JPH0237374B2 - - Google Patents
Info
- Publication number
- JPH0237374B2 JPH0237374B2 JP9538181A JP9538181A JPH0237374B2 JP H0237374 B2 JPH0237374 B2 JP H0237374B2 JP 9538181 A JP9538181 A JP 9538181A JP 9538181 A JP9538181 A JP 9538181A JP H0237374 B2 JPH0237374 B2 JP H0237374B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- parts
- coating
- resins
- dispersion
- 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
- 239000007788 liquid Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 17
- 229920006122 polyamide resin Polymers 0.000 claims description 17
- 229920005672 polyolefin resin Polymers 0.000 claims description 16
- 239000003973 paint Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 6
- 239000003849 aromatic solvent Substances 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 229920003180 amino resin Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 34
- 239000011248 coating agent Substances 0.000 description 33
- 239000006185 dispersion Substances 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 229920001187 thermosetting polymer Polymers 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000002609 medium Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 7
- -1 ethylene, propylene Chemical group 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229920000571 Nylon 11 Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000013555 soy sauce Nutrition 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000004826 seaming Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011282 treatment Methods 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
- 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
- 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
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical group C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process 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
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000011859 microparticle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】
本発明は缶胴接合部の補修塗料に用いる缶用塗
料組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a can coating composition used as a repair coating for can body joints.
従来、金属缶缶胴の接合は、ロツクシームを行
い半田付する方法が一般的であつた。近年になつ
て缶胴素材の両切断端部を重ね合わせ、溶接によ
り接合する方法(溶接缶)が普及しつつある。こ
のような溶接缶では、切断端面が未塗装のまま、
金属缶内面に露出するため、腐食が起りやすい欠
点を有している。そのため接合後に切断端面を補
修塗装するのが普通である。しかしながら、切断
端面のエツジ部を完全に被覆することは困難であ
り、補修方法および塗料組成物に関し、多くの提
案がなされている。 Conventionally, metal can bodies have generally been joined together by lock seaming and soldering. In recent years, a method in which both cut ends of can body materials are overlapped and joined by welding (welded can) has become popular. With such welded cans, the cut end surface remains unpainted.
Since it is exposed on the inner surface of the metal can, it has the disadvantage of being susceptible to corrosion. For this reason, it is common practice to repaint the cut end surfaces after joining. However, it is difficult to completely cover the edges of the cut end surface, and many proposals have been made regarding repair methods and coating compositions.
特開昭54−138039は、ポリアミド粉末をポリア
ミドと実質的に等比重の貧溶剤中に分散せしめた
分散液で切断端面の補修塗装を行うものであり、
本発明者等の研究によれば、分散媒が実質的に等
比重の貧溶媒に限定されているため、乾燥速度の
コントロールが困難で乾燥時間がなくなり、製缶
コストを上げる欠点を有していると共に、ポリア
ミド樹脂は金属との接着性に乏しいため煮沸等の
過酷な殺菌処理を行つた場合剥離しやすい欠点を
有している。また、特開昭56−13350では熱硬化
性樹脂溶液中に熱可塑性樹脂を95:5ないし25:
75の体積比で分散させた分散液を補修塗装に用い
るものである。この方法で溶接缶の缶胴接合部を
補修した場合、切断端面の避覆性及び耐食性に優
れた補修塗膜が得られるが、板厚の厚い溶接缶の
場合のように厚い補修塗膜を必要とする場合には
乾燥過程で発泡が起きやすいとの欠点がある。 JP-A-54-138039 discloses repair coating of cut end surfaces using a dispersion liquid in which polyamide powder is dispersed in a poor solvent having a specific gravity substantially equal to that of the polyamide.
According to the research conducted by the present inventors, since the dispersion medium is limited to a poor solvent having substantially the same specific gravity, it is difficult to control the drying rate, and there is no drying time, which has the disadvantage of increasing can manufacturing costs. In addition, polyamide resin has poor adhesion to metals, so it has the disadvantage that it easily peels off when subjected to severe sterilization treatment such as boiling. In addition, in JP-A-56-13350, a thermoplastic resin was mixed in a thermosetting resin solution with a ratio of 95:5 to 25:
A dispersion liquid dispersed at a volume ratio of 75% is used for repair painting. When the can body joint of a welded can is repaired using this method, a repair coating with excellent shielding properties and corrosion resistance can be obtained on the cut end surface. If necessary, there is a drawback that foaming tends to occur during the drying process.
本発明者等は溶接缶の缶胴接合部の補修塗装に
ついて、鋭意研究を行つた結果、新規な缶用塗料
組成物を見出した。 The inventors of the present invention conducted intensive research on repair coating of the can body joints of welded cans, and as a result, discovered a new paint composition for cans.
すなわち、本発明は、カルボキシル基含有ポリ
オレフイン樹脂1ないし70重量部とポリアミド樹
脂30ないし99重量部を、少なくとも芳香族系溶剤
を含む有機溶剤中に必要に応じて可溶性樹脂を溶
解せしめた液状媒体中に固体状態で分散せしめて
なる缶胴接合部補修塗料を提供するものである。 That is, the present invention comprises 1 to 70 parts by weight of a carboxyl group-containing polyolefin resin and 30 to 99 parts by weight of a polyamide resin in a liquid medium in which a soluble resin is dissolved as necessary in an organic solvent containing at least an aromatic solvent. The object of the present invention is to provide a can body joint repair paint made by dispersing in a solid state.
本発明の重要な特徴は、カルボキシル基含有ポ
リオレフイン樹脂を塗膜形成物質の一成分として
使用することにあり、さらに塗膜形成物質の大部
分を液状媒体中に分散させることにある。カルボ
キシル基含有ポリオレフイン樹脂は、それ自体金
属に対する接着性に特に優れており、塗膜形成物
質の一部に使用することにより、塗膜と金属間の
接着性を著しく向上させる効果がある。溶接缶の
缶胴接合部の補修塗膜は使用する金属板の厚みに
よつても異るが切断端面を完全に被覆するために
は通常30ないし200ミクロン程度の塗膜厚が必要
である。また、補修塗膜はフランジ加工、巻締加
工等の加工工程を受けるため、加工性に優れたポ
リアミド樹脂を塗膜形成物質として使用すること
が必要である。しかしながらこれらの熱可塑性樹
脂は、金属に対する接着性に乏しく、金属缶とし
て内容物が充てんされた後煮沸のような過酷な処
理を受けた場合に、剥離を起し、腐食の原因とな
つている。本発明は、カルボキシル基含有ポリオ
レフイン樹脂を塗料の一成分として使用すること
により、金属との接着性を改善したもので、これ
により、煮沸処理はもとより、120ないし130℃で
の蒸気殺菌処理をも可能としたものである。 An important feature of the present invention is that a carboxyl group-containing polyolefin resin is used as a component of the film-forming material, and that the majority of the film-forming material is dispersed in a liquid medium. The carboxyl group-containing polyolefin resin itself has particularly excellent adhesion to metals, and when used as part of a coating film-forming substance, it has the effect of significantly improving the adhesion between the coating film and the metal. The repair coating for the joint of the can body of a welded can varies depending on the thickness of the metal plate used, but usually a coating thickness of about 30 to 200 microns is required to completely cover the cut end surface. Furthermore, since the repair coating film undergoes processing steps such as flanging and seaming, it is necessary to use a polyamide resin with excellent workability as the coating film forming material. However, these thermoplastic resins have poor adhesion to metals, and when metal cans are filled with contents and subjected to harsh treatments such as boiling, they peel off, causing corrosion. . The present invention improves adhesion to metal by using carboxyl group-containing polyolefin resin as a component of the paint, which allows it to be sterilized not only by boiling but also by steam sterilization at 120 to 130°C. This made it possible.
カルボキシル基含有ポリオレフイン樹脂の効果
として、接着性の改善の他に、ポリアミド樹脂の
液状媒体中での沈降を防止する効果がある。通常
液状媒体として使用する芳香族系溶剤を含む有機
溶剤は、その比重が1以下の場合が殆どである
が、固体状態で分散させるポリアミド樹脂の比重
は1よりも大きいため、特別な分散剤を使用しな
い限りポリアミド樹脂は沈降するのが普通であ
る。沈降しやすい分散液を塗装することは可能で
あるが、いかなる方法を取るにしても作業性を著
しく低下させる。カルボキシル基含有ポリオレフ
イン樹脂粒子は、ポリアミド樹脂粒子に比べて芳
香族系溶剤を含む液状媒体中でかなり膨潤した状
態で分散しており、系をチクソトロピツクにして
いる。そのため、ポリアミド樹脂粒子の沈降防止
に極めて効果的である。前述した特開昭54−
138039では沈降防止の目的で実質的に等比重の溶
剤を使用しているが、本発明によれば、等比重の
溶剤に限定する必要はなく、塗装および乾燥の作
業性のよい溶剤を自由に選択することができる。 In addition to improving adhesion, the carboxyl group-containing polyolefin resin has the effect of preventing the polyamide resin from settling in a liquid medium. Most organic solvents, including aromatic solvents, that are normally used as liquid media have a specific gravity of 1 or less, but the specific gravity of polyamide resin that is dispersed in a solid state is greater than 1, so a special dispersant is required. Polyamide resins typically settle unless used. Although it is possible to coat a dispersion liquid that tends to settle, any method used significantly reduces workability. Carboxyl group-containing polyolefin resin particles are dispersed in a considerably swollen state in a liquid medium containing an aromatic solvent compared to polyamide resin particles, making the system thixotropic. Therefore, it is extremely effective in preventing sedimentation of polyamide resin particles. The aforementioned Japanese Patent Application Publication No. 1973-
138039 uses a solvent with substantially equal specific gravity for the purpose of preventing sedimentation, but according to the present invention, there is no need to limit the solvent to a solvent with equal specific gravity, and a solvent with good workability for painting and drying can be freely used. You can choose.
カルボキシル基含有ポリオレフイン樹脂とポリ
アミド樹脂とから形成される塗膜は一般的にエポ
キシ・フエノール系塗料、エポキシ・アミノ系塗
料と比較して耐食性が不十分である。これは主と
して金属との接着性に起因する場合と塗膜そのも
のの耐内容物性に起因する場合とがある。接着性
に起因する問題については、カルボキシル基含有
ポリオレフイン樹脂を使用することにより接着性
が向上する効果に伴つて向上するが、塗膜の耐内
容物性に関しては上述した熱可塑性樹脂のみでは
改善は困難である。本発明では、液状媒体をエポ
キシ樹脂、フエノール樹脂、アミノ樹脂、熱硬化
性アクリル樹脂、熱硬化性ポリエステル樹脂(ア
ルキツド樹脂、オイルフリーアルキツド樹脂を含
む)の一種もしくは二種以上の熱硬化性樹脂の溶
液とすることが好ましい。前述の特開昭56−
13350は熱硬化性樹脂と熱可塑性樹脂を併用する
技術を開示しているが、熱硬化性樹脂が連続相
で、熱可塑性樹脂を分散相とする塗膜構造を生成
している。本発明では熱可塑性樹脂を加熱溶融す
ることにより連続塗膜とする方法であり、従つ
て、熱硬化性樹脂を塗膜中の25容量%以上に限定
する必要はなく、それ以下の量でも十分使用でき
るものである。 Coating films formed from carboxyl group-containing polyolefin resins and polyamide resins generally have insufficient corrosion resistance compared to epoxy/phenol paints and epoxy/amino paints. This may be mainly due to the adhesion to metals, or may be due to the content resistance of the coating itself. Problems caused by adhesion can be improved by using a carboxyl group-containing polyolefin resin, but it is difficult to improve the coating film's resistance to contents with just the thermoplastic resin mentioned above. It is. In the present invention, the liquid medium is one or more thermosetting resins selected from epoxy resins, phenolic resins, amino resins, thermosetting acrylic resins, and thermosetting polyester resins (including alkyd resins and oil-free alkyd resins). It is preferable to use a solution of The aforementioned Japanese Patent Application Publication No. 1983-
13350 discloses a technology that uses a thermosetting resin and a thermoplastic resin in combination, creating a coating structure in which the thermosetting resin is the continuous phase and the thermoplastic resin is the dispersed phase. The present invention is a method of forming a continuous coating film by heating and melting the thermoplastic resin, so there is no need to limit the thermosetting resin to 25% by volume or more in the coating film, and a smaller amount is sufficient. It can be used.
以上詳述したように、本発明はカルボキシル基
含有ポリオレフイン樹脂を一部使用することによ
り、ポリアミド樹脂粒子の分散液の沈降を防止す
ると共に塗膜としての金属との接着性を著るしく
改善し、かつ耐食性を向上させた缶胴接合部の補
修塗装に用いる缶用塗料組成物を提供するもので
ある。 As detailed above, the present invention prevents sedimentation of a dispersion of polyamide resin particles and significantly improves adhesion to metal as a coating film by partially using a carboxyl group-containing polyolefin resin. The present invention provides a can coating composition that is used for repair painting of can body joints and has improved corrosion resistance.
以下本発明に用いられる構成要素について説明
する。 The constituent elements used in the present invention will be explained below.
本発明に用いるカルボキシル基含有ポリオレフ
イン樹脂としては、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また
はその酸無水物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。缶体が高温蒸気殺菌
を受ける場合には、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望ましい。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および沈降防止の効果が
弱く50重量部以上では接着向上の効果が認められ
ず加工性が低下する。このようなカルボキシル基
含有ポリオレフイン樹脂を、液状媒体中に固体状
態として分散させる方法としては、公知の任意の
方法を用いることができる。例えば構成単量体を
乳化重合あるいは懸濁重合することにより分散液
を得る方法、また樹脂を冷却下に粉砕して得た樹
脂粉末を液状媒体中に分散させる方法、樹脂を高
温で溶解した溶液を冷却して析出させ分散液を得
る方法、樹脂溶液を非溶媒と接触させて析出させ
分散液を得る方法、樹脂溶液を気流中に噴霧・乾
燥して樹脂粉末得、液状媒体中に分散させる方法
等の手段をとることができる。液状媒体中のカル
ボキシル基含有ポリオレフイン樹脂の平均粒子径
は、100ミクロン以下であることが好ましい。100
ミクロンを越えた場合接着に関する特性は影響が
ないものの、沈降防止の効果は薄く、塗装作業が
低下する。また沈降防止に関しては20ミクロン以
下の粒径が好ましいが、平均粒径が20ミクロン以
下になる必要はなく、粒子中に20ミクロン以下の
微小粒子が存在していれば効果はある。 The carboxyl group-containing polyolefin resin used in the present invention includes olefinic monomers such as ethylene, propylene, or butene, and ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and maleic anhydride. It is a product obtained by copolymerizing an acid, or a product obtained by graft polymerizing an ethylenically unsaturated carboxylic acid or its acid anhydride onto a 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 the can body is subjected to high-temperature steam sterilization, high-density polyethylene, polypropylene, or the like is preferable as the polyolefin. The amount of ethylenically unsaturated carboxylic acid is the olefin component
It is preferably 0.01 to 50 parts by weight per 100 parts by weight.
If it is less than 0.01 part by weight, the effect of adhesion and prevention of sedimentation is weak, and if it is more than 50 parts by weight, the effect of improving adhesion is not observed and processability is reduced. Any known method can be used to disperse such carboxyl group-containing polyolefin resin in a solid state in a liquid medium. For example, a method of obtaining a dispersion liquid by emulsion polymerization or suspension polymerization of constituent monomers, a method of dispersing a resin powder obtained by crushing a resin under cooling in a liquid medium, a method of dispersing a resin powder at a high temperature, and a method of dispersing a resin powder at a high temperature. A method in which a dispersion liquid is obtained by cooling and precipitation, a method in which a resin solution is brought into contact with a non-solvent to precipitate and a dispersion liquid is obtained, a method in which a resin solution is sprayed into an air stream and dried to obtain a resin powder, and the resin powder is obtained and dispersed in a liquid medium. method etc. can be taken. The average particle size of the carboxyl group-containing polyolefin resin in the liquid medium is preferably 100 microns or less. 100
If it exceeds a micron, adhesion properties are not affected, but the effect of preventing sedimentation is weak and painting work is reduced. Further, in terms of preventing sedimentation, a particle size of 20 microns or less is preferable, but the average particle size does not need to be 20 microns or less, and it is effective as long as microparticles of 20 microns or less are present in the particles.
本発明に上記のカルボキシル基含有ポリオレフ
イン樹脂と共に用いられるポリアミド樹脂は、塗
膜の主たる成分であり、加工性、柔軟性に富み、
内容物が食品であつても衛生性に問題がない。ポ
リアミド樹脂は、例えば6―,6.6―,6.10―,
11―,12―ポリアミド樹脂あるいはこれらの共重
合物、混合物を使用することができる。またポリ
アミド樹脂の分散液中で粒度は平均粒子径として
100ミクロン以下であることが好ましく、60ミク
ロン以下であればより平滑な塗面が得られる。 The polyamide resin used in the present invention together with the carboxyl group-containing polyolefin resin is the main component of the coating film, and has excellent processability and flexibility.
Even if the contents are food, there is no problem with hygiene. Polyamide resins are, for example, 6-, 6.6-, 6.10-,
11-, 12-polyamide resins or copolymers and mixtures thereof can be used. In addition, the particle size in the polyamide resin dispersion is expressed as the average particle diameter.
It is preferably 100 microns or less, and a smoother coated surface can be obtained if it is 60 microns or less.
本発明に用いられる液状媒体としては、前述し
たポリアミド樹脂を溶解しない範囲で、乾燥性、
塗装適性に優れているトルエン、キシレン等の芳
香族系溶剤を使用することが必要であるが、芳香
族系有機溶剤とエステル系溶剤等の他の溶剤との
混合溶剤とすることも可能である。補修塗膜に強
い耐食性能が要求される場合には、液状媒体中に
エポキシ樹脂、フエノール樹脂、アミノ樹脂、熱
硬化性アクリル樹脂、熱硬化性ポリエステル樹脂
等の熱硬化性樹脂を溶解させることができる。こ
れらの熱硬化性樹脂としては、エポキシ―フエノ
ール系、エポキシ―アミノ系、アクリル―アミノ
系、ポリエステル―アミノ系を使用すると耐食性
は極めて改善させる。また缶内面(補修部分以
外)に塗装される内面塗膜と補修塗膜との接着性
を改善するために、前述した熱硬化性樹脂以外に
ポリ塩化ビニル樹脂、塩化ビニル系共重合体、熱
可塑性アクリル樹脂、熱可塑性ポリエステル樹
脂、ポリブタジエン樹脂等の熱可塑性樹脂を溶解
させることもできる。これらの熱硬化性樹脂ある
いは熱可塑性樹脂は、分散液中に固体状態で分散
しているカルボキシル基含有ポリオレフイン樹脂
とポリアミド樹脂の連続膜に補助的な機能を持た
せるものであり量としては、特に制限なく使用す
ることができ塗膜形成物質中の25容量%以下でも
十分に効果のあるものである。 The liquid medium used in the present invention has drying properties,
It is necessary to use aromatic solvents such as toluene and xylene, which have excellent coating suitability, but it is also possible to use a mixed solvent of aromatic organic solvents and other solvents such as ester solvents. . When strong corrosion resistance is required for repair coatings, thermosetting resins such as epoxy resins, phenolic resins, amino resins, thermosetting acrylic resins, and thermosetting polyester resins can be dissolved in the liquid medium. can. As these thermosetting resins, use of epoxy-phenol, epoxy-amino, acrylic-amino, and polyester-amino resins significantly improves corrosion resistance. In addition, in order to improve the adhesion between the inner coating film applied to the inner surface of the can (other than the repaired area) and the repair coating film, in addition to the thermosetting resins mentioned above, polyvinyl chloride resin, vinyl chloride copolymer, Thermoplastic resins such as plastic acrylic resin, thermoplastic polyester resin, and polybutadiene resin can also be dissolved. These thermosetting resins or thermoplastic resins provide an auxiliary function to the continuous film of carboxyl group-containing polyolefin resin and polyamide resin that are dispersed in a solid state in the dispersion liquid, and the amount is particularly limited. It can be used without any restrictions and is sufficiently effective even at 25% by volume or less in the coating film-forming substance.
かくして得られた分散液状の缶用塗料組成物の
固形分は適度の作業性と厚盛り適性が付与できる
範囲、好ましくは5ないし50重量%であればよ
い。本発明による缶用塗料組成物を適用する缶体
の素材としては、ブリキ、亜鉛メツキ鋼板、クロ
ムメツキ鋼板等のメツキ鋼板、クロム酸、リン酸
等で化学処理を行つた鋼板、化成処理鋼板、未処
理の鋼板、さらにはアルミニウム等の軽金属板等
が用いられ。缶の用途、形状にかかわらず缶胴接
合部に適用することができる。 The solid content of the thus obtained dispersion liquid can coating composition may be within a range that provides appropriate workability and suitability for thick coating, preferably 5 to 50% by weight. Materials for cans to which the can coating composition of the present invention is applied include tinplate, galvanized steel sheets, chrome-plated steel sheets, steel sheets chemically treated with chromic acid, phosphoric acid, etc., chemically treated steel sheets, and untreated steel sheets. Treated steel plates and even light metal plates such as aluminum are used. It can be applied to the can body joint, regardless of the purpose or shape of the can.
本発明による缶用塗料組成物を缶胴接合部に塗
装する方法としては、ローラー塗装、スプレー塗
装、フローコート、ハケ塗り、浸漬塗装等の任意
の手段で塗装することができる。塗装した後、カ
ルボキシル基含有ポリオレフイン樹脂およびポリ
アミド樹脂の軟化点以上に加熱し溶融することに
より連続塗膜とするが、有機溶剤を蒸発させる過
程とカルボキシル基含有ポリオレフイン樹脂およ
びポリアミド樹脂を溶融させる過程を経るのが好
ましい。加熱方法としては、直火、熱オーブン、
誘導加熱、抵抗加熱、赤外線加熱等を用いること
ができ150℃ないし400℃で1秒ないし10分間の範
囲から適当な条件を選択することができる。 The coating composition for cans according to the present invention can be applied to the can body joint by any method such as roller coating, spray coating, flow coating, brush coating, and dip coating. After coating, a continuous coating film is created by heating and melting the carboxyl group-containing polyolefin resin and polyamide resin above their softening points. It is preferable to go through the process. Heating methods include direct heat, hot oven,
Induction heating, resistance heating, infrared heating, etc. can be used, and appropriate conditions can be selected from the range of 1 second to 10 minutes at 150° C. to 400° C.
本発明による缶用塗料組成物は、溶接缶の缶胴
接合部の補修塗装に特に有用であるが、接着缶、
半田缶の缶胴接合部の補修塗装にも使用すること
はできる。 The can coating composition according to the present invention is particularly useful for repair painting of can body joints of welded cans;
It can also be used to repair and paint the joints of solder can bodies.
以下、本発明を、例をもつて具体的に説明す
る。例中部は重量部を示す。 Hereinafter, the present invention will be specifically explained using examples. The middle part of the example shows parts by weight.
実施例 1
マレイン酸グラフトポリプロピレン(東亜燃料
工業(株)商品名、C―902X―MA)10部とキシレ
ン40部を120℃に撹拌しながら加熱した後、50部
の冷キシレン中に、撹拌しながら滴下して平均粒
径15ミクロンの白色分散液を得た。得られた分散
液100部、トルエン210部、日本リルサン(株)製のポ
リアミド―11の粉末90部(平均粒子径38ミクロ
ン)を十分に撹拌し分散液を得た。分散液は均一
な分散状態を示し1週間後も変化は見られなかつ
た。Example 1 10 parts of maleic acid grafted polypropylene (Toa Fuel Industries Co., Ltd. trade name, C-902X-MA) and 40 parts of xylene were heated to 120°C with stirring, and then stirred into 50 parts of cold xylene. The mixture was added dropwise to obtain a white dispersion with an average particle size of 15 microns. 100 parts of the obtained dispersion, 210 parts of toluene, and 90 parts of polyamide-11 powder (average particle size 38 microns) manufactured by Nippon Rilsan Co., Ltd. were thoroughly stirred to obtain a dispersion. The dispersion liquid showed a uniform dispersion state and no change was observed even after one week.
得られた分散液を溶接缶(クロム処理板18缶
の缶胴接合部にスプレーガン(ノズル径0.55mm)
により、巾15mm厚さ約100ミクロンになるように
帯状に補修塗装を行い、ただちに250℃の熱風を
裏側から60秒間あてることにより乾燥溶融させ、
補修塗膜とした。補修塗膜にナイフで傷を入れ剥
離させたが剥離は起きなかつた。また補修切片を
醤油に浸漬し50℃にて3ケ月間保存したが変化は
見られなかつた。 The obtained dispersion was sprayed onto the can body joint of a welded can (chromium-treated plate 18 cans) with a spray gun (nozzle diameter 0.55 mm).
Then, we applied a repair coat to a width of 15 mm and a thickness of about 100 microns, and immediately blown it with 250℃ hot air from the back side for 60 seconds to dry and melt it.
It was used as a repair coating. I scratched the repair coating with a knife and peeled it off, but no peeling occurred. In addition, the repaired sections were immersed in soy sauce and stored at 50°C for 3 months, but no changes were observed.
比較例 1
トルエン200部と、日本リルサン(株)製のポリア
ミド―11の粉末90部(平均粒子径38ミクロン)を
十分に撹拌し分散液は数分で粒子が沈降する不安
定なものであつた。分散液を十分に撹拌しながら
実施例1と同様に溶接缶(クロム処理鋼板製18
缶)の缶胴接合部に補修塗装および乾燥溶融を行
つた。補修塗膜にナイフで傷を入れ剥離を行う
と、塗膜は容易に剥離した。また補修した切片を
醤油に浸漬し50℃にて3ケ月保存したところ気液
の界面および気相部に錆がみられた。Comparative Example 1 200 parts of toluene and 90 parts of polyamide 11 powder (average particle size 38 microns) manufactured by Nippon Rilsan Co., Ltd. were sufficiently stirred to form an unstable dispersion in which the particles settled within a few minutes. Ta. While thoroughly stirring the dispersion liquid, welded a can (made of chromium-treated steel plate 18 mm) in the same manner as in Example 1.
Repair painting and dry melting were performed on the can body joints of cans. When the repaired paint film was scratched with a knife and peeled off, the paint film was easily peeled off. Furthermore, when the repaired section was immersed in soy sauce and stored at 50°C for 3 months, rust was observed at the gas-liquid interface and in the gas phase.
実施例 2
ビスフエノールA型エポキシ樹脂(油化シエ
ル・エポキシ(株)商品名、エピコート1007)8部お
よび尿素樹脂(大日本インキ化学(株)商品名、ベツ
カミンP―138)4部をトルエン9部とエチレン
グリコールモノメチルエーテル9部に溶解したエ
ポキシ・尿素樹脂溶液30部、実施例1と同様に調
整したマレイン酸グラフトポリプロピレン分散液
100部、トルエン180部、および日本リルサン(株)製
のポリアミド―11の粉末90部(平均粒子径38ミク
ロン)とを十分に撹拌し分散液を得た。分散液は
均一な分散状態を示し、1週間後も変化は見られ
なかつた。得られた分散液を実施例1と同様に溶
接缶(クロム処理鋼板18缶)の缶胴接合部に補
修塗装し乾燥溶融を行つた。得られた補修塗膜に
ナイフで傷を入れ剥離を行つたが、剥離は起きな
かつた。また補修切片を醤油に浸漬し50℃にて3
ケ月保存したが変化はみられなかつた。また実施
例1で得られた補修切片および、比較例2で得ら
れた補修切片と共に塩化ナトリウムとクエン酸を
それぞれ2%溶解した水溶液に浸漬し50℃で3ケ
月保存したところ、比較例1の切片はかなり腐食
が進行しており、塗膜の剥離も見られた。実施例
1のサンプルは剥離はみられないものの、気液界
面部分で若干腐食が認められた。これに対して本
実施例の切片は全く変化が認められなかつた。Example 2 8 parts of bisphenol A epoxy resin (trade name, Epicoat 1007, manufactured by Yuka Ciel Epoxy Co., Ltd.) and 4 parts of urea resin (trade name, Betsukamine P-138, manufactured by Dainippon Ink Chemical Co., Ltd.) were mixed with 9 parts of toluene. 1 part, 30 parts of an epoxy/urea resin solution dissolved in 9 parts of ethylene glycol monomethyl ether, and a maleic acid grafted polypropylene dispersion prepared in the same manner as in Example 1.
100 parts of toluene, 180 parts of toluene, and 90 parts of polyamide-11 powder (average particle size 38 microns) manufactured by Nippon Rilsan Co., Ltd. were thoroughly stirred to obtain a dispersion. The dispersion liquid showed a uniform dispersion state, and no change was observed even after one week. The resulting dispersion was applied to the joints of the can bodies of welded cans (18 chromium-treated steel plates) for repair in the same manner as in Example 1, and then dried and melted. The resulting repaired coating film was scratched with a knife and peeled off, but no peeling occurred. In addition, the repaired section was immersed in soy sauce and heated to 50°C for 3 days.
Although it was stored for several months, no change was observed. In addition, the repaired sections obtained in Example 1 and Comparative Example 2 were immersed in an aqueous solution containing 2% sodium chloride and citric acid, respectively, and stored at 50°C for 3 months. The section showed considerable corrosion, and peeling of the paint film was also observed. Although no peeling was observed in the sample of Example 1, some corrosion was observed at the gas-liquid interface. In contrast, no change was observed in the sections of this example.
比較例 2
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部をフラスコに仕込
み130℃に加熱溶解し、0.1部の過酸化ベンゾイル
を添加して60分間加熱反応した後、60分かけて室
温まで冷却した。得られた懸濁物をロ過した後メ
チルエチルケトンで未反応の無水マレイン酸を2
回洗浄し乾燥した。得られたポリプロピレン―無
水マレイン酸共重合体は、平均粒径34ミクロンの
粉末であつた。この粉末100部をエチルアルコー
ル200部中に十分撹拌し分散液を得た。分散液は
均一な分散状態を示し、安定であつた。Comparative Example 2 100 parts of polypropylene (MI value 10), 20 parts of maleic anhydride and 375 parts of xylene were placed in a flask, heated and dissolved at 130°C, and 0.1 part of benzoyl peroxide was added and reacted by heating for 60 minutes. Cooled to room temperature over several minutes. After filtering the resulting suspension, unreacted maleic anhydride was removed with methyl ethyl ketone.
Washed twice and dried. The obtained polypropylene-maleic anhydride copolymer was a powder with an average particle size of 34 microns. 100 parts of this powder was sufficiently stirred in 200 parts of ethyl alcohol to obtain a dispersion. The dispersion liquid exhibited a uniform dispersion state and was stable.
得られた分散液を用いて、実施例1と同様に溶
接缶の缶胴接合部に補修塗装し、乾燥、溶融を行
つた。得られた補修塗膜にナイフで傷を入れたと
ころ、傷の周辺でクラツクが発生した。また180゜
折り曲げ試験でもクラツクがはいり接合部の補修
塗膜としては柔軟性が不十分であつた。 Using the obtained dispersion liquid, repair coating was applied to the joint portion of the can body of a welded can in the same manner as in Example 1, followed by drying and melting. When the resulting repaired coating was scratched with a knife, cracks occurred around the scratches. In addition, cracks appeared in the 180° bending test, and the flexibility was insufficient to be used as a repair coating for joints.
Claims (1)
いし70重量部とポリアミド樹脂30ないし99重量部
を、少なくとも芳香族系溶剤を含む有機溶剤中に
必要に応じて可溶性樹脂を溶解せしめた液状媒体
中に固体状態で分散せしめてなる缶胴接合部補修
塗料。 2 可溶性樹脂がエポキシ樹脂、フエノール樹
脂、アミノ樹脂、アクリル樹脂、塩化ビニル樹
脂、塩化ビニル系共重合体、ポリエステル樹脂、
ポリブタジエン樹脂からなる群の一種もしくは二
種以上である特許請求の範囲第1項記載の缶胴接
合部補修塗料。[Scope of Claims] 1. A liquid medium containing 1 to 70 parts by weight of a carboxyl group-containing polyolefin resin and 30 to 99 parts by weight of a polyamide resin, in which a soluble resin is dissolved as necessary in an organic solvent containing at least an aromatic solvent. Can body joint repair paint that is dispersed in a solid state. 2 Soluble resin is epoxy resin, phenolic resin, amino resin, acrylic resin, vinyl chloride resin, vinyl chloride copolymer, polyester resin,
The can body joint repair paint according to claim 1, which is one or more of the group consisting of polybutadiene resins.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9538181A JPS57209961A (en) | 1981-06-22 | 1981-06-22 | Paint composition for can |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9538181A JPS57209961A (en) | 1981-06-22 | 1981-06-22 | Paint composition for can |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57209961A JPS57209961A (en) | 1982-12-23 |
JPH0237374B2 true JPH0237374B2 (en) | 1990-08-23 |
Family
ID=14136061
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9538181A Granted JPS57209961A (en) | 1981-06-22 | 1981-06-22 | Paint composition for can |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57209961A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5930841A (en) * | 1982-08-12 | 1984-02-18 | Showa Denko Kk | Composition for fluidization dip coating |
JP4499071B2 (en) * | 1996-10-02 | 2010-07-07 | 大成化工株式会社 | Metal extruded tube, its production method and its use |
JP5040082B2 (en) * | 2004-08-19 | 2012-10-03 | 三菱化学株式会社 | Resin dispersion |
JP5184216B2 (en) * | 2008-05-30 | 2013-04-17 | ユニチカ株式会社 | Aqueous dispersion and laminate |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52142686A (en) * | 1976-05-24 | 1977-11-28 | Toyo Soda Mfg Co Ltd | Carboxylated ethylene-vinyl acetate copolymer emulsion |
-
1981
- 1981-06-22 JP JP9538181A patent/JPS57209961A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS57209961A (en) | 1982-12-23 |
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