JP4463632B2 - Hot rolling oil for aluminum and aluminum alloy sheets - Google Patents
Hot rolling oil for aluminum and aluminum alloy sheets Download PDFInfo
- Publication number
- JP4463632B2 JP4463632B2 JP2004198737A JP2004198737A JP4463632B2 JP 4463632 B2 JP4463632 B2 JP 4463632B2 JP 2004198737 A JP2004198737 A JP 2004198737A JP 2004198737 A JP2004198737 A JP 2004198737A JP 4463632 B2 JP4463632 B2 JP 4463632B2
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- JP
- Japan
- Prior art keywords
- oil
- component
- aluminum
- weight
- hot rolling
- 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.)
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- 239000010731 rolling oil Substances 0.000 title claims description 47
- 238000005098 hot rolling Methods 0.000 title claims description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 27
- 229910052782 aluminium Inorganic materials 0.000 title claims description 26
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 19
- 238000005096 rolling process Methods 0.000 claims description 51
- 239000010687 lubricating oil Substances 0.000 claims description 30
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 29
- 239000000194 fatty acid Substances 0.000 claims description 29
- 229930195729 fatty acid Natural products 0.000 claims description 29
- 150000004665 fatty acids Chemical class 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000002480 mineral oil Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 235000010446 mineral oil Nutrition 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
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- 235000019198 oils Nutrition 0.000 description 21
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- 229910052742 iron Inorganic materials 0.000 description 9
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- 235000011187 glycerol Nutrition 0.000 description 4
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
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- 238000005498 polishing Methods 0.000 description 3
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- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 2
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
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- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
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- HKZQDFSXDXTEEC-UHFFFAOYSA-N dodecyl 16-methylheptadecanoate Chemical compound CCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC(C)C HKZQDFSXDXTEEC-UHFFFAOYSA-N 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
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- 230000000670 limiting effect Effects 0.000 description 1
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- IQBHTRVNLWHNBL-UHFFFAOYSA-N n-(diethylaminomethyl)-2-methylprop-2-enamide Chemical compound CCN(CC)CNC(=O)C(C)=C IQBHTRVNLWHNBL-UHFFFAOYSA-N 0.000 description 1
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- RCLLINSDAJVOHP-UHFFFAOYSA-N n-ethyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCN(N(C)C)C(=O)C=C RCLLINSDAJVOHP-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
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- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ALSTYHKOOCGGFT-MDZDMXLPSA-N oleyl alcohol Chemical compound CCCCCCCC\C=C\CCCCCCCCO ALSTYHKOOCGGFT-MDZDMXLPSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
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- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- SVETUDAIEHYIKZ-IUPFWZBJSA-N tris[(z)-octadec-9-enyl] phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(=O)(OCCCCCCCC\C=C/CCCCCCCC)OCCCCCCCC\C=C/CCCCCCCC SVETUDAIEHYIKZ-IUPFWZBJSA-N 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
Landscapes
- Lubricants (AREA)
Description
本発明は圧延潤滑性、板表面品質性及び耐鉄腐食性に優れたアルミニウム及びアルミニウム合金板用熱間圧延油用潤滑油、それを含有する熱間圧延油及び該圧延油を用いた熱間圧延方法に関する。 The present invention relates to a lubricating oil for hot rolling oil for aluminum and aluminum alloy sheets excellent in rolling lubricity, sheet surface quality and iron corrosion resistance, hot rolling oil containing the same, and hot using the rolling oil. It relates to a rolling method.
アルミニウム及びアルミニウム合金（以下、アルミニウムと称する）板の熱間圧延では、圧延板表面から圧延ロール表面へアルミニウムが移着して、ロールコーティングが形成される。従って、圧延板はロールコーティングと接触して圧延されることになるので、圧延板の表面品質はロールコーティングの性状によって左右される。熱間圧延時に発生した板の表面欠陥は冷間圧延後の板表面品質にも影響するので、熱間圧延におけるロールコーティング性状は非常に重要といえる。ロールコーティング性状は圧延諸条件（板材質、板温度、板表面粗さ、ロール温度、ロール表面粗さ、圧下率、圧延速度、ブラシロール操業条件など）と圧延油により変化する。従って、圧延油の選択は、ロールコーティングを制御する上で不可欠なものである。熱間圧延では充分なロール冷却性が必要となるので圧延油はエマルションの形で使用されている。アルミニウム板の熱間圧延油に要求される性能として、圧延潤滑性、ロールコーティング性、板表面品質性、乳化安定性、耐鉄腐食性等が挙げられる。 In the hot rolling of aluminum and aluminum alloy (hereinafter referred to as aluminum) plates, aluminum is transferred from the surface of the rolled plate to the surface of the rolling roll to form a roll coating. Therefore, since the rolled plate is rolled in contact with the roll coating, the surface quality of the rolled plate depends on the properties of the roll coating. Since the surface defects of the plate generated during hot rolling also affect the plate surface quality after cold rolling, it can be said that roll coating properties in hot rolling are very important. Roll coating properties vary depending on various rolling conditions (plate material, plate temperature, plate surface roughness, roll temperature, roll surface roughness, rolling reduction, rolling speed, brush roll operating conditions, etc.) and rolling oil. Therefore, the selection of rolling oil is essential for controlling roll coating. Hot rolling requires sufficient roll cooling, so that rolling oil is used in the form of an emulsion. The performance required for the hot rolling oil of the aluminum plate includes rolling lubricity, roll coating property, plate surface quality, emulsification stability, iron corrosion resistance and the like.
従来、一般にアルミニウム板の熱間圧延油としては、鉱物油を基油として、脂肪酸、天然油脂、脂肪酸エステル等の油性向上剤、極圧剤、防錆剤、酸化防止剤等を配合し、これを主に陰イオン性界面活性剤で乳化した、通常２〜１０％濃度エマルションとして使用されている。しかし、従来の乳化剤を用いたアルミニウム板用熱間圧延油は、圧延潤滑性と乳化安定性とは相反する傾向を示し、両性能を共に満足させることは出来なかった。すなわち圧延潤滑性を増すと乳化安定性は低下し、その結果圧延潤滑性の経時安定性も低下するため、アルミニウム板表面の品質安定性が問題となった。一方、乳化安定性を増すと充分な圧延潤滑性は得られず、その結果、アルミニウム板表面に種々の欠陥が発生した。 Conventionally, as a hot rolling oil for aluminum plates, generally, mineral oil is used as a base oil, and oiliness improvers such as fatty acids, natural fats and oils, fatty acid esters, extreme pressure agents, rust inhibitors, antioxidants, etc. are blended. Is mainly emulsified with an anionic surfactant, and is usually used as a 2 to 10% concentration emulsion. However, the conventional hot rolling oil for aluminum plates using an emulsifier has a tendency that the rolling lubricity and the emulsification stability are contradictory, and both performances cannot be satisfied. That is, when the rolling lubricity is increased, the emulsification stability is lowered, and as a result, the stability of rolling lubrication with time is also lowered, so that the quality stability of the aluminum plate surface becomes a problem. On the other hand, when the emulsification stability was increased, sufficient rolling lubricity was not obtained, and as a result, various defects occurred on the aluminum plate surface.
このように相反する特性である圧延潤滑性、乳化安定性及び板表面品質性を同時に満足させるために、特許文献１では、特定の潤滑油成分と特定の水溶性陽イオン性高分子化合物の組み合わせを開示している。しかし、近年、大量生産化とアルミニウム圧延品の高品質指向から、圧延潤滑性を向上させる油性向上剤である脂肪酸を増量することで対応しているが、脂肪酸は１５％以上に増量するとかなり強い腐食性を有するとともに、圧延の進行に伴い生成する金属石鹸は高粘度物質のため圧延機周辺を汚染させるといった課題もある。 In order to satisfy the rolling lubricity, the emulsion stability and the plate surface quality, which are contradictory properties as described above, Patent Document 1 discloses a combination of a specific lubricating oil component and a specific water-soluble cationic polymer compound. Is disclosed. However, in recent years, it has been dealt with by increasing the amount of fatty acid, which is an oil improver that improves rolling lubricity, from the viewpoint of mass production and high-quality aluminum rolled products. However, increasing the amount of fatty acid to 15% or more is quite strong. In addition to being corrosive, the metal soap produced with the progress of rolling has a problem of contaminating the periphery of the rolling mill because of its high viscosity material.
このため、耐鉄腐食性を悪化させず、圧延潤滑性を向上させる工夫として、特許文献２では、天然油脂、合成エステルを比較的多量に使用することによって、脂肪酸の含有量の制限と圧延潤滑性の向上を達成している。しかし、圧延潤滑性、板表面品質性を共に、満足させるものではなかった。
本発明は、圧延潤滑性及び耐鉄腐食性に優れ、且つ優れた板表面品質性を有する圧延板を得ることができるアルミニウム及びアルミニウム合金板用熱間圧延油用潤滑油、該潤滑油を含有する圧延油、及びその熱間圧延方法を提供することを課題とする。 The present invention is a lubricant for hot rolling oil for aluminum and aluminum alloy plates, which can provide a rolled plate having excellent rolling lubricity and iron corrosion resistance and having excellent sheet surface quality, and contains the lubricating oil An object of the present invention is to provide a rolling oil and a hot rolling method thereof.
本発明者等は、脂肪酸と特定量の高級アルコールと天然油脂及び／又は合成エステルとを含有させることで、脂肪酸の含有量が１４重量％以下でも優れた圧延潤滑性、板表面品質性が得られることを見い出し、本発明を完成した。 The inventors of the present invention can obtain excellent rolling lubricity and plate surface quality even when the fatty acid content is 14% by weight or less by containing a fatty acid, a specific amount of higher alcohol, and natural fats and oils and / or synthetic esters. The present invention has been completed.
すなわち本発明は、下記（ａ）、（ｂ）、（ｃ）及び（ｄ）成分を含有し、（ｂ）成分の含有量が１〜１４重量％、（ｃ）成分の含有量が２〜５０重量％、（ｄ）成分の含有量が２〜３０重量％である、アルミニウム及びアルミニウム合金板用熱間圧延油用潤滑油、この潤滑油、水及び乳化剤を含有する、アルミニウム及びアルミニウム合金板用熱間圧延油、この熱間圧延油を、アルミニウム及びアルミニウム合金板の熱間圧延に用いる熱間圧延方法を提供する。
（ａ）動粘度８０ｍｍ2／ｓ（４０℃）以下の鉱物油
（ｂ）炭素数１０〜２２の脂肪酸
（ｃ）天然油脂及び１価高級脂肪酸又は多塩基酸とアルコールから得られる合成エステルから選ばれる少なくとも１種
（ｄ）炭素数８〜２６の高級アルコール
That is, the present invention contains the following components (a), (b), (c) and (d), the content of the component (b) is 1 to 14% by weight, and the content of the component (c) is 2 to 2%. Aluminum and aluminum alloy plate containing 50% by weight, (d) component content of 2 to 30% by weight, and a lubricating oil for hot rolling oil for aluminum and aluminum alloy plate, this lubricating oil, water and emulsifier The present invention provides a hot rolling method for use in hot rolling of aluminum and aluminum alloy sheets.
(A) Mineral oil having a kinematic viscosity of 80 mm 2 / s (40 ° C.) or less (b) Fatty acids having 10 to 22 carbon atoms (c) Natural fats and oils and monovalent higher fatty acids or synthetic esters obtained from polybasic acids and alcohols At least one (d) higher alcohol having 8 to 26 carbon atoms
本発明の熱間圧延油を用いることで、圧延潤滑性、ロールコーティング性、板表面品質性の優れたアルミニウム圧延板を得ることができる。また、脂肪酸の含有量が少ないため、金属石鹸の発生が抑制され、圧延機周辺やクーラントタンク等の汚れが改善されると同時に、防食剤の添加なしでも圧延機やその周辺設備の鉄鋼材料を腐食させる問題を解決することができる。 By using the hot rolling oil of the present invention, an aluminum rolled sheet having excellent rolling lubricity, roll coating property, and sheet surface quality can be obtained. In addition, since the fatty acid content is low, the generation of metal soap is suppressed, dirt around the rolling mill and coolant tank is improved, and at the same time, steel materials for the rolling mill and its peripheral equipment can be used without adding anticorrosive agents. The problem of corroding can be solved.
［潤滑油］
本発明の熱間圧延油用潤滑油は、上記（ａ）、（ｂ）、（ｃ）及び（ｄ）成分を含有し、特に（ｄ）成分を含有することに特徴がある。
[Lubricant]
The lubricating oil for hot rolling oil of the present invention contains the components (a), (b), (c) and (d), and is particularly characterized by containing the component (d).
本発明の潤滑油の（ａ）成分である鉱物油としては、例えばスピンドル油、マシン油、タービン油、シリンダー油、ニュートラル油等が挙げられ、パラフィン系鉱物油、ナフテン系鉱物油のいずれでもよいが、４０℃の動粘度が８０ｍｍ2／ｓ以下であることが必要であり、この粘度範囲であれば板表面品質性は優れており、熱間圧延した板への残油も少なく良好である。また、パラフィン系鉱物油であれば耐熱性、潤滑性に優れるのでより好ましい。この（ａ）成分は基油であり、本発明の潤滑油中の（ａ）成分の含有量は特に制限されないが、１０〜９５重量％が好ましく、３０〜６５重量％が更に好ましい。 Examples of the mineral oil as the component (a) of the lubricating oil of the present invention include spindle oil, machine oil, turbine oil, cylinder oil, neutral oil and the like, and any of paraffinic mineral oil and naphthenic mineral oil may be used. However, the kinematic viscosity at 40 ° C. is required to be 80 mm 2 / s or less, and within this viscosity range, the plate surface quality is excellent, and the residual oil on the hot-rolled plate is small and good. . Paraffin mineral oils are more preferred because they are excellent in heat resistance and lubricity. The component (a) is a base oil, and the content of the component (a) in the lubricating oil of the present invention is not particularly limited, but is preferably 10 to 95% by weight, more preferably 30 to 65% by weight.
（ｂ）成分である炭素数１０〜２２の脂肪酸としては、カプリン酸、ラウリン酸、パルミチン酸、ステアリン酸、イソステアリン酸、オレイン酸、ベヘニン酸、エルカ酸、ヤシ油脂肪酸、パーム油脂肪酸、牛脂脂肪酸等を１種以上用いることができ、取扱上、常温（２５℃）液体の脂肪酸（カプリン酸、イソステアリン酸、オレイン酸、エルカ酸、ヤシ油脂肪酸）が好ましい。本発明の潤滑油中の（ｂ）成分の含有量は１〜１４重量％であり、３〜１０重量％が好ましい。（ｂ）成分は圧延潤滑性を向上させる目的で添加する。（ｂ）成分はロールコーティング性や板表面品質性への悪影響が少なく、境界潤滑特性の非常に優れた油性向上剤ではあるが、１４重量％を超えると金属腐食性が高くなる。また、圧延の進行に伴い生成する金属石鹸は圧延機周辺を汚染させたり、製品汚れの原因になる。上記配合量であれば潤滑性、耐金属腐食性及び耐汚れ性に優れるので好ましい。 As the fatty acid having 10 to 22 carbon atoms as component (b), capric acid, lauric acid, palmitic acid, stearic acid, isostearic acid, oleic acid, behenic acid, erucic acid, coconut oil fatty acid, palm oil fatty acid, beef tallow fatty acid 1 or more can be used, and a normal temperature (25 ° C.) liquid fatty acid (capric acid, isostearic acid, oleic acid, erucic acid, coconut oil fatty acid) is preferable for handling. Content of (b) component in the lubricating oil of this invention is 1 to 14 weight%, and 3 to 10 weight% is preferable. Component (b) is added for the purpose of improving rolling lubricity. Component (b) has little adverse effect on roll coating properties and plate surface quality, and is an oiliness improver with very excellent boundary lubrication properties. However, when it exceeds 14% by weight, the metal corrosivity increases. Further, the metal soap generated as the rolling progresses contaminates the periphery of the rolling mill and causes product contamination. If it is the said compounding quantity, since it is excellent in lubricity, metal corrosion resistance, and dirt resistance, it is preferable.
（ｃ）成分である天然油脂及び／又は合成エステルは、（ｂ）成分に次ぐ優れた油性向上剤であり圧延潤滑性を向上させる目的で添加する。 Component (c), natural fats and oils and / or synthetic esters, is an excellent oiliness improver after component (b) and is added for the purpose of improving rolling lubricity.
天然油脂としては、例えば鯨油、牛脂、豚脂、ナタネ油、ヒマシ油、パーム油、ヤシ油等の動植物油脂が挙げられる。潤滑性、板表面品質性及び融点の観点からは豚脂、パーム油がより好ましい。圧延油の融点の点から、その含有量は、２〜３０重量％が好ましい。 Examples of natural fats and oils include animal and vegetable fats and oils such as whale oil, beef tallow, lard, rapeseed oil, castor oil, palm oil and coconut oil. From the viewpoints of lubricity, plate surface quality and melting point, lard and palm oil are more preferred. From the viewpoint of the melting point of the rolling oil, the content is preferably 2 to 30% by weight.
合成エステルとしては、好ましくは炭素数１０〜２２の１価高級脂肪酸又は多塩基酸とアルコールのエステルが挙げられる。アルコールとしては、好ましくは炭素数１〜２２の脂肪族１価アルコール、あるいはジエチレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール、グリセリン等の多価アルコールが挙げられる。脂肪酸やアルコールとしては飽和のもの不飽和のものいずれも使用できるが、板表面品質性の観点からは飽和のものがより好ましい。合成エステルとしてはフルエステル、部分エステルのいずれでもよい。より好ましい合成エステルの具体例としては、カプリン酸メチル、ステアリン酸ブチル、イソステアリン酸ラウリル等の飽和脂肪酸モノエステル；アジピン酸ジラウリル、フタル酸ジラウリル、トリメリット酸トリデシル等の多塩基酸と飽和脂肪族１価アルコールのエステル；ネオペンチルポリオール飽和脂肪酸エステル（ネオペンチルグリコールジラウレート、トリメチロールプロパン椰子油脂肪酸トリエステル、トリメチロールプロパンイソステアリン酸トリエステル、トリメチロールプロパンジラウレート、ペンタエリスリトールモノラウレート、ペンタエリスリトールテトララウレート、ペンタエリスリトールイソステアリン酸テトラエステル等）、グリセリン飽和脂肪酸エステル（グリセリン椰子油脂肪酸ジエステル、グリセリントリラウレート等）、ジエチレングリコール飽和脂肪酸エステル等の１価高級脂肪酸と多価アルコールのエステルが挙げられる。 The synthetic ester is preferably an ester of a monovalent higher fatty acid having 10 to 22 carbon atoms or a polybasic acid and an alcohol. The alcohol is preferably an aliphatic monohydric alcohol having 1 to 22 carbon atoms, or a polyhydric alcohol such as diethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, or glycerin. As the fatty acid and alcohol, any saturated or unsaturated fatty acid can be used, but a saturated one is more preferable from the viewpoint of plate surface quality. The synthetic ester may be a full ester or a partial ester. Specific examples of more preferred synthetic esters include saturated fatty acid monoesters such as methyl caprate, butyl stearate, lauryl isostearate; polybasic acids such as dilauryl adipate, dilauryl phthalate, tridecyl trimellitic acid and saturated aliphatic 1 Esters of monohydric alcohols; Neopentyl polyol saturated fatty acid esters (neopentyl glycol dilaurate, trimethylolpropane palm oil fatty acid triester, trimethylolpropane isostearic acid triester, trimethylolpropane dilaurate, pentaerythritol monolaurate, pentaerythritol tetralaurate , Pentaerythritol isostearic acid tetraester), glycerin saturated fatty acid ester (glycerin coconut oil fatty acid diester, glycerin) Riraureto etc.), and a monovalent higher fatty acid esters of polyhydric alcohols such as diethylene glycol saturated fatty acid esters.
潤滑性、板表面品質性及び融点の観点からは、多価アルコールと炭素数１０〜２２の１価飽和高級脂肪酸とのエステルが特に好ましい。合成エステルの含有量は、圧延油の価格の点から、２〜３０重量％が好ましい。 From the viewpoint of lubricity, plate surface quality, and melting point, an ester of a polyhydric alcohol and a monovalent saturated higher fatty acid having 10 to 22 carbon atoms is particularly preferable. The content of the synthetic ester is preferably 2 to 30% by weight from the viewpoint of the price of the rolling oil.
これら（ｃ）成分は、単独でもよいが、それぞれ１種以上を混合して使用することもできる。天然油脂や合成エステルは、一般にロールコーティング性や板表面品質性への悪影響があるため過度の多量配合は望ましくないが、高級アルコールと共存させることで、その含有量を増加させることができる。本発明の潤滑油中の（ｃ）成分の含有量は、圧延潤滑性、融点、板表面品質性及び価格のバランスの点から、２〜５０重量％であり、１０〜４０重量％が好ましい。 These components (c) may be used singly or in combination of one or more. Natural fats and oils and synthetic esters generally have an adverse effect on roll coating properties and plate surface quality, so that excessive amounts are not desirable, but their content can be increased by coexisting with higher alcohols. The content of the component (c) in the lubricating oil of the present invention is 2 to 50% by weight, preferably 10 to 40% by weight, from the viewpoint of rolling lubricity, melting point, plate surface quality and price balance.
（ｄ）成分である炭素数８〜２６の高級アルコールは、圧延潤滑性及び板表面品質性を向上させる目的で添加する。 The higher alcohol having 8 to 26 carbon atoms as component (d) is added for the purpose of improving rolling lubricity and plate surface quality.
（ｄ）成分は冷間圧延油には油性向上剤として一般的に添加されているが、熱間圧延油においてはこれまで添加されたことはない。これは、板温度から考えて油性向上効果は示さず、また熱安定性にも問題があると思われてきた。 The component (d) is generally added as an oiliness improver to cold rolled oil, but has never been added to hot rolled oil. It has been considered that this does not show an effect of improving oiliness in view of the plate temperature and has a problem in thermal stability.
しかし、種々検討した結果、（ｄ）成分を熱間圧延用潤滑油のような冷間圧延油より、高温・高潤滑の油において用いた際に、（ｂ）成分と同等の境界潤滑性を示し、熱的にも分解・揮発がなく比較的安定であり、板表面品質性を向上させることを見い出した。また、（ｄ）成分を添加すれば（ｃ）成分を多量配合しても板表面品質性の低下が少なくなる特徴がある。 However, as a result of various studies, when the component (d) is used in a high temperature and high lubrication oil rather than a cold rolling oil such as a hot rolling lubricant, the boundary lubricity equivalent to the component (b) is obtained. It was found that there is no thermal decomposition or volatilization and it is relatively stable and improves the surface quality of the plate. Further, if the component (d) is added, the deterioration of the plate surface quality is reduced even if the component (c) is added in a large amount.
（ｄ）成分は多量添加すると潤滑油の粘度を低下させるため、本発明の潤滑油中の（ｄ）成分の含有量は２〜３０重量％であり、潤滑性の点から１０〜３０重量％が好ましい。 When component (d) is added in a large amount, the viscosity of the lubricating oil is lowered. Therefore, the content of component (d) in the lubricating oil of the present invention is 2 to 30% by weight, and 10 to 30% by weight from the viewpoint of lubricity. Is preferred.
（ｄ）成分は直鎖でも分岐鎖でもよく、また飽和のもの不飽和のものいずれも使用できる。また、１価アルコールでも２価以上の多価アルコールでもよい。潤滑性の観点からは直鎖部分の炭素数が８〜１８のものがより好ましい。より好ましい（ｄ）成分の具体例としては、デシルアルコ−ル、ラウリルアルコール、ミリスチルアルコ−ル、セチルアルコール、ステアリルアルコール、オレイルアルコール、エライジルアルコール、リノレイルアルコール、椰子油還元アルコール、パーム油還元アルコール、牛脂還元アルコール、炭素数１１〜１８のオキソアルコール、炭素数１２〜１８のチーグラーアルコール、炭素数１２〜２６のゲルベアルコール、オクタデカン１，２−ジオール、ラウリルアルコールエチレンオキサイド付加物（２モル以下）等が挙げられる。潤滑性、板表面品質性の観点からは、直鎖若しくは分岐鎖のアルキル基を有する１価アルコールが好ましく、１価飽和アルコールが特に好ましい。 The component (d) may be linear or branched, and either saturated or unsaturated can be used. Moreover, monohydric alcohol or polyhydric alcohol more than bivalence may be sufficient. From the viewpoint of lubricity, those having 8 to 18 carbon atoms in the straight chain portion are more preferable. Specific examples of the more preferable component (d) include decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, palm oil reduced alcohol, palm oil reduced alcohol. Tallow reduced alcohol, oxo alcohol having 11 to 18 carbon atoms, Ziegler alcohol having 12 to 18 carbon atoms, Gerve alcohol having 12 to 26 carbon atoms, octadecane 1,2-diol, lauryl alcohol ethylene oxide adduct (2 mol or less) Etc. From the viewpoint of lubricity and plate surface quality, monohydric alcohols having a linear or branched alkyl group are preferred, and monovalent saturated alcohols are particularly preferred.
本発明の潤滑油中の（ｃ）成分と（ｄ）成分の重量比は、圧延潤滑性及び板表面品質性の観点から、（ｄ）成分／（ｃ）成分＝１／１〜１／１０が好ましく、１／１〜１／５が更に好ましい。 The weight ratio of the component (c) and the component (d) in the lubricating oil of the present invention is as follows: (d) component / (c) component = 1/1 to 1/10 from the viewpoint of rolling lubricity and plate surface quality. Is preferable, and 1/1 to 1/5 is more preferable.
また、本発明の潤滑油は、板表面品質性を向上させる目的でリン系極圧剤（以下（ｅ）成分という）を含有することが好ましい。リン系極圧剤の具体例としては、トリクレジルホスフェート、ジブチルホスフェート、モノオクチルホスフェート、トリオレイルホスフェート、トリブチルホスファイト、ジイソオクチルホスファイト、トリイソオクチルホスファイト、トリオレイルホスファイト等が挙げられる。本発明の潤滑油中の（ｅ）成分の含有量は０．５〜１０重量％が好ましく、３〜１０重量％が更に好ましい。（ｅ）成分は、１種でもよいが、２種以上を混合して使用することもできる。 The lubricating oil of the present invention preferably contains a phosphorus-based extreme pressure agent (hereinafter referred to as “component (e)”) for the purpose of improving plate surface quality. Specific examples of phosphorus extreme pressure agents include tricresyl phosphate, dibutyl phosphate, monooctyl phosphate, trioleyl phosphate, tributyl phosphite, diisooctyl phosphate, triisooctyl phosphite, trioleyl phosphite, etc. It is done. The content of the component (e) in the lubricating oil of the present invention is preferably 0.5 to 10% by weight, more preferably 3 to 10% by weight. Although (e) component may be 1 type, 2 or more types can also be mixed and used for it.
［アルミニウム及びアルミニウム合金板用熱間圧延油］
本発明のアルミニウム及びアルミニウム合金板用熱間圧延油は、前記本発明の潤滑油、乳化剤及び水を含有する。
[Hot rolling oil for aluminum and aluminum alloy sheets]
The hot rolling oil for aluminum and aluminum alloy sheet of the present invention contains the lubricating oil, emulsifier and water of the present invention.
本発明の熱間圧延油中の本発明の潤滑油の含有量は、圧延潤滑性や板表面品質性の観点から１〜１０重量％が好ましく、乳化剤の含有量は０．１〜５重量％が好ましく、水の含有量は８５〜９８．９重量％が好ましい。 The content of the lubricating oil of the present invention in the hot rolled oil of the present invention is preferably 1 to 10% by weight from the viewpoint of rolling lubricity and plate surface quality, and the content of the emulsifier is 0.1 to 5% by weight. The water content is preferably 85 to 98.9% by weight.
また、本発明の熱間圧延油は、Ｏ（潤滑油）／Ｗ（水）型であることが、圧延潤滑性や冷却性や乳化安定性の点から好ましい。 In addition, the hot rolling oil of the present invention is preferably O (lubricating oil) / W (water) type from the viewpoint of rolling lubricity, cooling properties, and emulsion stability.
乳化剤としては、例えばオレイン酸トリエタノールアミン塩、石油スルホネートナトリウム塩等の陰イオン性界面活性剤、ポリオキシエチレンラウリルエーテル等の非イオン性界面活性剤、ベンザルコニウム型等の４級アンモニウム塩等のカチオン性界面活性剤、一般の高分子型分散剤等が挙げられる。乳化剤は、潤滑油１００重量部に対して０．１〜５重量部で用いることが好ましい。 Examples of the emulsifier include anionic surfactants such as oleic acid triethanolamine salt and petroleum sulfonate sodium salt, nonionic surfactants such as polyoxyethylene lauryl ether, and quaternary ammonium salts such as benzalkonium type. Cationic surfactants, general polymer-type dispersants, and the like. The emulsifier is preferably used in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of the lubricating oil.
これらの乳化剤の中でも、下記一般式（１）で表される単量体又はその塩若しくはその４級化物の重合体又は共重合体であって、その重量平均分子量が１０，０００〜１，０００，０００である高分子化合物（以下（ｆ）成分という）の少なくとも１種を用いることが、大粒子径且つ安定な乳化分散性のエマルションを得ることができるため好ましい。 Among these emulsifiers, a monomer or a salt thereof or a quaternized polymer or copolymer represented by the following general formula (1) having a weight average molecular weight of 10,000 to 1,000 It is preferable to use at least one polymer compound (hereinafter referred to as “component (f)”) having a large particle diameter and a stable emulsion-dispersible emulsion.
（式中、Ｒ1は水素原子又はメチル基、Ｒ2及びＲ3は、同一又は異なって、炭素数１〜３のアルキル基、ｍは１〜３の整数を示す。）
（ｆ）成分において、一般式（１）で表される単量体の具体例としては、ジメチルアミノエチルアクリルアミド、ジメチルアミノプロピルアクリルアミド、ジエチルアミノメチルアクリルアミド、ジメチルアミノエチルメタクリルアミド、ジメチルアミノプロピルメタクリルアミド、ジエチルアミノメチルメタクリルアミド等が挙げられる。
(In the formula, R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are the same or different, an alkyl group having 1 to 3 carbon atoms, and m is an integer of 1 to 3).
In the component (f), specific examples of the monomer represented by the general formula (1) include dimethylaminoethylacrylamide, dimethylaminopropylacrylamide, diethylaminomethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylmethacrylamide, Examples include diethylaminomethyl methacrylamide.
一般式（１）で表される単量体の塩を得るための好ましい酸としては、例えば酢酸、酪酸、カプロン酸、カプリル酸、グリコール酸、コハク酸、酒石酸、燐酸、酸性アルキルリン酸エステル（ブチルアシッドホスフェート、オクチルアシッドホスフェート等）、ホウ酸等が挙げられる。塩は、単量体を、又は重合後に重合体を中和することにより形成される。 Preferred acids for obtaining a salt of the monomer represented by the general formula (1) include, for example, acetic acid, butyric acid, caproic acid, caprylic acid, glycolic acid, succinic acid, tartaric acid, phosphoric acid, acidic alkyl phosphate ester ( Butyl acid phosphate, octyl acid phosphate, etc.), boric acid and the like. The salt is formed by neutralizing the monomer or the polymer after polymerization.
一般式（１）で表される単量体の４級化物を得るための好ましい４級化剤としては、塩化メチル、塩化エチル、臭化メチル、ヨウ化メチル等のハロゲン化アルキル、硫酸ジメチル、硫酸ジエチル、硫酸ジ−ｎ−プロピル等の一般的なアルキル化剤が挙げられる。 Preferred quaternizing agents for obtaining a quaternized product of the monomer represented by the general formula (1) include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, Common alkylating agents such as diethyl sulfate and di-n-propyl sulfate can be mentioned.
（ｆ）成分は、一般式（１）で表される単量体と、（メタ）アクリル酸若しくはその塩、（メタ）アクリル酸アルキルエステル、（メタ）アクリルアミド等の共重合可能な単量体との共重合体でもよい。共重合可能な単量体の具体例としては、アルキル基が、炭素数１〜２２の直鎖又は分岐鎖のアルキル基である、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル等の（メタ）アクリル酸アルキルエステル；（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド等の（メタ）アクリルアミド等が挙げられる。また、（メタ）アクリル酸塩の具体例としては、アクリル酸ナトリウム、メタクリル酸カリウム等のアルカリ金属塩が挙げられる。尚、（メタ）アクリルはアクリル又はメタクリルを意味する。 Component (f) is a copolymerizable monomer such as a monomer represented by the general formula (1), (meth) acrylic acid or a salt thereof, (meth) acrylic acid alkyl ester, (meth) acrylamide, and the like. And a copolymer thereof. As specific examples of the copolymerizable monomer, the alkyl group is a linear or branched alkyl group having 1 to 22 carbon atoms, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include (meth) acrylic acid alkyl esters such as (meth) lauryl acrylate and stearyl (meth) acrylate; (meth) acrylamides such as (meth) acrylamide and N-methyl (meth) acrylamide. Specific examples of the (meth) acrylate include alkali metal salts such as sodium acrylate and potassium methacrylate. In addition, (meth) acryl means acryl or methacryl.
一般式（１）で表される単量体又はその塩若しくはその４級化物由来の構成単位は、（ｆ）成分中、５０〜１００重量％であることが好ましい。 The structural unit derived from the monomer represented by the general formula (1) or a salt thereof or a quaternized product thereof is preferably 50 to 100% by weight in the component (f).
（ｆ）成分の重量平均分子量は、１０，０００〜１，０００，０００の範囲であり、重量平均分子量がこの範囲であれば乳化安定性に優れ、高分子化合物自体の安定性も良好で取扱いも容易である。より好ましい重量平均分子量は３０，０００〜３００，０００である。なお、（ｆ）成分の重量平均分子量は、（ｆ）成分を加水分解（試料１ｇにＮ／２ ＫＯＨ溶液２０ｍｌを添加し、約９５℃で２時間加熱する）後、下記条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）法で分子量を分析し、その結果から元の分子量を換算したものである。 The weight average molecular weight of the component (f) is in the range of 10,000 to 1,000,000. If the weight average molecular weight is in this range, the emulsion stability is excellent, and the stability of the polymer compound itself is also good and handled. Is also easy. A more preferred weight average molecular weight is 30,000 to 300,000. The weight average molecular weight of component (f) was determined by hydrolyzing component (f) (adding 20 ml of N / 2 KOH solution to 1 g of sample and heating at about 95 ° C. for 2 hours), and then gel permeation under the following conditions: The molecular weight is analyzed by a chromatography (GPC) method, and the original molecular weight is converted from the result.
＜条件＞
・カラム：Ｇ２０００ＳＷ（東ソー（株）製）×２本
・カラム温度：４０℃
・溶離液：０．１Ｎ塩化ナトリウム水溶液／アセトニトリル＝７０／３０
・検出器：ＲＩ（屈折率計）
・注入量：１重量％溶離液溶液，２０μｌ
・液流速：０．４ｍｌ／ｍｉｎ
・分子量標準：ポリスチレンスルホン酸Ｎａ。
<Conditions>
-Column: G2000SW (manufactured by Tosoh Corporation) x 2-Column temperature: 40 ° C
Eluent: 0.1N sodium chloride aqueous solution / acetonitrile = 70/30
・ Detector: RI (refractometer)
Injection volume: 1% by weight eluent solution, 20 μl
・ Liquid flow rate: 0.4 ml / min
-Molecular weight standard: Na polystyrene sulfonate.
（ｆ）成分は１種又は２種以上を混合して使用することができる。圧延油粒子の表面電位は負であるが、（ｆ）成分を添加するに従い圧延油粒子の表面電位はほぼ零となり、圧延油粒子は凝集して粗大粒子径となる。（ｆ）成分をさらに添加すると、圧延油粒子の表面電位は正となるとともに保護コロイド作用により、圧延油粒子は大粒子径で且つ乳化分散性も良好となるため、プレートアウト性が良好となり優れた潤滑性を示し、長期循環安定性も良好となる。（ｆ）成分をさらに添加すると、乳化分散性は非常に良好となるが、圧延油粒子径は中粒子径となるため、プレートアウト性が不十分となり潤滑性不良を示す。本発明の熱間圧延油としては、圧延油粒子径と長期循環安定性の観点から、潤滑油１００重量部に対して、（ｆ）成分は０．１〜５重量部用いることがより好ましく、０．３〜２重量部用いることが特に好ましい。（ｆ）成分がこの範囲であると圧延油粒子径は大きく長期循環安定性にも優れる。圧延油中での潤滑油粒子の体積平均粒子径（２０℃）は、１〜２０μｍであることが好ましい。 (F) A component can be used 1 type or in mixture of 2 or more types. Although the surface potential of the rolling oil particles is negative, the surface potential of the rolling oil particles becomes almost zero as the component (f) is added, and the rolling oil particles are aggregated to have a coarse particle diameter. When the component (f) is further added, the surface potential of the rolled oil particles becomes positive and the protective colloid action causes the rolled oil particles to have a large particle diameter and good emulsification and dispersibility. It exhibits excellent lubricity and long-term circulation stability. When the component (f) is further added, the emulsification dispersibility becomes very good, but the rolling oil particle size becomes the medium particle size, so that the plate-out property becomes insufficient and the lubricity is poor. As the hot rolling oil of the present invention, from the viewpoint of rolling oil particle size and long-term circulation stability, it is more preferable to use 0.1 to 5 parts by weight of component (f) with respect to 100 parts by weight of the lubricating oil. It is particularly preferable to use 0.3 to 2 parts by weight. When the component (f) is in this range, the rolling oil particle size is large and the long-term circulation stability is also excellent. The volume average particle diameter (20 ° C.) of the lubricating oil particles in the rolling oil is preferably 1 to 20 μm.
本発明の潤滑油及び／又は圧延油には、上記成分の他に必要に応じて公知添加剤、例えば防錆・防食剤、酸化防止剤等を添加することもできる。 In addition to the above components, known additives such as a rust / corrosion inhibitor and an antioxidant can be added to the lubricating oil and / or rolling oil of the present invention as necessary.
防錆・防食剤としては、例えばアルケニルコハク酸及びその誘導体、オレイン酸等の脂肪酸、ソルビタンモノオレート等のエステル、アミン類等を用いることができ、これらは潤滑油及び／又は圧延油成分全量に対して２重量％以下で添加することができる。 As the anticorrosive and anticorrosive agent, for example, alkenyl succinic acid and derivatives thereof, fatty acids such as oleic acid, esters such as sorbitan monooleate, amines and the like can be used, and these can be used for the total amount of lubricating oil and / or rolling oil components. On the other hand, it can be added at 2% by weight or less.
また、酸化防止剤としては、例えば２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール等のフェノール系化合物、フェニルα−ナフチルアミン等の芳香族アミン等を用いることができ、これらは潤滑油及び／又は圧延油成分全量に対して５重量％以下で添加することができる。 As the antioxidant, for example, phenol compounds such as 2,6-di-tert-butyl-p-cresol, aromatic amines such as phenyl α-naphthylamine, and the like can be used. Alternatively, it can be added at 5% by weight or less based on the total amount of the rolling oil component.
本発明の熱間圧延油は、本発明の潤滑油と乳化剤と水をどの順序で混合してもよいが、好ましくは水と乳化剤と混合した後、本発明の潤滑油と混合することが好ましい。 The hot rolling oil of the present invention may be mixed with the lubricating oil of the present invention, the emulsifier and water in any order, but preferably mixed with the lubricating oil of the present invention after mixing with water and the emulsifier. .
［熱間圧延方法］
本発明の熱間圧延方法は、アルミニウム及びアルミニウム合金板の熱間圧延に、上記本発明の熱間圧延油を用いる方法である。用いる圧延油の温度は、１０〜９０℃が好ましい。本発明の熱間圧延油は、アルミニウム及びアルミニウム合金板の熱間圧延時に、１〜３０ｍ3／分の流量で圧延加工部にスプレー供給して用いることが好ましい。
[Hot rolling method]
The hot rolling method of the present invention is a method in which the hot rolling oil of the present invention is used for hot rolling of aluminum and aluminum alloy sheets. The temperature of the rolling oil used is preferably 10 to 90 ° C. The hot-rolled oil of the present invention is preferably used by spray-suppliing to the rolled portion at a flow rate of 1 to 30 m 3 / min during hot rolling of aluminum and aluminum alloy sheets.
例中の「部」は、「重量部」である。 “Parts” in the examples is “parts by weight”.
実施例１
下記配合成分を用い、表１及び表２に示す組成の各種熱間圧延油用潤滑油及び乳化剤を調製し、更にこの潤滑油と、乳化剤と水を用い、濃度（圧延油中の潤滑油と乳化剤の合計重量）が４重量％（ただし、本発明品１と比較品１は８重量％）の圧延油（Ｏ／Ｗ型乳化エマルション）を常法に従い調製した（本発明品１〜９及び比較品１〜６）。潤滑油と乳化剤の配合割合は表に記載したとおりである。
Example 1
Using the following blending ingredients, various lubricating oils and emulsifiers for hot rolling oils having the compositions shown in Tables 1 and 2 were prepared. Further, using this lubricating oil, the emulsifier and water, the concentration (the lubricating oil in the rolling oil and A rolling oil (O / W emulsified emulsion) having a total weight of emulsifier of 4% by weight (however, the present product 1 and the comparative product 1 is 8% by weight) was prepared according to a conventional method (the present products 1 to 9 and Comparative products 1-6). The blending ratio of the lubricating oil and the emulsifier is as described in the table.
得られた圧延油について、以下に示す方法で、平均粒子径を測定し、圧延潤滑性、板表面品質性及び鉄防食性を評価した。その結果を表１及び表２に示す。 About the obtained rolling oil, the average particle diameter was measured by the method shown below, and rolling lubricity, plate | board surface quality, and iron corrosion resistance were evaluated. The results are shown in Tables 1 and 2.
＜配合成分＞
（ａ）成分
・鉱物油Ａ…パラフィン系鉱物油（４０℃の動粘度６０ｍｍ2／ｓ）
・鉱物油Ｂ…ナフテン系鉱物油（４０℃の動粘度６８ｍｍ2／ｓ）
（ｂ）成分
・脂肪酸Ａ…オレイン酸
（ｃ）成分
・油脂Ａ…精製パーム油（ヨウ素価６０、融点１５℃）
・油脂Ｂ…豚脂（ヨウ素価５５、融点２５℃）
・エステルＡ…フタル酸ジラウリル
・エステルＢ…トリメチロールプロパン椰子油脂肪酸トリエステル（椰子油脂肪酸はルナックＬ−５０ 花王（株）製）
・エステルＣ…トリメチロールプロパンイソステアリン酸トリエステル
（ｄ）成分
・アルコールＡ…椰子油還元アルコール（カルコール２４５５ 花王（株）製）
・アルコールＢ…炭素数１１〜１５のオキソアルコール（ダイヤドール１３５ 三菱化学（株）製）
・アルコールＣ…オレイルアルコール
（ｅ）成分
・極圧剤Ａ…トリイソオクチルホスファイト
・極圧剤Ｂ…トリクレジルホスフェート
その他の添加剤
・添加剤Ａ…トリエタノールアミン
・添加剤Ｂ…防錆剤（ヘキサデセニルコハク酸）
・添加剤Ｃ…酸化防止剤（２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール）
乳化剤
・高分子Ａ…ジメチルアミノプロピルメタクリルアミド／アクリルアミド／アクリル酸ナトリウム＝８４／１／１５（重量比）の共重合物の１００％グリコール酸中和物（分子量＝５万）
・高分子Ｂ…ジメチルアミノプロピルアクリルアミド／アクリルアミド／アクリル酸ナトリウム＝８０／５／１５（重量比）の共重合物の１００％酢酸中和物（分子量＝４０万）
・界面活性剤Ａ…ポリオキシエチレンラウリルエーテル、ＨＬＢ＝１２．１（エマルゲン１０８ 花王（株）製）
＜圧延潤滑性評価法及び平均粒子径測定法＞
熱間圧延油について、二段圧延機（２００ｍｍφ×２００ｍｍ幅、ＳＵＪ−２、Ｈｓ＝９０）を用い、下記条件で短冊単パス圧延試験を行い、圧下率＝４０％時の圧延荷重により圧延潤滑性を評価した。圧延荷重が４５０ＭＰａ以下であれば圧延潤滑性は良好である。なお、圧延時の圧延油エマルションの平均粒子径（体積分布）をコールターカウンター（２５℃）にて測定した。
<Blending ingredients>
(A) Component / Mineral oil A: Paraffinic mineral oil (kinematic viscosity at 40 ° C. 60 mm 2 / s)
Mineral oil B: Naphthenic mineral oil (kinematic viscosity at 40 ° C. 68 mm 2 / s)
(B) Component / Fatty Acid A ... Oleic Acid (c) Component / Oil A ... Refined Palm Oil (Iodine Value 60, Melting Point 15 ° C.)
・ Oil B: Pork fat (iodine value 55, melting point 25 ° C.)
・ Ester A… Dilauryl phthalate ・ Ester B… Trimethylolpropane coconut oil fatty acid triester (coconut oil fatty acid is manufactured by LUNAC L-50 Kao Corporation)
Ester C: Trimethylolpropane isostearic acid triester (d) component Alcohol A: Palm oil reduced alcohol (Calcoal 2455 manufactured by Kao Corporation)
Alcohol B: oxo alcohol having 11 to 15 carbon atoms (Diadol 135 manufactured by Mitsubishi Chemical Corporation)
・ Alcohol C: oleyl alcohol (e) component ・ Extreme pressure agent A: Triisooctyl phosphite ・ Extreme pressure agent B: tricresyl phosphate Other additives / additives A… Triethanolamine / additive B ... rust prevention Agent (hexadecenyl succinic acid)
Additive C: antioxidant (2,6-di-tert-butyl-p-cresol)
Emulsifier / polymer A: 100% glycolic acid neutralized product of dimethylaminopropylmethacrylamide / acrylamide / sodium acrylate = 84/1/15 (weight ratio) (molecular weight = 50,000)
Polymer B: 100% acetic acid neutralized product of dimethylaminopropylacrylamide / acrylamide / sodium acrylate = 80/5/15 (weight ratio) (molecular weight = 400,000)
Surfactant A: polyoxyethylene lauryl ether, HLB = 12.1 (Emulgen 108 manufactured by Kao Corporation)
<Rolling lubricity evaluation method and average particle size measurement method>
The hot rolling oil was subjected to a strip single pass rolling test under the following conditions using a two-stage rolling mill (200 mmφ × 200 mm width, SUJ-2, Hs = 90), and rolling lubrication was performed with a rolling load at a reduction ratio of 40%. Sex was evaluated. If the rolling load is 450 MPa or less, the rolling lubricity is good. In addition, the average particle diameter (volume distribution) of the rolling oil emulsion at the time of rolling was measured with the Coulter counter (25 degreeC).
（１）圧延条件
・圧延材：アルミニウム合金材（Ａ５１８２，４０ｍｍ幅×７００ｍｍ長×３．５ｍｍ厚）
・ロール粗度：研磨紙により圧延方向に研磨し、板幅方向の粗度がＲａ＝０．３〜０．４μｍ（Ｒｚ＝３．５〜４．０μｍ）に調整する。
・板温度：４２０℃
・圧延速度：４０ｍ／分
・圧下率：２５％、３５％、４５％
・予備圧延：予め純アルミニウム材（Ａ１１００，４０ｍｍ幅×７００ｍｍ長×３．５ｍｍ厚）を圧下率７０％で１０枚圧延する。
・圧延枚数：各圧下率について４枚ずつ
（２）圧延油条件
・液温度：６０℃
・撹拌機：Ｍ型ホモミキサー（特殊機化工業）
・回転数：８０００ｒ／ｍｉｎ
・スプレー量：２Ｌ／ｍｉｎ×上下各１本、２００ｋＰａ
・粒径測定：コールターカウンターマルチサイザー（ＢＥＣＫＭＡＮ ＣＯＵＬＴＥＲ）
＜板表面品質性評価法＞
上記圧延潤滑性評価時に得られた圧下率＝４５％の圧延板について、下記条件でアルマイト処理を行い、板表面の黒点状焼付欠陥の状態により板表面品質性を評価した。判定は黒点状焼付欠陥の数で、下記基準の５段階（１〜５点）とし、数が少ないほど板表面品質性は良好であり、一番少ないものを５点、一番多いものを１点とした。判定が４点以上であれば板表面品質性は良好である。
(1) Rolling conditions / rolled material: aluminum alloy material (A5182, 40 mm width × 700 mm length × 3.5 mm thickness)
Roll roughness: Polishing in the rolling direction with abrasive paper, and adjusting the roughness in the plate width direction to Ra = 0.3 to 0.4 μm (Rz = 3.5 to 4.0 μm).
・ Plate temperature: 420 ℃
・ Rolling speed: 40 m / min ・ Rolling rate: 25%, 35%, 45%
Pre-rolling: Pure aluminum material (A1100, 40 mm width × 700 mm length × 3.5 mm thickness) is rolled in advance at a rolling reduction of 70%.
・ Number of rolled sheets: 4 sheets for each reduction ratio (2) Rolling oil conditions ・ Liquid temperature: 60 ° C.
・ Agitator: M-type homomixer (Special Machine Industries)
・ Rotation speed: 8000r / min
・ Spray amount: 2L / min x 1 each for top and bottom, 200kPa
・ Particle size measurement: Coulter counter multisizer (BECKMAN COULTER)
<Surface quality evaluation method>
The rolled plate having a rolling reduction of 45% obtained during the rolling lubricity evaluation was subjected to an alumite treatment under the following conditions, and the plate surface quality was evaluated according to the state of black spot-like seizure defects on the plate surface. Judgment is based on the number of black spot-like seizure defects, and the following standard 5 levels (1 to 5 points). The smaller the number, the better the surface quality of the plate. Points. If the determination is 4 points or more, the plate surface quality is good.
（１）処理条件
・処理溶液：１５ｗ／ｖ％硫酸水溶液
・処理温度：２０℃
・電流密度：２Ａ／ｄｍ2
・処理時間：２０ｍｉｎ
・洗浄方法：流水中に１０ｍｉｎ間浸漬
（２）評価基準
５点：黒点状焼付欠陥が板全面にほとんどなく、優れた品質
４点：黒点状焼付欠陥が幅中央部はほとんどないが、板端部にわずかにある状態
３点：黒点状焼付欠陥が幅中央部、板端部ともにわずかにある状態
２点：黒点状焼付欠陥が幅中央部にわずかにあり、板端部に多くある状態
１点：黒点状焼付欠陥が板全面に多くある状態
＜鉄防食性評価法＞
熱間圧延油について、下記条件で腐食試験を行い、腐食速度（ｍｇ／ｍ2・ｄａｙ）により鉄防食性を評価した。腐食速度が２００ｍｇ／ｍ2・ｄａｙ以下であれば鉄防食性は良好である。
(1) Treatment conditions / treatment solution: 15 w / v% sulfuric acid aqueous solution / treatment temperature: 20 ° C.
・ Current density: 2 A / dm 2
・ Processing time: 20 min
・ Cleaning method: Immersion in running water for 10 min (2) Evaluation criteria 5 points: There are almost no black spot-like seizure defects on the entire surface of the plate, and excellent quality 4 points: There are almost no black spot-like seizure defects in the center of the width, but the edge of the plate 3 points: Slightly black spot-like seizure defects at the center of the width and the edge of the plate 2 points: Slightly black spot-like defects at the center of the width, and many at the edge of the plate 1 Point: State where there are many black spot-like seizure defects on the entire surface of the plate <Iron corrosion protection evaluation method>
The hot rolled oil was subjected to a corrosion test under the following conditions, and the iron corrosion resistance was evaluated based on the corrosion rate (mg / m 2 · day). If the corrosion rate is 200 mg / m 2 · day or less, the iron corrosion resistance is good.
（１）試験条件
・試験片：ＳＳ−４００板（３ｍｍ厚×５０ｍｍ×５０ｍｍ）
・前処理：＃２４０研磨紙にて研磨後、溶剤にて脱脂する。
・浸漬方法：Ｍ型ホモミキサー６０００ｒ／ｍｉｎ撹拌中に全浸漬
・試験温度：６０℃
・試験時間：３日間
(1) Test conditions / Test piece: SS-400 plate (3 mm thickness × 50 mm × 50 mm)
-Pretreatment: After polishing with # 240 polishing paper, degrease with solvent.
・ Immersion method: M type homomixer 6000r / min total agitation during stirring ・ Test temperature: 60 ° C.
・ Test time: 3 days
表１及び表２から明らかなように、圧延潤滑性、板表面品質性及び鉄防食性の全てを満足するものは本発明品のみである。比較品は３つの性能のうち少なくとも１つの性能が劣ることがわかる。 As is apparent from Tables 1 and 2, only the product of the present invention satisfies the rolling lubricity, plate surface quality and iron corrosion resistance. It can be seen that the comparative product is inferior in at least one of the three performances.
Claims (5)
（ａ）動粘度８０ｍｍ2／ｓ（４０℃）以下の鉱物油
（ｂ）炭素数１０〜２２の脂肪酸
（ｃ）天然油脂及び炭素数１０〜２２の１価高級脂肪酸又は多塩基酸とアルコールから得られる合成エステルから選ばれる少なくとも１種
（ｄ）直鎖又は分岐鎖のアルキル基又はアルケニル基を有する炭素数８〜２６の１価アルコール
（ｅ）リン系極圧剤 The following (a), (b), (c), (d) and (e) components are contained, the content of (b) component is 1 to 14% by weight, and the content of (c) component is 2 to 50%. 1% to 10% by weight of lubricating oil for hot rolling oil for aluminum and aluminum alloy sheets, and 0.1 to 5% by weight of emulsifier and 85 to 98% of water. Hot rolling oil for aluminum and aluminum alloy sheets, containing 9% by weight.
(A) Mineral oil having a kinematic viscosity of 80 mm 2 / s (40 ° C.) or less (b) Fatty acid having 10 to 22 carbon atoms (c) Natural oil and fat and monovalent higher fatty acid or polybasic acid having 10 to 22 carbon atoms and alcohol C8-C26 monohydric alcohol (e) phosphorus-based extreme pressure agent having at least one (d ) linear or branched alkyl group or alkenyl group selected from the resulting synthetic esters
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| JP2008201856A (en) * | 2007-02-16 | 2008-09-04 | Kobe Steel Ltd | Method for rolling aluminum plate or aluminum alloy plate |
| JP2008200689A (en) * | 2007-02-16 | 2008-09-04 | Kobe Steel Ltd | Rolling method for aluminum sheet or aluminum alloy sheet |
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| CN102031184B (en) * | 2010-12-24 | 2013-05-15 | 上海锦海特种润滑油厂 | High-quality saponifiable oil and preparation method thereof |
| JP6884601B2 (en) * | 2017-03-02 | 2021-06-09 | 株式会社Uacj | Method for manufacturing hot-rolled oil for aluminum, hot-rolled coolant for aluminum, and rolled aluminum plate |
| CN107974338A (en) * | 2017-11-24 | 2018-05-01 | 东莞市伟思化学科技有限公司 | A kind of fully synthetic aqueous stamping oil of carbon steel and preparation method thereof |
| JP6981888B2 (en) * | 2018-01-26 | 2021-12-17 | トヨタ自動車株式会社 | Lubricating mold release agent for hot forging |
| JP7140396B2 (en) * | 2019-12-24 | 2022-09-21 | 大同化学株式会社 | Hot rolling oil composition for aluminum and hot rolling method for aluminum |
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