl ketone in Example 1, there was almost no problem when making the paint, and when measuring electrical conductivity, no current flow was detected, proving that there were no eyeholes or pinholes. It was done. In addition, the retortability, bending resistance, etc. were sufficient for practical use.
実施例 ３
実施例１においてポリプロピレンに代えて高密
度ポリエチレン（M15）を用い同様の操作を行
う。得られたポリエチレン−無水マレイン酸共重
合体樹脂（無水マレイン酸グラフト率0.7％）と
水酸化アルミニウム0.5部、キシレン320部、メチ
ルイソブチルケトン80部とを窒素ガス雰囲気下で
130℃に加熱し、完全に溶解する。これを下部を
水冷したバツトに厚さ約0.5cmになるように注い
で急冷する。平均粒径10μの乳白色分散体を得
た。この塗料は作製直後は勿論、３ケ月間経時後
でも安定であり、塗装時のガンのつまりはない。
エポキシ−尿素系塗料を塗布したスチール缶に上
記塗料をエアスプレーガンにより100mg／100cm2の
割合で施し、180℃−５分焼付けを行つた。この
塗装物は平滑であり、レトルト試験（120℃−30
分）前後の密着性は良好であり、白化およびブリ
スターの発生はなく、耐屈曲性、フレーバー性等
は良好であり、十分実用に耐えるものであつた。Example 3 The same operation as in Example 1 is carried out using high-density polyethylene (M15) instead of polypropylene. The obtained polyethylene-maleic anhydride copolymer resin (maleic anhydride grafting rate 0.7%), 0.5 parts of aluminum hydroxide, 320 parts of xylene, and 80 parts of methyl isobutyl ketone were mixed in a nitrogen gas atmosphere.
Heat to 130℃ and dissolve completely. Pour this into a vat with a water-cooled bottom to a thickness of about 0.5 cm and cool quickly. A milky white dispersion with an average particle size of 10μ was obtained. This paint is stable not only immediately after preparation, but also after three months of aging, and does not clog the gun during painting.
The above paint was applied to a steel can coated with an epoxy-urea paint at a rate of 100 mg/100 cm 2 using an air spray gun, and baked at 180°C for 5 minutes. This coated object was smooth and retort test (120℃-30℃)
) The adhesion between the front and back was good, there was no whitening or blistering, and the bending resistance, flavor properties, etc. were good, and it was sufficiently durable for practical use.
実施例 ４
実施例３における変性ポリオレフインに代えて
変性ポリオレフイン80部、高密度ポリエチレン
（ハイゼツクス1300J、密度0.965、MI14、三井石
油化学工業(株)製）20部を用いて塗料を作製し、同
様の試験を行い、実施例３と同等の結果が得られ
た。Example 4 A paint was prepared using 80 parts of modified polyolefin and 20 parts of high-density polyethylene (HIZEX 1300J, density 0.965, MI14, manufactured by Mitsui Petrochemical Industries, Ltd.) in place of the modified polyolefin in Example 3, and a similar coating was prepared. A test was conducted and results equivalent to those of Example 3 were obtained.
比較例 １
実施例１のソルベツソ100に代えてセロソルブ
アセテートを用いたが加熱後溶解せず、塗料化は
因難であつた。Comparative Example 1 Cellosolve acetate was used in place of Solbetsuso 100 in Example 1, but it did not dissolve after heating, making it difficult to form into a paint.
実施例 ５
実施例４における高密度ポリエチレンに代えて
エチレン−α−オレフイン共重合エラストマー
（タフマーＰ−0280、MI3.2、密度0.88、三井石油
化学工業(株)製）を用いて塗料を作製し、ホモジナ
イザーを通過させることにより平均粒径8μの乳
白色分散体を得た。この塗料は作製直後は勿論、
３カ月間経時後でも安定である。Example 5 A paint was produced using an ethylene-α-olefin copolymer elastomer (Tafmer P-0280, MI3.2, density 0.88, manufactured by Mitsui Petrochemical Industries, Ltd.) in place of the high-density polyethylene in Example 4. A milky white dispersion with an average particle size of 8 μm was obtained by passing through a homogenizer. Of course, this paint can be used immediately after it is made.
It is stable even after aging for 3 months.
アルミニウム板へ上記塗料をロールコーターに
より100mg／100cm2の割合で施し、180℃、５分間
焼付けを行う。 The above paint was applied to an aluminum plate at a rate of 100 mg/100 cm 2 using a roll coater, and baked at 180°C for 5 minutes.
この塗装物は平滑であり、ピンホール、アイホ
ールはなく、又、レトルト試験（120℃−30分）
によつても白化およびブリスターの発生はなく、
実用に耐えるものであつた。 This coated product is smooth, with no pinholes or eyeholes, and is retort tested (120°C for 30 minutes).
There is no whitening or blistering even with
It was practical.
第１図は本発明に係わる通電試験に供する装置
の概要を表わす断面図を示す。
１……缶の金属部分、２……塗膜、３……１％
食塩水溶液、４……アンメーター。
FIG. 1 shows a cross-sectional view showing an outline of an apparatus used for an electric current test according to the present invention. 1... Metal part of the can, 2... Paint film, 3... 1%
Saline solution, 4... ammeter.
Claims (1)
合物を配合した変性ポリオレフインもしくは該変
性ポリオレフインと未変性ポリオレフインとの混
合物をポリオレフインの親溶媒もしくは、親溶媒
と貧溶媒との混合溶媒に分散せしめてなることを
特徴とする缶内面塗料。 ２ カルボキシル基含有ポリオレフインはポリオ
レフインにエチレン性不飽和カルボン酸をグラフ
ト重合したものである特許請求の範囲第１項記載
の缶内面塗料。 ３ 変性ポリオレフインはカルボキシル基含有ポ
リオレフイン100重量部に0.05〜10重量部の金属
化合物を配合したものである特許請求の範囲第１
項または第２項記載の缶内面塗料。 ４ 変性ポリオレフインと未変性ポリオレフイン
との混合物において、エチレン性不飽和カルボン
酸の量が変性ポリオレフインおよび未変性ポリオ
レフインのオレフイン成分に対して0.01〜６重量
％となるように混合したものである特許請求の範
囲第１項〜第３項いずれか記載の缶内面塗料。[Scope of Claims] 1 A modified polyolefin in which a metal compound is blended into a carboxyl group-containing polyolefin or a mixture of the modified polyolefin and an unmodified polyolefin is dispersed in a parent solvent of the polyolefin or a mixed solvent of a parent solvent and a poor solvent. A paint for the inside of a can that is characterized by: 2. The can inner surface paint according to claim 1, wherein the carboxyl group-containing polyolefin is obtained by graft polymerizing ethylenically unsaturated carboxylic acid to a polyolefin. 3. The modified polyolefin is obtained by blending 0.05 to 10 parts by weight of a metal compound with 100 parts by weight of a carboxyl group-containing polyolefin.
Can inner surface paint as described in Item 2 or Item 2. 4. In a mixture of modified polyolefin and unmodified polyolefin, the amount of ethylenically unsaturated carboxylic acid is 0.01 to 6% by weight based on the olefin component of the modified polyolefin and unmodified polyolefin. Can inner surface paint according to any one of ranges 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8593980A JPS5712072A (en) | 1980-06-26 | 1980-06-26 | Paint for inner face of can |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8593980A JPS5712072A (en) | 1980-06-26 | 1980-06-26 | Paint for inner face of can |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5712072A JPS5712072A (en) | 1982-01-21 |
| JPS6324028B2 true JPS6324028B2 (en) | 1988-05-19 |
Family
ID=13872721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8593980A Granted JPS5712072A (en) | 1980-06-26 | 1980-06-26 | Paint for inner face of can |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5712072A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006315768A (en) * | 1996-10-02 | 2006-11-24 | Taisei Kako Co Ltd | Metallic collapsible tube, its manufacturing method and use |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5930841A (en) * | 1982-08-12 | 1984-02-18 | Showa Denko Kk | Composition for fluidization dip coating |
| GB8508461D0 (en) * | 1985-04-01 | 1985-05-09 | Nicholson J W | Coating processes |
| US8927474B2 (en) * | 2012-03-16 | 2015-01-06 | S.C. Johnson & Son, Inc. | Compressed gas aerosol composition in steel can |
-
1980
- 1980-06-26 JP JP8593980A patent/JPS5712072A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006315768A (en) * | 1996-10-02 | 2006-11-24 | Taisei Kako Co Ltd | Metallic collapsible tube, its manufacturing method and use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5712072A (en) | 1982-01-21 |
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