JP4500115B2 - Aluminum alloy material for beverage containers with excellent black water resistance against boiling water - Google Patents
Aluminum alloy material for beverage containers with excellent black water resistance against boiling water Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 56
- 238000009835 boiling Methods 0.000 title claims description 32
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 23
- 235000013361 beverage Nutrition 0.000 title claims description 22
- 239000000956 alloy Substances 0.000 title claims description 20
- 239000010866 blackwater Substances 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 76
- 229910052782 aluminium Inorganic materials 0.000 claims description 73
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 72
- 239000000126 substance Substances 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- 238000004458 analytical method Methods 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229940085991 phosphate ion Drugs 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005238 degreasing Methods 0.000 claims description 7
- 230000036571 hydration Effects 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 description 35
- 239000004094 surface-active agent Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005237 degreasing agent Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- -1 containers Substances 0.000 description 6
- 239000013527 degreasing agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002826 coolant Substances 0.000 description 5
- 239000008235 industrial water Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010669 acid-base reaction Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 235000013353 coffee beverage Nutrition 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 235000014214 soft drink Nutrition 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical group 0.000 description 1
- 238000005187 foaming Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical group CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- Rigid Containers With Two Or More Constituent Elements (AREA)
- Chemical Treatment Of Metals (AREA)
Description
本発明は、ソフトドリンク類、コーヒー、ビールなどの飲料用アルミニウム製容器(以下「アルミ容器」という。)や食品用容器等、主として飲料容器等に用いられるアルミニウム合金(以下「アルミ」という。)材に関する。特に板材に成形し、引き続き脱脂処理及びZr系化成処理剤で処理し、アルミ容器に成形したあと、沸騰水等で殺菌処理される際の黒変防止に優れた性能を有するアルミ容器用アルミ材に関する。 The present invention relates to aluminum alloys (hereinafter referred to as “aluminum”) mainly used for beverage containers such as soft drinks, coffee beverages, beverages such as aluminum containers (hereinafter referred to as “aluminum containers”) and food containers. Regarding materials. In particular, aluminum material for aluminum containers that has excellent performance in preventing blackening when it is molded into plate material, subsequently treated with degreasing treatment and Zr chemical conversion treatment agent, molded into an aluminum container, and then sterilized with boiling water, etc. About.
アルミ材は華麗な金属光沢、軽量、適度な機械的特性を有する金属材で、成形加工性、耐食性等に優れるという特徴を有しているため、各種包装材、容器類、車両、構造材等に広く使われている。飲料容器分野では、アルミを板材に成形加工後、脱脂処理、化成処理を経てアルミ容器に成形して用いられている。ただし内容物によっては、殺菌等のために、内容物を充填後、容器を沸水または蒸気に曝すレトルト処理が行われる。 Aluminum material is a metal material with a brilliant metallic luster, light weight, and moderate mechanical properties, and has characteristics such as excellent moldability, corrosion resistance, etc., so various packaging materials, containers, vehicles, structural materials, etc. Widely used in In the beverage container field, after forming aluminum into a plate material, it is used after being degreased and converted into an aluminum container. However, depending on the contents, a retort treatment is performed in which the container is exposed to boiling water or steam after filling the contents for sterilization or the like.
アルミ容器の場合、容器内面は容器の腐食防止と内容物保護のために化成処理後塗装が施されるが、容器外面、特に容器の底部付近は塗装等の処理が行われず、化成処理により施された化成皮膜のままで使われることが多い。化成皮膜の形成が不十分であったり、皮膜が緻密でない場合、沸水との接触によって容器表面が黒色に変色、所謂黒変を生じる場合がある。黒変は容器外観の美麗性を損ない商品性を著しく低下させるために、化成処理後のアルミ材には沸水処理による変色を引き起こさないことが要求される。 In the case of an aluminum container, the inner surface of the container is coated after chemical conversion to prevent corrosion of the container and protect the contents, but the outer surface of the container, particularly the bottom of the container, is not subjected to any treatment such as coating, and is applied by chemical conversion. It is often used as it is. If the formation of the chemical conversion film is insufficient or the film is not dense, the container surface may turn black due to contact with boiling water, so-called blackening. In order for the black discoloration to deteriorate the appearance of the container and to significantly reduce the merchantability, the aluminum material after the chemical conversion treatment is required not to cause discoloration due to boiling water treatment.
このような不具合を防止するためにこれまで幾つかの提案がなされている。
例えば特許文献1や特許文献2に記載されているように化成処理浴の改良が行われてきた。これらの中では、アルミニウム材の表面に酸化皮膜あるいは水酸化皮膜が形成されると化成皮膜が不均一となり、沸水との接触による黒変発生抑止力が低下するため、化成皮膜を厚く付けなければならないが、化成皮膜が厚くなると金属面と塗膜の密着性が低下すると指摘されている。
Several proposals have been made so far to prevent such problems.
For example, as described in Patent Document 1 and Patent Document 2, the chemical conversion bath has been improved. Among these, if an oxide film or a hydroxide film is formed on the surface of the aluminum material, the chemical conversion film becomes non-uniform and the ability to prevent blackening due to contact with boiling water decreases. However, it is pointed out that the adhesion between the metal surface and the coating film decreases as the chemical conversion film becomes thicker.
アルミ材表面に水酸化物や水和酸化物(以下両者を「水酸化物等」という。)皮膜等が付着していなければ黒変性がなく、塗膜密着性が共に優れた化成皮膜が得られるわけだが、一般的にアルミ材に酸化膜または水酸化膜のような皮膜を形成させないということは工業的には難しく、その厚みも何らかの処理を行わない限り、アルミ材の履歴、備蓄の際の雰囲気の変動等から考えるとこれを一定量に制御することは事実上できない。従って化成処理に先立ってアルミ材表面に形成される皮膜等は個々変動することになるので、最適化成条件が常に変動することになり、脱脂浴、化成浴の改良のみではアルミ材の黒変性を改良することは難しい。 If there is no hydroxide or hydrated oxide (both referred to as “hydroxide, etc.”) film on the surface of the aluminum material, there is no blackening and a chemical film with excellent coating adhesion is obtained. However, in general, it is difficult industrially to prevent the aluminum material from forming a film such as an oxide film or a hydroxide film, and unless the thickness of the aluminum material is treated in some way, Considering the change in atmosphere, etc., it is virtually impossible to control this to a certain amount. Therefore, the film formed on the surface of the aluminum material prior to the chemical conversion treatment will fluctuate individually, so the optimum chemical conversion conditions will always fluctuate, and the improvement of the degreasing bath and chemical conversion bath alone will cause blackening of the aluminum material. It is difficult to improve.
また特許文献3に記載されているように沸水処理に使用する沸水の含有成分による改良も行われてきた。しかし沸水処理に使用する沸水の成分を常に制御すると、必然的にコストアップ要因ができるという好ましくない側面も生まれる。
アルミ側改良としては特許文献4に記載されているように極力酸化皮膜あるいは水酸化皮膜を形成させずに、アルミ表面を洗浄する方法も提案されている。しかしこのような技術によっても洗浄した後のアルミ材が置かれた雰囲気によっては新たな酸化皮膜が形成されるために、防ぎきれない場合も生まれるとの懸念がある。
以上のように従来方法では黒変発生を防止できない場合がある。特にZr系化合物を主成分とする化成皮膜を形成せしめた場合に、化成皮膜量によらず黒変するなど、化成皮膜量を増やしても解決しないという事例も発生した。
In addition, as described in Patent Document 3, improvements have been made with components containing boiling water used for boiling water treatment. However, when the component of boiling water used for boiling water treatment is always controlled, there is an undesirable aspect that inevitably increases costs.
As an improvement on the aluminum side, a method of cleaning the aluminum surface without forming an oxide film or a hydroxide film as much as possible has been proposed as described in Patent Document 4. However, there is a concern that even with such a technique, a new oxide film may be formed depending on the atmosphere in which the cleaned aluminum material is placed, so that it may be impossible to prevent.
As described above, the conventional method may not prevent the occurrence of blackening. In particular, when a chemical conversion film containing a Zr-based compound as a main component is formed, there are cases where it does not resolve even if the amount of chemical conversion film is increased, such as blackening regardless of the amount of chemical conversion film.
本発明は上記のような課題を解決するために研究した結果、黒変の発生は微細孔を有する粗悪な化成皮膜が形成される場合に発生し、極端な場合(例えばZr付着量で1mg/m2しかないといったような)を除くと化成皮膜量とは無関係であること、粗悪な化成皮膜は化成処理時のアルミ材表面にカップルブ及びボディメーカークーラント等の油分が残留している場合に形成されやすく、酸化皮膜または水酸化皮膜量とは直接関係ないこと、油分の残留はアルミ材表面の酸化皮膜または水酸化皮膜の性質により大きく左右され、良質な水酸化皮膜が形成されている場合はむしろ均一な化成皮膜の形成を促進することを見出したことに基き成されたものである。本発明は化成処理に先立ちあらかじめアルミ板上に良質な水酸化皮膜を適量形成させることにより、経時変化を受けない安定したアルミ材表面を作り、均一な化成皮膜を形成させ、沸水等との接触によるアルミ材表面の黒変を防止することを目的とする。 As a result of studying the present invention to solve the above-mentioned problems, the occurrence of blackening occurs when a poor chemical conversion film having fine pores is formed, and in an extreme case (for example, 1 mg / kg of Zr adhesion amount). Except for m 2 only), it is irrelevant to the amount of chemical conversion film, and a poor chemical film is formed when oil such as couples and body maker coolant remains on the aluminum surface during chemical conversion treatment. If there is a good quality hydroxide film, it is not directly related to the amount of oxide film or hydroxide film, and the residual oil content depends greatly on the properties of the oxide film or hydroxide film on the aluminum surface. Rather, it is based on the finding that it promotes the formation of a uniform chemical conversion film. Prior to the chemical conversion treatment, the present invention forms an appropriate amount of a good quality hydroxide film on an aluminum plate in advance, thereby creating a stable aluminum material surface that is not subject to change over time, forming a uniform chemical conversion film, and contacting with boiling water or the like. The purpose is to prevent blackening of the surface of the aluminum material.
本発明は、
[1] 圧延処理した、必須成分としてMgを含み、表面にMg化合物の濃化層を有するアルミ材を脱脂した後、Zr系化成処理剤で化成処理する前の該アルミ材が、表面の深さ方向分析をグロー放電発光分光分析装置(GDS)で行なったときのMgの最大発光強度が2V以下であり、その全水和酸化皮膜が10mg/m2〜150mg/m2の厚みであることを特徴とする沸水耐黒変性に優れた飲料容器用アルミ合金材の製造方法、
The present invention
[1] After degreasing the rolled aluminum material containing Mg as an essential component and having a Mg compound concentrated layer on the surface, the aluminum material before chemical conversion treatment with the Zr chemical conversion treatment it is the maximum emission intensity of Mg when the direction analysis was performed in a glow discharge optical emission spectrometer (GDS) is below 2V, the entire hydration oxide film the thickness of 10mg / m 2 ~150mg / m 2 A method for producing an aluminum alloy material for beverage containers excellent in boiling water blackening resistance, characterized by
[2] 冷間圧延板を、Zr系化成処理剤で化成処理するに先立ち、pH4以上、8未満,硫酸イオン濃度≦500ppm、リン酸イオン濃度≦500ppmでかつ、かつ50℃〜100℃の水を、5秒以上アルミ表面と接触させることにより、表面の深さ方向分析をグロー放電発光分光分析装置(GDS)で行なったときのMgの最大発光強度が2V以下であり、水酸化皮膜を10〜150mg/m2の厚さで形成させたことを特徴とする耐沸騰水黒変性に優れた飲料容器用アルミ合金材の製造法、
[3] 冷間圧延板を、Zr系化成処理剤で化成処理するに先立ち、pH=9〜12、かつ硫酸イオン濃度≦500ppm、リン酸イオン濃度≦500ppmで、30℃〜90℃のアルカリ性水溶液を、2秒以上、アルミ表面と接触させることにより、表面の深さ方向分析をグロー放電発光分光分析装置(GDS)で行なったときのMgの最大発光強度が2V以下であり、水酸化皮膜を10〜150mg/m2の厚さで形成させたことを特徴とする耐沸騰水黒変性に優れた飲料容器用アルミ合金材の製造法、
[2] Prior to chemical conversion treatment of a cold-rolled sheet with a Zr-based chemical conversion treatment agent, water having a pH of 4 or more and less than 8, sulfate ion concentration ≦ 500 ppm, phosphate ion concentration ≦ 500 ppm, and 50 ° C. to 100 ° C. Is contacted with the aluminum surface for 5 seconds or more, and the maximum emission intensity of Mg when the depth direction analysis of the surface is performed with a glow discharge emission spectrometer (GDS) is 2 V or less, and the hydroxide film is 10 A method for producing an aluminum alloy material for beverage containers excellent in boiling water blackening resistance, characterized by being formed at a thickness of ˜150 mg / m 2 ;
[3] Prior to chemical conversion treatment of a cold-rolled sheet with a Zr-based chemical conversion treatment agent, an alkaline aqueous solution having a pH of 9 to 12, a sulfate ion concentration of ≦ 500 ppm, a phosphate ion concentration of ≦ 500 ppm, and 30 ° C. to 90 ° C. Is contacted with the aluminum surface for 2 seconds or more, and the maximum emission intensity of Mg when the depth direction analysis of the surface is performed with a glow discharge emission spectrometer (GDS) is 2 V or less. A method for producing an aluminum alloy material for beverage containers excellent in boiling water blackening resistance, characterized by being formed at a thickness of 10 to 150 mg / m 2 ;
[4] 圧延処理した、必須成分としてMgを含み、表面にMg化合物の濃化層を有するアルミ材であって、表面の深さ方向分析をグロー放電発光分光分析装置(GDS)で行なったときのMgの最大発光強度が2V以下であり、その全水和酸化皮膜が10mg/m2〜150mg/m2の厚みであることを特徴とする沸水耐黒変性に優れた飲料容器用アルミ合金材、 [4] A rolled aluminum material containing Mg as an essential component and having a concentrated layer of Mg compound on the surface, and when the depth direction analysis of the surface is performed with a glow discharge optical emission spectrometer (GDS) maximum emission intensity is below 2V, the entire hydration oxide film 10mg / m 2 ~150mg / m 2 of a beverage container aluminum alloy material excellent in boiling water resistance to blackening, which is a thickness of Mg ,
[5] Zr系化成処理剤で化成処理する前の該アルミ材が、表面の深さ方向分析をグロー放電発光分光分析装置(GDS)で行なったときのMgの最大発光強度が2V以下であり、その全水和酸化皮膜が10mg/m2〜150mg/m2の厚みであるアルミ材をZr系化成処理剤で化成処理したことを特徴とする沸水耐黒変性に優れた飲料容器用アルミ合金材、及び
[6] 請求項5に記載の製造方法により製造された飲料容器用アルミ合金材から製造されたことを特徴とする沸水耐黒変性に優れたアルミ製飲料容器、を開発することにより上に子課題を解決した。
[5] The aluminum material before chemical conversion treatment with a Zr chemical conversion treatment agent has a maximum emission intensity of Mg of 2 V or less when surface depth direction analysis is performed with a glow discharge optical emission spectrometer (GDS). , the entire hydration oxide film 10mg / m 2 ~150mg / m 2 of boiling water blackening excellent beverage container aluminum alloy aluminum material is thick, characterized in that the chemical conversion treatment with Zr-based chemical conversion treatment agent [6] By developing an aluminum beverage container excellent in boiling water blackening resistance, which is manufactured from the aluminum alloy material for beverage containers manufactured by the manufacturing method according to claim 5. Solved the child problem above.
以上のように、本発明の化成処理に先立ちあらかじめアルミ板上に良質な水酸化皮膜を適量形成させることにより、経時変化を受けない安定したアルミ材表面を作り、均一な化成皮膜を形成させたアルミ容器用アルミ材は、内容物充填後において行われる沸騰水等で殺菌処理あるいはホット販売などで高温の保持される場合の黒変防止に優れた性能を有するアルミ容器用アルミ材が開発できた。 As described above, prior to the chemical conversion treatment of the present invention, by forming an appropriate amount of a good quality hydroxide film on the aluminum plate in advance, a stable aluminum material surface that is not subject to change with time was created, and a uniform chemical conversion film was formed. Aluminum materials for aluminum containers have been developed with excellent performance in preventing blackening when boiled water etc. is used after filling the contents and sterilization treatment or hot selling keeps the temperature high. .
一般的なアルミ材のZr系化成処理は脱脂処理、リンスを経た後、Zrイオン(錯化合物等を含む)、その他イオンを含有するZr系化成処理剤に浸漬またはスプレーにより吹き付けることにより得られる。元のZr溶液のpHはZrまたはZr化合物がイオンまたは錯イオンの形態で溶解し得るように低く設定されている。アルミ板がこのようなZr化合物液に接触すると、アルミの溶解に伴い発生した電子により水の還元が起こるか、アルミ板上の水酸化物または酸化物の溶解による酸塩基反応により、Zr系化成処理剤のpHが上昇し、所謂沈殿pH以上のpHになる。その結果、それまで化成液中に溶解していたZr成分がアルミ板状に析出・付着することを基本原理としている。従って化成液と接触したときに溶解しないような表面はZr皮膜の形成を妨げることになる。 A general Zr-based chemical conversion treatment of an aluminum material is obtained by spraying a Zr-based chemical conversion treatment agent containing Zr ions (including complex compounds) and other ions by dipping or spraying after degreasing and rinsing. The pH of the original Zr solution is set low so that the Zr or Zr compound can be dissolved in the form of ions or complex ions. When the aluminum plate comes into contact with such a Zr compound solution, the reduction of water occurs due to the electrons generated along with the dissolution of aluminum, or the acid-base reaction due to the dissolution of hydroxide or oxide on the aluminum plate causes a Zr-based chemical conversion. The pH of the treatment agent rises to a pH higher than the so-called precipitation pH. As a result, the basic principle is that the Zr component that has been dissolved in the chemical conversion solution is deposited and adhered in the form of an aluminum plate. Therefore, a surface that does not dissolve when it comes into contact with the chemical conversion solution prevents formation of a Zr film.
水酸化皮膜形成処理に先立ち、通常、アルミ板表面をあらかじめ脱脂処理しておくことが好ましい。冷間圧延上がりの状態ではアルミ板上に冷延油等の多量の油分が付着しており、水をはじくため本発明の水酸化皮膜形成を阻害する。具体的には軽質油と接触させ圧延油と置換した後、ドライヤー等で加熱し揮発させることや、界面活性剤を含む洗浄液で洗うことによって行われる。 Prior to the hydroxide film formation treatment, it is usually preferable to degrease the surface of the aluminum plate in advance. In the state after the cold rolling, a large amount of oil such as cold-rolled oil adheres on the aluminum plate and repels water, thereby inhibiting the formation of the hydroxide film of the present invention. Specifically, it is performed by contacting with light oil and replacing with rolling oil, and then heating and volatilizing with a drier or the like, or washing with a cleaning liquid containing a surfactant.
この場合、アルミ表面に一定量以上のMg水酸化物または水和酸化物(以下「Mg水酸化物等」とも言う。)が存在するとリオイル、ボディメーカークーラント等に由来する油分が残留することが避けられず、そのような表面に化成処理を行うと、アルミ表面のpH上昇が不均一となり、結果的に十分な厚さのZr皮膜が形成されなかったり、若干量残った油層の上にZr皮膜層が形成されたりするため、化成処理後沸水に浸漬したときにアルミ表面と沸水が反応したり、油層上のZrが簡単に流出し、結果的にアルミ面と沸水が反応し、アルミ面に黒色の皮膜が形成されることが判明した。
結局、沸水浸漬における黒変を防止するには、アルミ表面のMg水酸化物等の量をコントロールすること必要であることが判明した。
In this case, if there is a certain amount or more of Mg hydroxide or hydrated oxide (hereinafter also referred to as “Mg hydroxide”) on the aluminum surface, oil components derived from reoil, body maker coolant, etc. may remain. When chemical conversion treatment is performed on such a surface, the pH increase on the aluminum surface becomes non-uniform, resulting in the formation of a Zr film with a sufficient thickness or a small amount of Zr on the remaining oil layer. Since a film layer is formed, the aluminum surface reacts with boiling water when immersed in boiling water after chemical conversion treatment, or Zr on the oil layer flows out easily, resulting in a reaction between the aluminum surface and boiling water. It was found that a black film was formed.
Eventually, it was found that it is necessary to control the amount of Mg hydroxide and the like on the aluminum surface in order to prevent blackening in boiling water immersion.
一方アルミニウム水酸化物や水和酸化物(以下「Al水酸化物等」とも言う。)は中性の水には溶けにくく、沸水中での黒変を抑止する効果があるので、ある程度残っている方が耐沸水黒変には良い効果がある。またAl水酸化物等は溶解したときに化成液のpHを上昇させる効果があり、Zr系化成皮膜の形成を促進するので、この面からもこれはある程度残留していても良いと言える。
しかしあまり皮膜が厚いと、元々固い皮膜のためにクラックを生じ易く、加工成形時にキズの発生を誘発したり、急激な温度上昇・下降が起こった時に皮膜が割れる結果、最上層に塗った塗膜が酸化皮膜(または水酸化皮膜)ごと剥離を生じるため、酸化皮膜もしくは水酸化皮膜の厚みには上限がある。
On the other hand, aluminum hydroxide and hydrated oxide (hereinafter also referred to as “Al hydroxide, etc.”) are hardly soluble in neutral water and have the effect of suppressing blackening in boiling water. It has a good effect on boiling water blackening. Moreover, since Al hydroxide has the effect of increasing the pH of the chemical conversion solution when dissolved, it promotes the formation of a Zr-based chemical conversion film, so it can be said that this may remain to some extent.
However, if the film is too thick, it is prone to cracking due to the originally hard film, causing scratches during processing molding, and cracking the film when sudden temperature rises or falls. Since the film peels off together with the oxide film (or hydroxide film), there is an upper limit to the thickness of the oxide film or hydroxide film.
もう少し詳細にAl及びMgの酸化物及び水酸化物と黒変の関係を以下に述べる。
Al合金板を酸洗(例えば硫酸酸洗)すると表面のMg化合物が溶解・除去され、主にその後のリンス・乾燥工程でアルミ材表面に酸化Alを主体とする酸化皮膜が形成されることは一般的に知られている。このような表面にリオイルを塗油し、さらにボディメーカークーラントと接触させて圧延し、さらに酸系脱脂剤で脱脂処理をした後、Zr系化成処理剤で化成処理をしてから沸水浸漬しても黒変は生じなかった。このことは酸化Alを主体とする皮膜が表面を覆っていても黒変には影響しないことを示している。
一方酸洗・リンス後、一定の湿度雰囲気に曝すと(例えば40℃、相対湿度80%の雰囲気中に7日間暴露)、表面が水酸基化されることも広く知られているが、そのような表面も黒変するようなことは無かった。
The relationship between Al and Mg oxides and hydroxides and blackening will be described below in a little more detail.
When an Al alloy plate is pickled (for example, sulfate pickled), the Mg compound on the surface is dissolved and removed, and an oxide film mainly composed of Al oxide is formed on the surface of the aluminum material mainly in the subsequent rinsing / drying process. Generally known. Apply reoil to such a surface, roll it in contact with a body maker coolant, further degrease with an acid-based degreasing agent, then perform a chemical conversion treatment with a Zr-based chemical conversion treatment agent and then immerse in boiling water. No blackening occurred. This indicates that the blackening is not affected even if the film mainly composed of Al oxide covers the surface.
On the other hand, after pickling and rinsing, when exposed to a constant humidity atmosphere (for example, exposure to an atmosphere of 40 ° C. and 80% relative humidity for 7 days), it is widely known that the surface is hydroxylated. The surface did not turn black.
すなわち水酸化Alも黒変に影響することは無いことを示している。酸洗・リンス後、素材を一定温度で焼鈍(例えば400℃で20分保持)すると、表面にMgが析出し、大気雰囲気または酸化性の雰囲気に曝されると酸化Mgが表面に形成されることもこれまた一般的に知られている。このような表面においても黒変は発生せず、酸化Mgも黒変に影響しないことが判明した。
しかし酸洗・リンス後、素材を一定温度で焼鈍して酸化Mg層を形成せしめた後、一定の湿度雰囲気に曝して表面に水酸化Mg層を形成したときは、この時のみ顕著な黒変が発生した。このことはMg水酸化物等が黒変の主な要因であることを示している。
That is, Al hydroxide does not affect the blackening. After pickling and rinsing, when the material is annealed at a constant temperature (for example, held at 400 ° C. for 20 minutes), Mg is deposited on the surface, and Mg oxide is formed on the surface when exposed to the atmosphere or oxidizing atmosphere. This is also generally known. It has been found that no blackening occurs on such a surface, and Mg oxide does not affect the blackening.
However, after pickling and rinsing, the material is annealed at a constant temperature to form an Mg oxide layer, and then exposed to a constant humidity atmosphere to form a Mg hydroxide layer on the surface. There has occurred. This indicates that Mg hydroxide or the like is the main cause of blackening.
一方、これらの試験においてリオイル塗油及びボディメーカークーラントとの接触をさせないで、すなわち有機物との接触無しで沸水浸漬しても顕著な黒変は発生しなかった。このことはMg水酸化物等自体は黒変に影響しないものの、有機物と結びつくと黒変を誘発することを示していると考えられる。Mg水酸化物等が形成されていると、なぜ油分が残留しやすいかといった点に関しての詳細は未だ不明であるが、Mg水酸化物等と油分、特に脂肪酸エステルや脂肪酸といった極性基を有する有機物が非常に強固に結びつきやすいのに対し、それ以外の物質、例えばAl水酸化物等といった物質は油分との結びつきが緩いためと推定される。 On the other hand, in these tests, no significant blackening occurred even when immersed in boiling water without contact with reoiled oil and body maker coolant, that is, without contact with organic matter. This suggests that Mg hydroxide itself does not affect blackening, but induces blackening when combined with organic matter. Details regarding the reason why oil is likely to remain when Mg hydroxide and the like are formed are still unclear, but Mg hydroxide and the oil, especially organic substances having polar groups such as fatty acid esters and fatty acids. It is presumed that the other substances such as Al hydroxide are loosely associated with the oil, whereas the other substances such as Al hydroxide are loosely bonded.
Mg酸化物またはMg水酸化物等に由来するOH吸収量を以下のように推定している。
酸洗済み板を一定湿度雰囲気中に暴露する際、暴露時間を変え、FT−IRを用いて各処理時間ごとのOH吸収量を求めた。このOH量は表面に形成されたAl水酸化物等に由来するOH量と考えられる。これとは別に酸洗済み板を400℃で種々の時間加熱し、表面に酸化Mgを析出させた試験片を調整し、グロー放電発光分光分析装置(GDS)デプスプロファイルによりMgの最大発光強度を測定した。これらの試験片を暴露時間を変えて湿度雰囲気中に曝し、前記試料と同様にOH吸収量を測定した。
The OH absorption amount derived from Mg oxide or Mg hydroxide is estimated as follows.
When the pickled plate was exposed to a constant humidity atmosphere, the exposure time was changed, and the OH absorption amount for each treatment time was determined using FT-IR. This OH amount is considered to be the OH amount derived from Al hydroxide formed on the surface. Separately, the pickled plate is heated at 400 ° C. for various times to prepare a test piece in which Mg oxide is deposited on the surface, and the maximum emission intensity of Mg is determined by a glow discharge emission spectrometer (GDS) depth profile. It was measured. These test pieces were exposed to a humidity atmosphere while changing the exposure time, and the OH absorption amount was measured in the same manner as the sample.
この時同一暴露時間同士のOH吸収量は、表面のMg量、すなわちグロー放電発光分光分析装置(GDS)デプスプロファイルによるMgの最大発光強度に従って増加した。従ってMg析出の無い状態でのOH量とMgを析出させた状態でのOH量の差分がMg水酸化物またはMg水和酸化物量に相当すると考えられる。
一例を示すと、酸洗板を40℃、相対湿度80%の雰囲気に90日間曝露するとOH吸収量は約1.1%であった。これは水酸化Al等に由来するOH吸収量である。一方、表面にMgを析出させた試料で同様の試験を行ったところ、Mg最大発光強度が1.7Vの場合は約1.6%、Mg最大発光強度が4.5Vの場合は約2.8%、Mg最大発光強度が5.1Vの場合は約3.8%であった。従ってMg水酸化物等に由来するOH吸収量は各々0.5%、1.7%、2.7%と見積もられる。
At this time, the amount of OH absorbed during the same exposure time increased according to the amount of Mg on the surface, that is, the maximum emission intensity of Mg according to the glow discharge emission spectrometer (GDS) depth profile. Therefore, it is considered that the difference between the amount of OH without Mg precipitation and the amount of OH with Mg precipitated corresponds to the amount of Mg hydroxide or Mg hydrated oxide.
As an example, when the pickled plate was exposed to an atmosphere of 40 ° C. and a relative humidity of 80% for 90 days, the OH absorption amount was about 1.1%. This is the OH absorption amount derived from Al hydroxide and the like. On the other hand, when a similar test was performed on a sample having Mg deposited on the surface, the sample was about 1.6% when the maximum Mg emission intensity was 1.7 V, and about 2.2 when the Mg maximum emission intensity was 4.5 V. In the case of 8% and Mg maximum emission intensity of 5.1V, it was about 3.8%. Therefore, the OH absorption amount derived from Mg hydroxide and the like is estimated to be 0.5%, 1.7%, and 2.7%, respectively.
このような試料を一連の前処理を経た後黒変試験を行ったところ、Mg水酸化物等に由来するOH量が2.7%の試料は黒変し、1.7%以下の試料では黒変を生じなかった。以上説明したようにMg水酸化物等量が一定量以下であれば黒変しないことが判明した。 When such samples were subjected to a series of pretreatments and then subjected to a blackening test, a sample having an OH amount of 2.7% derived from Mg hydroxide and the like turned black, and a sample having a concentration of 1.7% or less There was no blackening. As described above, it has been found that if the amount of Mg hydroxide is equal to or less than a certain amount, it does not turn black.
次ぎに発明者等はさらに踏み込んだ試験を行い、Mg水酸化物等が無いだけでは黒変を防ぎきれず、Mg水酸化物等が一定量以下の全水酸化物等皮膜の皮膜が一定量以上必要であることを見出した。
しかし通常のアルミ材製品表面においては、複数の金属イオンの酸化物と水酸化物が混在しているため、Mg水酸化物等のみを測定することは難しい。種々検討した結果、直接Mg水酸化物量を求めなくても、Mg析出量を一定値以下に抑え、かつ水酸化物皮膜総量を一定量にすれば、初期の目的を達成できることを見出した。具体的にはグロー放電発光分光分析装置(GDS)によるMgの最大発光強度が2V以下で、かつ10mg/m2以上の水酸化皮膜がアルミ表面に形成されている時に黒変を生じないことを見出した。
Next, the inventors conducted further tests, and it was not possible to prevent blackening only by the absence of Mg hydroxide, etc., and a certain amount of the coating film of all hydroxides, etc. with less than a certain amount of Mg hydroxide etc. I found out that it is necessary.
However, it is difficult to measure only Mg hydroxide or the like because a plurality of metal ion oxides and hydroxides are mixed on the surface of a normal aluminum product. As a result of various investigations, it has been found that the initial purpose can be achieved if the Mg precipitation amount is suppressed to a certain value or less and the total amount of the hydroxide film is kept constant, without directly determining the Mg hydroxide amount. Specifically it is at 2V below the maximum luminous intensity of the Mg by glow discharge optical emission spectrometer (GDS) is and that does not cause blackening when 10 mg / m 2 or more hydroxide film is formed on the aluminum surface I found it.
SEM観察によれば、Zr系化成皮膜の構造が水酸化皮膜総量により変化し、全水酸化物等皮膜が10mg/m2未全満の時はZr系化成皮膜に微細な孔が生じているのに対して、全水酸化物等皮膜が10mg/m2以上の場合は微細孔の無い均一な化成皮膜が形成されていた。このような幾何学的形状の違いにより黒変発生有無を生じたものと考えられる。
すなわち微細孔を有するZr系皮膜は沸水が微細孔を通ってアルミ素地と反応し黒変を生じるのに対して、微細孔の無いZr系皮膜が形成されていると沸水とアルミ素地が直接接触出来ないために黒変を生じないと推定される。
According to SEM observation, the structure of the Zr-based chemical conversion film changes depending on the total amount of the hydroxide film, and when the total hydroxide film is less than 10 mg / m 2 , fine pores are formed in the Zr-based chemical conversion film. On the other hand, when the total hydroxide film was 10 mg / m 2 or more, a uniform chemical conversion film without micropores was formed. It is considered that the presence or absence of blackening occurred due to such a difference in geometric shape.
In other words, while Zr-based coatings with micropores react with the aluminum substrate through the micropores and cause blackening, when Zr-based coatings without micropores are formed, the boiling water and the aluminum substrate are in direct contact. It is presumed that blackening does not occur because it is not possible.
一定量以上の全水酸化物等皮膜が存在すると微細孔の無いZr系皮膜が形成されるメカニズムは不明確であるが、以下のように考えている。
既に記載したようにZr系化成液のpHが上昇するとアルミ表面にZr系皮膜が形成される。pH上昇を推し進める反応として、金属アルミが溶解し放出される電子により水が還元される電気化学的な反応と、水酸化物が溶解し中和反応が起こる酸塩基反応の2つが考えられる。酸化還元反応では水素等の気泡発生を伴うことや、また通常のアルミ材ではアノード及びカソードとして働く部分が不均一に存在するため、微細孔を有する不均一な皮膜が形成されやすい。これに対し水酸化物の溶解による酸塩基反応においては、水酸化物が均一もしくは局部的な欠損なしに表面を被覆している場合、全表面で化成液のpHを上昇させ、また溶解に際して気泡発生を伴わないので、均一なZr系化成皮膜を形成させると推定している。
The mechanism of forming a Zr-based film without fine pores when a film of a certain amount or more of total hydroxide is present is unclear, but is considered as follows.
As already described, when the pH of the Zr-based chemical is increased, a Zr-based film is formed on the aluminum surface. There are two possible reactions that promote the increase in pH: an electrochemical reaction in which water is reduced by electrons dissolved and released by metal aluminum, and an acid-base reaction in which a hydroxide dissolves and a neutralization reaction occurs. In the oxidation-reduction reaction, bubbles such as hydrogen are generated, and in a normal aluminum material, portions that function as an anode and a cathode are present non-uniformly, so that a non-uniform film having fine pores is easily formed. On the other hand, in the acid-base reaction by dissolution of hydroxide, if the hydroxide coats the surface without uniform or local defects, the pH of the chemical conversion solution is raised on the entire surface, and bubbles are generated during dissolution. Since no generation occurs, it is estimated that a uniform Zr-based chemical conversion film is formed.
水酸化皮膜を形成させる具体的手段としては、液体の水または水蒸気と表面を接触させるこよにより達成できる。
ただし、水蒸気浴は工業的にはコイル状のアルミ板を連続的に、かつ均一に水酸化皮膜を低コストで形成させることは難しい。従って実際上は液体状の水分との接触が水酸化皮膜形成に有利である。
この時、水中に硫酸イオンまたはリン酸イオンが多量に存在すると水酸化皮膜の形成を妨害するため十分な厚みの水酸化皮膜が得られない。研究の結果、その他成分は直接的には影響せず、水の電気伝導度も直接の影響を与えなかった。具体的にはpH4以上,8未満、好ましくはpH5以上、7以下で、硫酸イオンまたはリン酸イオンの濃度を500ppm以下にコントロールすれば良い。イオン交換水はMg除去効果が強いので最も好ましい。
A specific means for forming the hydroxide film can be achieved by bringing the surface into contact with liquid water or water vapor.
However, it is difficult industrially to form a hydroxide film continuously and uniformly at a low cost in a steam bath. Therefore, in practice, contact with liquid water is advantageous for forming a hydroxide film.
At this time, if a large amount of sulfate ion or phosphate ion is present in water, the formation of a hydroxide film is hindered, so that a hydroxide film having a sufficient thickness cannot be obtained. As a result of the study, the other components did not directly affect the water, and the electrical conductivity of the water did not directly. Specifically, the concentration of sulfate ions or phosphate ions may be controlled to 500 ppm or less at pH 4 or more and less than 8, preferably pH 5 or more and 7 or less. Ion exchange water is most preferable because of its strong Mg removal effect.
水温に特に制限はないが、低温では水酸化物等皮膜の形成が遅く、高温では装置管理上不具合を生じる場合がある。具体的には50℃〜100℃、好ましくは60〜90℃である。
液体状の水との接触方法には特に制限はないが、スプレーによる吹き付けまたは浸漬が、コイル状アルミ板処理に向いている。
There is no particular limitation on the water temperature, but formation of a film such as hydroxide is slow at low temperatures, and problems may occur in device management at high temperatures. Specifically, it is 50-100 degreeC, Preferably it is 60-90 degreeC.
Although there is no restriction | limiting in particular in the contact method with liquid water, Spraying or immersion by spraying is suitable for coiled aluminum board processing.
接触時間は装置の構造、その他条件で種々変わるので、特に限定は無く適宜設計すれば良いが、水酸化物等皮膜として10〜150mg/m2、好ましくは15〜100mg/m2 となるように調整すれば良い。ただし余りに長い接触時間をかけると装置長が長く設備費が嵩むので好ましくない。工業的には5〜180秒が好ましい。 Since the contact time varies depending on the structure of the apparatus and other conditions, it is not particularly limited and may be appropriately designed. However, the film such as hydroxide is 10 to 150 mg / m 2 , preferably 15 to 100 mg / m 2. Adjust it. However, too long contact time is not preferable because the apparatus length is long and the equipment cost increases. Industrially, 5 to 180 seconds are preferable.
また、アルカリ性水使用の水酸化皮膜の形成にあたってはpH=9〜12、かつ硫酸イオン濃度≦500ppm、リン酸イオン濃度≦500ppmのアルカリ性水溶液を、2〜20秒、浸漬またはスプレーによりアルミ表面と接触させても良く、このような液体では、Mg除去と水酸化皮膜形成が促進されるので効率が良い。 Further, in forming a hydroxide film using alkaline water, an alkaline aqueous solution having a pH of 9 to 12, a sulfate ion concentration of ≦ 500 ppm, and a phosphate ion concentration of ≦ 500 ppm is contacted with the aluminum surface by dipping or spraying for 2 to 20 seconds. Such a liquid is efficient because Mg removal and formation of a hydroxide film are promoted.
pH<9では水酸化皮膜の形成が遅く、pH≧12ではアルミのエッチング量が多いため、処理中に発生するスラッジ量が多く、またMg除去効果が低減するので好ましくない。
浴温、時間等は適宜定めれば良いが、浴温は30〜90℃、好ましくは40〜80℃で時間は2〜20秒程度で良い。30℃未満の場合、短時間では十分な水酸化皮膜形成効果を得るための時間が長く、工業生産には不向きである。また使用する界面活性剤によっては発泡性が強くなるため好ましくない。90℃を越えると使用する界面活性剤の種類にもよるが界面活性剤が乳化力を失ったり、特にノニオン系界面活性剤の場合は界面活性剤の析出が起こる(所謂曇点)ことや、エッチング量が高くなりスラッジが発生しやすい等の不具合を生じるので好ましくない。
At pH <9, the formation of a hydroxide film is slow, and at pH ≧ 12, the amount of aluminum etching is large, so that the amount of sludge generated during the treatment is large and the effect of removing Mg is reduced.
The bath temperature, time, etc. may be determined as appropriate, but the bath temperature is 30 to 90 ° C., preferably 40 to 80 ° C., and the time may be about 2 to 20 seconds. When it is less than 30 ° C., it takes a long time to obtain a sufficient effect of forming a hydroxide film in a short time, which is not suitable for industrial production. Also, depending on the surfactant used, foaming properties become strong, which is not preferable. If the temperature exceeds 90 ° C., the surfactant loses emulsifying power, depending on the type of surfactant used. In particular, in the case of a nonionic surfactant, precipitation of the surfactant occurs (so-called cloud point). This is not preferable because the etching amount becomes high and sludge is likely to occur.
時間は2秒以上で良いが、20秒を越えて処理する場合、水酸化皮膜が厚くなりすぎ成形に際して黒スジ発生等の不具合を生じる場合があるので、やはり好ましくない。
アルカリビルダーとしてはリン酸塩、硫酸塩以外のものが好ましく、具体的には硼酸ナトリウム等の硼酸塩、炭酸カリウム等の炭酸塩、炭酸水素ナトリウム等の重炭酸塩、水酸化ナトリウムのような水酸化物、ケイ酸ナトリウムのようなケイ酸化合物が上げられる。またこれらの内の2種以上の混合物であっても良い。ただし硼酸塩は殺菌作用が強く、活性汚泥中のバクテリアも殺すため生物化学的廃水処理を行うには不都合で、化学的処理をする必要がある。
The time may be 2 seconds or more, but if the treatment is performed for more than 20 seconds, the hydroxide film becomes too thick, which may cause problems such as black streaks during molding.
Alkaline builders other than phosphates and sulfates are preferred. Specifically, borates such as sodium borate, carbonates such as potassium carbonate, bicarbonates such as sodium bicarbonate, and water such as sodium hydroxide. Oxides, silicate compounds such as sodium silicate are raised. Moreover, the mixture of 2 or more types of these may be sufficient. However, borate has a strong bactericidal action and kills bacteria in the activated sludge, which is inconvenient for biochemical wastewater treatment and requires chemical treatment.
濃度は前記pHに入るようにすれば良い。また建浴時のpHが12を越えていても、空気のバブリング、攪拌等による巻き込み、炭酸ガスの吹き込み等の手段でpH≦12となるように調整した後に使用しても良い。 The concentration should be within the above pH. Even if the pH during the bathing exceeds 12, it may be used after adjusting so that pH ≦ 12 by means such as bubbling of air, agitation by stirring, or blowing of carbon dioxide gas.
建浴に際しては硫酸イオン濃度≦500ppm及びリン酸イオン濃度≦500ppmとなるような水を用いれば良いが、イオン交換水は純度が高いので好ましい。
界面活性剤としては洗浄力のある界面活性剤を併用すれば良く特に制限は無いが、硫酸エステルナトリウム塩、リン酸エステルナトリウム塩、リン酸エステルのアミン中和物といった硫酸化合物やリン酸化合物は遊離の硫酸イオンやリン酸イオンを生成する可能性があるので使用量に制限がある。好適にはポリオキシエチレンアルキルエーテルやソルビタン脂肪酸エステルといったノニオン系界面活性剤や、炭酸エステル、脂肪酸エステル、高級アルコール系界面活性剤等、硫酸イオン、リン酸イオンを含まない界面活性剤を挙げることが出来る。
In the bath, water having a sulfate ion concentration ≦ 500 ppm and a phosphate ion concentration ≦ 500 ppm may be used, but ion-exchanged water is preferable because of its high purity.
There is no particular limitation as long as a surfactant having a detergency is used as the surfactant, but sulfate compounds and phosphate compounds such as sulfate sodium salt, phosphate sodium salt, and phosphate neutralized amines are not available. Since there is a possibility of generating free sulfate ions and phosphate ions, the amount used is limited. Preferred examples include nonionic surfactants such as polyoxyethylene alkyl ethers and sorbitan fatty acid esters, and surfactants that do not contain sulfate ions or phosphate ions, such as carbonate esters, fatty acid esters, and higher alcohol surfactants. I can do it.
また環境汚染の面から、ノニルフェニルエーテル系界面活性剤を始めとするフェニル基を含む界面活性剤は避けるべきであろう。
界面活性剤濃度に特に制限はないが、多量に入れても溶解しないため無駄であり、廃水処理費用も嵩むことと、少量に過ぎると乳化力を失うので、使用する界面活性剤に合わせて最適濃度を維持するようにすれば良い。
From the viewpoint of environmental pollution, surfactants containing phenyl groups such as nonylphenyl ether surfactants should be avoided.
There is no particular restriction on the surfactant concentration, but it is useless because it does not dissolve even when added in large amounts, and wastewater treatment costs increase, and if it is too little, emulsifying power is lost, so it is optimal for the surfactant used What is necessary is just to maintain a density | concentration.
表面分析
[a.アルミ板表面のMg量測定]
マーカス型高周波グロー放電発光分光分析装置(GDS)を用い測定した。機種はホリバ製作所製JY−5000RF型を用い、アノード径4mm、出力30Wで、アルゴンガス(ガス圧600Pa)にてスパッタリングを行い、フォトマルチプライヤー(電圧750V)にてMgからの発光強度(測定波長383nm)測定した。データ取得時間は0.001秒/1データで、スパッタ速度は約5.56nm/分であった。
Surface analysis [a. Measurement of Mg content on aluminum plate surface]
Measurement was performed using a Marcus type high-frequency glow discharge optical emission spectrometer (GDS). The model is a JY-5000RF type manufactured by Horiba Seisakusho. Sputtering is performed with argon gas (gas pressure 600 Pa) at an anode diameter of 4 mm and an output of 30 W. Luminescence intensity from Mg with a photomultiplier (voltage 750 V) (measurement wavelength) 383 nm). The data acquisition time was 0.001 sec / data, and the sputtering rate was about 5.56 nm / min.
深さ方向分析結果(デプスプロファイル)の一例を図1に示す。Mgの発光強度は最表面ではやや低く、表面直下で最大発光強度を示す。その後バルクに向かって漸次減少する。表面付近のMg量の規定には最大発光強度を用いた。面積法、極大値から減少する斜面の接線とバルク部分の接線との交点の深さ測定、最大強度の1/2の強度を示す深さ方向の幅等、幾つかの評価法も検討した。
しかし、各試料間の表面付近のMg量の多少の順位はいずれの方法でも変わらず、最大発光強度の読み取りが最も迅速かつ容易なので、最大発光強度の読み値を以ってMg量とした。
An example of the depth direction analysis result (depth profile) is shown in FIG. The emission intensity of Mg is slightly low on the outermost surface, and shows the maximum emission intensity just below the surface. Thereafter, it gradually decreases toward the bulk. The maximum light emission intensity was used to define the amount of Mg near the surface. Several evaluation methods were also examined, such as the area method, the depth measurement of the intersection of the tangent of the slope decreasing from the maximum value and the tangent of the bulk part, the width in the depth direction indicating half the maximum intensity.
However, the order of the amount of Mg near the surface between the samples did not change by any method, and reading of the maximum emission intensity was the quickest and easiest, so the reading of maximum emission intensity was used as the Mg amount.
[b.水酸化物量の測定]
試験片の重量を測定した後、リン酸およびクロム酸の混酸に、90℃で1分浸漬し、続いて水洗・乾燥を経てから再度重量を測定した。浸漬前の重量と浸漬後の重量差を水酸化皮膜量とした。
[c.Zr付着量]
(株)リガク製ケイ光X線分析装置で測定した。
[B. Measurement of hydroxide amount]
After measuring the weight of the test piece, it was immersed in a mixed acid of phosphoric acid and chromic acid at 90 ° C. for 1 minute, followed by washing and drying, and then measuring the weight again. The difference between the weight before immersion and the weight after immersion was defined as the amount of the hydroxide film.
[C. Zr adhesion amount]
It measured with the Rigaku Co., Ltd. fluorescence X-ray-analysis apparatus.
(実施例1・比較例1)
JIS 3004−H19合金(板厚0.26mm)のアルミニウム冷延板を元材とした。次にこの元材をアルカリ系脱脂剤(日本パーカライジング製FC4498−SK3)にて脱脂処理した後、50℃の10重量%の硫酸浴に1分浸漬し、さらに工業用水でリンスした後、軽く純水で洗い、ドライヤーで乾燥して表面のMgを除去した。この後、一部試料を乾燥大気雰囲気中で300〜400℃で20分間焼鈍してMgを析出させ、炉から取り出し、直ちにデシケーター中に移し、種々のMg量を有する表面を調製した。
(Example 1 and Comparative Example 1)
An aluminum cold-rolled sheet of JIS 3004-H19 alloy (plate thickness 0.26 mm) was used as a base material. Next, this base material was degreased with an alkaline degreasing agent (Nippon Parkerizing FC4498-SK3), immersed in a 10 wt% sulfuric acid bath at 50 ° C. for 1 minute, rinsed with industrial water, and then lightly purified. It was washed with water and dried with a dryer to remove Mg on the surface. Thereafter, a part of the sample was annealed in a dry air atmosphere at 300 to 400 ° C. for 20 minutes to precipitate Mg, taken out from the furnace, and immediately transferred into a desiccator to prepare surfaces having various amounts of Mg.
次ぎにこれらの試料を40℃、相対湿度80%の恒温恒湿槽に24〜336H投入し、種々の水酸基化状態の表面を得た。
これらの試料のMg量及び水酸化皮膜量を各々GDS、重量法で測定した。酸洗ままの試料を加湿処理して増加したOH量はアルミニウム水酸化物に由来する。各加湿時間においてMg析出表面はそれ以上のOH量増加を示し、また同一加湿時間で比較するとMg析出量(GDS最大発光強度)に応じて増加量が変わる。酸洗まま表面のOH量とMg析出表面のOH量の差はMg水酸化物に由来するOH量を表しており、この差分を以ってMg水酸化物量とした。
Next, these samples were put into a constant temperature and humidity chamber having a temperature of 40 ° C. and a relative humidity of 80% in an amount of 24 to 336H to obtain various hydroxylated surfaces.
The amount of Mg and the amount of hydroxide film of these samples were measured by GDS and gravimetric method, respectively. The amount of OH increased by humidifying the pickled sample is derived from aluminum hydroxide. At each humidification time, the Mg precipitation surface shows a further increase in the OH amount, and when compared at the same humidification time, the increase amount changes according to the Mg precipitation amount (GDS maximum emission intensity). The difference between the amount of OH on the surface and the amount of OH on the Mg precipitation surface represents the amount of OH derived from Mg hydroxide, and this difference was used as the amount of Mg hydroxide.
これらの試料にエステル系潤滑油を300mg/m2塗油し、さらにエマルション系ボディメーカークーラント水溶液をくぐらせた後、脱脂処理及びZr系化成処理を行った。脱脂は3.4容量%の酸系脱脂剤にて、50℃、45秒間、スプレ−圧1MPaで行い、工業用水でリンスした。続いて、1.7容量%のリン酸Zr系化成処理剤にて、40℃、20秒間、スプレ−圧0.1MPaで化成処理皮膜を形成させ、直ちに工業用水でリンスした後、ドライヤーで乾燥し試験片とした。この時のZr付着量は約13〜15mg/m2であった。
このようにして得た試験片を、100℃の工業用水中に30分間浸漬した。試験片を取り出し、乾燥後、目視にて黒変程度を評価した。評価基準は、「○:黒変ナシ」、「×:黒変発生」とした。
These samples were coated with 300 mg / m 2 of an ester-based lubricating oil, passed through an emulsion-based body maker coolant solution, and then subjected to a degreasing process and a Zr-based chemical conversion process. Degreasing was performed with a 3.4% by volume acid-based degreasing agent at 50 ° C. for 45 seconds at a spray pressure of 1 MPa, and rinsed with industrial water. Subsequently, a chemical conversion treatment film was formed at 1.7 ° C. with a phosphoric acid Zr-based chemical conversion treatment agent at 40 ° C. for 20 seconds at a spray pressure of 0.1 MPa, immediately rinsed with industrial water, and then dried with a dryer. A test piece was prepared. At this time, the Zr adhesion amount was about 13 to 15 mg / m 2 .
The test piece thus obtained was immersed in industrial water at 100 ° C. for 30 minutes. The test piece was taken out, dried, and then visually evaluated for the degree of blackening. The evaluation criteria were “◯: black discoloration” and “×: black discoloration”.
表1に結果を示す。
Mg最大発光強度が2V以下で、かつ水酸化皮膜量が10mg/m2以上存在すると黒変を生じなかった。Mg最大発光強度が2V以下でも、水酸化皮膜量が10mg/m2未満であったり、Mg最大発光強度が2Vを越えていると水酸化皮膜量が10mg/m2以上あっても黒変を生じる。
Table 1 shows the results.
When the Mg maximum emission intensity was 2 V or less and the amount of the hydroxide film was 10 mg / m 2 or more, blackening did not occur. Even when the maximum Mg emission intensity is 2 V or less, the amount of the hydroxide film is less than 10 mg / m 2 , or when the maximum Mg emission intensity exceeds 2 V, even if the amount of the hydroxide film is 10 mg / m 2 or more, blackening occurs. Arise.
(実施例2・比較例2)
実施例1・比較例1と同様にJIS 3004−H19合金(板厚0.26mm)のアルミニウム冷延板を元材とした。
この元板のMg最大発光強度は2.3Vであった。この元板をヘキサンに浸漬して表面を脱脂した。次に表2に示すような各種の水で処理し、試験片とした。
処理は圧力=0.15MPaのスプレーを用いた。
表面Mg量測定、水酸化皮膜量測定、黒変試験は実施例1・比較例1と同様の方法で行なった。
結果を表2に示す。
浴中のリン酸イオン、硫酸イオン濃度が500ppm以下の温水で処理すると、Mg量の少ない水酸化皮膜が形成され、黒変性が良くなる。
(Example 2 and Comparative Example 2)
As in Example 1 and Comparative Example 1, an aluminum cold-rolled sheet of JIS 3004-H19 alloy (plate thickness 0.26 mm) was used as a base material.
The maximum emission intensity of Mg of this base plate was 2.3V. The base plate was immersed in hexane to degrease the surface. Next, it processed with various water as shown in Table 2, and it was set as the test piece.
For the treatment, a spray with a pressure = 0.15 MPa was used.
Surface Mg amount measurement, hydroxide film amount measurement, and blackening test were performed in the same manner as in Example 1 and Comparative Example 1.
The results are shown in Table 2.
When treated with warm water having a phosphate ion and sulfate ion concentration of 500 ppm or less in the bath, a hydroxide film with a small amount of Mg is formed and blackening is improved.
(実施例3・比較例3)
実施例1・比較例1と同様にJIS 3004−H19合金(板厚0.26mm)のアルミニウム冷延板を元材とした。この元板のMg最大発光強度は2.3Vであった。
この元板を表3に示すようなアルカリ性液を、スプレー圧=0.1MPaでスプレー処理した後、工業用水でリンスし、さらにドライヤーで乾燥し、試験片とした。アルカリ脱脂剤以外のアルカリ液の場合は、冷延板をあらかじめヘキサンに浸漬して表面を脱脂した後アルカリ性液と接触させた。
(Example 3 and Comparative Example 3)
As in Example 1 and Comparative Example 1, an aluminum cold-rolled sheet of JIS 3004-H19 alloy (plate thickness 0.26 mm) was used as a base material. The maximum emission intensity of Mg of this base plate was 2.3V.
The base plate was sprayed with an alkaline solution as shown in Table 3 at a spray pressure of 0.1 MPa, rinsed with industrial water, and then dried with a drier to obtain a test piece. In the case of an alkaline solution other than the alkaline degreasing agent, the cold-rolled plate was previously immersed in hexane to degrease the surface and then contacted with the alkaline solution.
アルカリ脱脂剤aには日本パーカライジング製FC4498−SK3、アルカリ脱脂剤bには日本パーカライジング製FC4498−SK4を用いた。両者ともノニルフェニル系界面活性剤及びリン酸塩を含まない環境対応型脱脂剤である。
表面Mg量測定、水酸化皮膜量測定、黒変試験は実施例1・比較例1と同様の方法で行なった。
結果を表3に示す。
浴中のリン酸イオン濃度及び硫酸イオン濃度が500ppm以下で、Mg最大発光強度が2V以下、かつ水酸化皮膜量が10〜150mg/m2の実施例はいずれも良好な耐黒変性を示した。
FC4498-SK3 manufactured by Nippon Parkerizing Co., Ltd. was used as the alkaline degreasing agent a, and FC4498-SK4 manufactured by Nippon Parkerizing Co., Ltd. was used as the alkaline degreasing agent b. Both are environmentally friendly degreasing agents that do not contain nonylphenyl surfactants and phosphates.
Surface Mg amount measurement, hydroxide film amount measurement, and blackening test were performed in the same manner as in Example 1 and Comparative Example 1.
The results are shown in Table 3.
Examples in which the phosphate ion concentration and the sulfate ion concentration in the bath were 500 ppm or less, the Mg maximum emission intensity was 2 V or less, and the amount of the hydroxide film was 10 to 150 mg / m 2 showed good blackening resistance. .
本発明方法により製造された飲料容器用アルミニウム合金材は、ソフトドリンク類、コーヒー、ビールなどの飲料用アルミニウム製容器や食品用容器等、主として飲料容器等に用いられるアルミニウム合金(以下「アルミ」という。)材として使用した場合に、アルミ材の表面に良質な水酸化被膜が形成されており、このためアルミ容器として必要とされるレトルト処理などの沸騰水等で殺菌処理、ホット販売などの高温において優れた黒変防止性能を有するアルミ容器用アルミ材として利用可能である。 The aluminum alloy material for beverage containers produced by the method of the present invention is an aluminum alloy (hereinafter referred to as “aluminum”) mainly used for beverage containers such as soft drinks, containers for beverages such as coffee and beer, and food containers. .) When used as a material, a high-quality hydroxide film is formed on the surface of the aluminum material. For this reason, boiled water such as retort treatment required for aluminum containers is used for high temperature such as sterilization treatment and hot sale. Can be used as an aluminum material for an aluminum container having excellent blackening prevention performance.
Claims (6)
An aluminum alloy beverage container excellent in boiling water blackening resistance, wherein the beverage container is manufactured from the aluminum alloy material for beverage containers manufactured by the manufacturing method according to claim 5.
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JP2000226674A (en) * | 1999-02-08 | 2000-08-15 | Sumitomo Light Metal Ind Ltd | Surface-treated aluminum material, coated-aluminum material and their production |
JP2000282264A (en) * | 1999-03-30 | 2000-10-10 | Nisshin Steel Co Ltd | Mg/Sr-CONTAINING HOT-DIP ALUMINIZED STEEL SHEET FREE FROM LIGHT BROWN INITIAL RUSTY STAIN, AND ITS MANUFACTURE |
JP2004035988A (en) * | 2002-07-08 | 2004-02-05 | Furukawa Sky Kk | Non-chromium type aluminum substrate treatment material having excellent coating film adhesion |
JP3850253B2 (en) * | 2001-10-15 | 2006-11-29 | 古河スカイ株式会社 | Aluminum substrate treatment material with excellent coating adhesion and corrosion resistance |
JP4429899B2 (en) * | 2002-05-31 | 2010-03-10 | 麒麟麦酒株式会社 | Surface-modified aluminum can and method for producing the same |
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JP2000282264A (en) * | 1999-03-30 | 2000-10-10 | Nisshin Steel Co Ltd | Mg/Sr-CONTAINING HOT-DIP ALUMINIZED STEEL SHEET FREE FROM LIGHT BROWN INITIAL RUSTY STAIN, AND ITS MANUFACTURE |
JP3850253B2 (en) * | 2001-10-15 | 2006-11-29 | 古河スカイ株式会社 | Aluminum substrate treatment material with excellent coating adhesion and corrosion resistance |
JP4429899B2 (en) * | 2002-05-31 | 2010-03-10 | 麒麟麦酒株式会社 | Surface-modified aluminum can and method for producing the same |
JP2004035988A (en) * | 2002-07-08 | 2004-02-05 | Furukawa Sky Kk | Non-chromium type aluminum substrate treatment material having excellent coating film adhesion |
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