JP5502848B2 - Anti-rust oil composition for processing - Google Patents
Anti-rust oil composition for processing Download PDFInfo
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- JP5502848B2 JP5502848B2 JP2011285724A JP2011285724A JP5502848B2 JP 5502848 B2 JP5502848 B2 JP 5502848B2 JP 2011285724 A JP2011285724 A JP 2011285724A JP 2011285724 A JP2011285724 A JP 2011285724A JP 5502848 B2 JP5502848 B2 JP 5502848B2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims description 70
- 239000000203 mixture Substances 0.000 title claims description 66
- 238000012545 processing Methods 0.000 title claims description 45
- 239000003921 oil Substances 0.000 claims description 70
- 230000003449 preventive effect Effects 0.000 claims description 45
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000002199 base oil Substances 0.000 claims description 26
- -1 fatty acid ester Chemical class 0.000 claims description 22
- 229910052788 barium Inorganic materials 0.000 claims description 18
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 150000004665 fatty acids Chemical group 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000002480 mineral oil Substances 0.000 claims description 9
- 235000010446 mineral oil Nutrition 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000003754 machining Methods 0.000 claims 1
- 238000005238 degreasing Methods 0.000 description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 229910001335 Galvanized steel Inorganic materials 0.000 description 9
- 239000008397 galvanized steel Substances 0.000 description 9
- 230000002265 prevention Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
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- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000005237 degreasing agent Methods 0.000 description 3
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- 150000002148 esters Chemical class 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- BTGGRPUPMPLZNT-PGEUSFDPSA-N 2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]butyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC BTGGRPUPMPLZNT-PGEUSFDPSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 150000008107 benzenesulfonic acids Chemical class 0.000 description 2
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- 235000011187 glycerol Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
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- 239000013521 mastic Substances 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
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- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 2
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- GSAHAZJWNMHSNI-UHFFFAOYSA-N 2,2-bis(dodecanoyloxymethyl)butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC(CC)(COC(=O)CCCCCCCCCCC)COC(=O)CCCCCCCCCCC GSAHAZJWNMHSNI-UHFFFAOYSA-N 0.000 description 1
- WAZOXQOFCQKLFT-QXMHVHEDSA-N 2,2-bis(hydroxymethyl)butyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CC)(CO)CO WAZOXQOFCQKLFT-QXMHVHEDSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QKJWEMFCEHDWQH-UHFFFAOYSA-N 3,3-bis(hydroxymethyl)butane-1,1,4-triol Chemical compound C(O)C(CC(O)O)(CO)CO QKJWEMFCEHDWQH-UHFFFAOYSA-N 0.000 description 1
- KZVOBYGWUVXBAK-UHFFFAOYSA-N 3,4-didodecyl-2-hexadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCC1=C(CCCCCCCCCCCC)C(CCCCCCCCCCCC)=CC=C1S(O)(=O)=O KZVOBYGWUVXBAK-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000823778 Homo sapiens Y-box-binding protein 2 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QTIMEBJTEBWHOB-PMDAXIHYSA-N [3-[(z)-octadec-9-enoyl]oxy-2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]propyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COC(=O)CCCCCCC\C=C/CCCCCCCC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC QTIMEBJTEBWHOB-PMDAXIHYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 150000004996 alkyl benzenes Chemical class 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
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- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- Lubricants (AREA)
Description
本発明は、加工兼用防錆油組成物に関し、詳しくは、熱延鋼板、冷延鋼板、亜鉛メッキ鋼板等に用いる防錆性に優れ、その後の脱脂性に優れ、かつ加工性に優れた加工兼用防錆油組成物に関する。 The present invention relates to a processing and rust preventive oil composition, and in particular, processing excellent in rust prevention used for hot rolled steel sheet, cold rolled steel sheet, galvanized steel sheet, etc., excellent in degreasing property and excellent in workability. The present invention relates to a combined anti-rust oil composition.
熱延鋼板、冷延鋼板、亜鉛メッキ鋼板は、通常、製鉄メーカーで製造された後、コイルに巻き取られる前に、静電塗油、ロールコーターなどの方法で防錆油が塗布される。これは鋼板が製造された後にコイルやシート状で出荷され、需要家において開梱され、加工されるまでの間に錆を生じさせないようにするためである。需要家では、入荷した鋼板をプレス加工等するが、通常、これら防錆油は充分な加工性を備えておらず、特に絞り加工を施した際には鋼板表面にかじりを発生する。そのため、加工業者にあっては、加工に先立って更に潤滑性に富む高粘度の潤滑油の塗油作業を行い、しかる後に所定の加工処理を施している。
この塗油作業は、通常、手作業であるため加工工程全体の生産性を低下せしめ、また作業環境の悪化をもたらし、更には加工後の脱脂不良やオイルステンなどの問題を派生させる。
Hot-rolled steel sheets, cold-rolled steel sheets, and galvanized steel sheets are usually coated with a rust preventive oil by a method such as electrostatic oil coating or roll coater after being manufactured by an iron manufacturer and before being wound on a coil. This is to prevent rust from being produced before the steel sheet is manufactured and shipped in the form of a coil or sheet, unpacked by the customer, and processed. The customer presses the received steel sheet, but usually these rust preventive oils do not have sufficient workability and generate galling on the surface of the steel sheet particularly when drawing. For this reason, prior to processing, a processor performs a coating operation of a high-viscosity lubricating oil that is further rich in lubricity, and then performs predetermined processing.
Since this oiling operation is usually a manual operation, the productivity of the entire processing process is lowered, the working environment is deteriorated, and further problems such as degreasing defects and oil stain after processing are derived.
また、最近高強度鋼板、亜鉛メッキ鋼板が増加しているが、その加工の際においては、処理工程の簡素化（例えば、現状の防錆潤滑油塗布ラインをそのまま使う）、処理油剤の一本化等の要望が高まっており、この要望に対応できるような防錆兼プレス加工油剤組成物の開発が望まれている。
このような状況下で、例えば、特定粘度範囲の潤滑油基油に、防錆剤，硫黄系極圧剤及び高塩基性スルホネートを添加した亜鉛メッキ鋼板用プレス加工兼防錆剤が提案されている（特許文献１、特許請求の範囲参照）。また、低粘度の溶剤に、スルホン酸塩，カルボン酸塩，リン酸エステル誘導体等、超塩基性スルホネート及びホウ酸カリウムを添加したプレス加工兼用防錆油が提案されている（特許文献２、特許請求の範囲参照）。さらには、潤滑油基油に、防錆剤、過塩基性Ｃａスルホネート、硫黄系極圧剤、及びホウ酸カリウム分散物を配合してなる防錆兼プレス加工油剤組成物が提案されている（特許文献３、特許請求の範囲参照）。
しかしながら、これらの加工兼用防錆油組成物はいずれも、アルカリ度の低い脱脂液や、ケイ酸ナトリウム系の脱脂液において、脱脂性に劣るものであった。また、これらの加工兼用防錆油組成物は、硫黄系の極圧剤を使用しているために、亜鉛メッキ鋼板を対象とする場合には、亜鉛メッキの剥離を促進し、摩擦係数を増大させてしまう場合がある。さらに、防錆性、潤滑性（プレス加工成形性）及び脱脂性を両立することが難しく、特にリン系、又は無リン系の脱脂剤による脱脂性に必ずしも優れたものではなく、さらなる改良が望まれていた。
Recently, high-strength steel sheets and galvanized steel sheets are increasing, but during processing, the processing process is simplified (for example, the current rust-preventive lubricating oil application line is used as it is), and one processing oil agent is used. Development of a rust preventive and press working oil composition that can meet this demand is desired.
Under such circumstances, for example, a press working and rust preventive agent for galvanized steel sheets in which a rust preventive agent, a sulfur-based extreme pressure agent and a high basic sulfonate are added to a lubricating base oil in a specific viscosity range has been proposed. (See Patent Document 1 and Claims). Further, there has been proposed a rust preventive oil for press working in which a low-viscosity solvent is added with a sulfonate, a carboxylate, a phosphate ester derivative, etc., an ultrabasic sulfonate, and potassium borate (Patent Document 2, Patent) See claims). Furthermore, a rust preventive and press working oil composition comprising a lubricating base oil and a rust inhibitor, an overbased Ca sulfonate, a sulfur-based extreme pressure agent, and a potassium borate dispersion has been proposed ( (See Patent Document 3 and Claims).
However, any of these processed and combined rust preventive oil compositions is inferior in degreasing properties in a degreasing solution having a low alkalinity or a sodium silicate-based degreasing solution. In addition, since these processing and rust preventive oil compositions use sulfur-based extreme pressure agents, when galvanized steel sheets are targeted, peeling of galvanizing is promoted and the coefficient of friction is increased. There is a case to let you. Furthermore, it is difficult to achieve both rust resistance, lubricity (press workability) and degreasing properties, and in particular, it is not necessarily excellent in degreasing properties with phosphorus-based or phosphorus-free degreasing agents, and further improvement is desired. It was rare.
また、これまでの防錆油組成物においては、通常、バリウムを２００質量ｐｐｍ以上含有するが、バリウムは欧米において環境上の問題から、使用に届出が必要な場合がある物質であり、安全性について注意を払う必要のある物質である。従って、バリウムの含有量を低減した防錆油組成物が求められていた。さらに、過塩基性スルホネートを含有する防錆油組成物は、自動車のマスチックシーラントの密着性を阻害する場合があるために、防錆油組成物中の過塩基性スルホネートの含有量を低減させる要望があった。 In addition, conventional rust preventive oil compositions usually contain 200 mass ppm or more of barium, but barium is a substance that may need to be reported for use due to environmental problems in Europe and the United States. Is a substance that needs to be paid attention to. Therefore, a rust preventive oil composition having a reduced barium content has been demanded. Furthermore, since the rust preventive oil composition containing an overbased sulfonate may inhibit the adhesion of the mastic sealant of an automobile, there is a demand for reducing the content of the overbased sulfonate in the rust preventive oil composition. was there.
本発明は、このような状況下でなされたもので、熱延鋼板、冷延鋼板、亜鉛メッキ鋼板に塗布して有効であり、防錆性、アルカリ脱脂剤等による脱脂性に優れ、かつ加工性に優れる加工兼用防錆油組成物を提供することを目的とする。特に、亜鉛メッキ鋼板においては、亜鉛メッキの剥離を抑制して摩擦係数を低減し、かつ、現状の防錆油塗布ラインでそのままトラブルなく塗布可能な加工兼用防錆油組成物を提供することを目的とする。 The present invention has been made under such circumstances, and is effective when applied to a hot-rolled steel sheet, a cold-rolled steel sheet, and a galvanized steel sheet, and is excellent in rust prevention, degreasing by an alkaline degreasing agent, and the like. An object of the present invention is to provide a processing and rust preventive oil composition having excellent properties. In particular, for galvanized steel sheets, to provide a processing and rust-preventive oil composition that reduces the coefficient of friction by suppressing galvanization peeling and can be applied without any trouble in the current rust-preventive oil application line. Objective.
本発明者は、前記目的を達成するために、鋭意研究を重ねた結果、特定の基油に、多価アルコールの脂肪酸エステル、過塩基性金属スルホネート、及び中性金属スルホネートを配合した組成物であって、バリウムを実質的に含有しない加工兼用防錆油組成物が、前記課題を解決し得ることを見出した。本発明はかかる知見に基づいて完成されたものである。
すなわち、本発明は、
（１）（Ａ）４０℃における動粘度が４〜５０ｍｍ2／ｓの鉱油及び／又は合成油を基油とし、これに（Ｂ）脂肪酸残基の炭素数が１４以上であり、かつ分子中のＯＨ基数が１未満である多価アルコールの脂肪酸エステル、（Ｃ）過塩基性金属スルホネート、及び（Ｄ）中性金属スルホネートを配合し、かつバリウムの含有量が組成物全量基準で５質量ｐｐｍ以下である加工兼用防錆油組成物であって、
（Ａ）基油が（ａ）４０℃における動粘度が１．５〜１０ｍｍ 2 ／ｓの低粘度基油と（ｂ）４０℃における動粘度が１０〜１００ｍｍ 2 ／ｓの高粘度基油を、（ａ）成分：（ｂ）成分の質量比で１：２〜１：１５の範囲で混合したものであり、
（Ｂ）成分及び（Ｃ）成分が、組成物全量を基準として、それぞれ１〜２０質量％配合され、（Ｄ）成分が組成物全量を基準として金属分として０．０２〜０．１質量％配合され、かつ、（Ｂ）成分と、（Ｃ）成分及び（Ｄ）成分との質量比（Ｂ）：［（Ｃ）＋（Ｄ）］が、１：１〜１：２の範囲である加工兼用防錆油組成物、
（２）（Ｃ）過塩基性金属スルホネートが過塩基性カルシウムスルホネートを含有し、かつ（Ｃ）成分中のカルシウム含有量が組成物全量を基準として２．５質量％以下である上記（１）に記載の加工兼用防錆油組成物、
（３）（Ａ）基油が環分析により測定した分子量で７００未満である上記（１）又は（２）に記載の加工兼用防錆油組成物、
（４）（Ｃ）成分の塩基価が３００ｍｇＫＯＨ／ｇ以上である上記（１）〜（３）のいずれかに記載の加工兼用防錆油組成物、
（５）４０℃における動粘度が５〜２０ｍｍ 2 ／ｓである上記（１）〜（４）のいずれかに記載の加工兼用防錆油組成物、及び
（６） 前記（Ｂ）成分と、（Ｃ）成分及び（Ｄ）成分との質量比（Ｂ）：［（Ｃ）＋（Ｄ）］が、１：１．５である（１）〜（５）のいずれかに記載の加工兼用防錆油組成物、
を提供するものである。
As a result of intensive studies to achieve the above object, the present inventor is a composition in which a fatty acid ester of a polyhydric alcohol, an overbased metal sulfonate, and a neutral metal sulfonate are blended with a specific base oil. Thus, it has been found that a processing and rust preventive oil composition substantially free of barium can solve the above-mentioned problems. The present invention has been completed based on such findings.
That is, the present invention
(1) (A) Mineral oil and / or synthetic oil having a kinematic viscosity at 40 ° C. of 4 to 50 mm 2 / s is used as the base oil, and (B) the fatty acid residue has 14 or more carbon atoms, and in the molecule A fatty acid ester of a polyhydric alcohol having an OH group number of less than 1, (C) an overbased metal sulfonate, and (D) a neutral metal sulfonate, and the barium content is 5 mass ppm based on the total amount of the composition It is the following processing combined rust prevention oil composition ,
(A) The base oil is (a) a low-viscosity base oil having a kinematic viscosity at 40 ° C. of 1.5 to 10 mm 2 / s and (b) a high-viscosity base oil having a kinematic viscosity at 40 ° C. of 10 to 100 mm 2 / s. , (A) component: (b) component is mixed at a mass ratio of 1: 2 to 1:15,
(B) component and (C) component are respectively mix | blended 1-20 mass% on the basis of the composition whole quantity, (D) component is 0.02-0.1 mass% as a metal part on the basis of the composition whole quantity. And the mass ratio (B): [(C) + (D)] of the component (B), the component (C) and the component (D) is in the range of 1: 1 to 1: 2. Anti-rust oil composition for processing
(2) The above (1), wherein (C) the overbased metal sulfonate contains an overbased calcium sulfonate, and the calcium content in the component (C) is 2.5% by mass or less based on the total amount of the composition. Anti-rust oil composition for processing and use as described in
(3) The processing and rust preventive oil composition according to (1) or (2) above, wherein (A) the base oil has a molecular weight measured by ring analysis of less than 700,
(4) The processing and rust preventive oil composition according to any one of the above (1) to (3), wherein the base number of the component (C) is 300 mgKOH / g or more,
(5) The processing and rust preventive oil composition according to any one of the above (1) to (4), wherein the kinematic viscosity at 40 ° C. is 5 to 20 mm 2 / s , and (6 ) the component (B), Combined processing according to any one of (1) to (5), wherein the mass ratio (B): [(C) + (D)] with the component (C) and the component (D) is 1: 1.5. Anti-rust oil composition,
Is to provide.
本発明によれば、従来の防錆油組成物に比較して脱脂性に優れ、かつ防錆性及び潤滑性にも優れる加工兼用防錆油組成物を提供することができる。また、防錆油が多量に混入したアルカリ脱脂液においても、優れた脱脂性を保つことができる。さらに、本発明の加工兼用防錆油組成物は、バリウムを実質的に含有しないため環境負荷が小さい。 ADVANTAGE OF THE INVENTION According to this invention, compared with the conventional rust preventive oil composition, it can provide the processing and rust preventive oil composition which is excellent in degreasing property, and is excellent also in rust preventive property and lubricity. Further, even in an alkaline degreasing solution in which a large amount of rust preventive oil is mixed, excellent degreasing properties can be maintained. Furthermore, since the processing and rust preventive oil composition of the present invention does not substantially contain barium, the environmental load is small.
本発明の加工兼用防錆油組成物は、（Ａ）４０℃における動粘度が４〜５０ｍｍ2／ｓの鉱油及び／又は合成油を基油とする。４０℃における動粘度が４ｍｍ2／ｓ以上であると、鋼板表面が乾きにくく、一方、５０ｍｍ2／ｓ以下であると、濡れ拡がりやすく塗布性が高いという利点があり、また、鋼板同士が接着せずに搬送しやすいという利点がある。以上の点から、４０℃における動粘度は、１０〜２０ｍｍ2／ｓの範囲がさらに好ましい。
また、４０℃における動粘度が上記範囲内にある基油を調製するにあたって、（ａ）４０℃における動粘度が１．５〜１０ｍｍ2／ｓの低粘度基油と（ｂ）４０℃における動粘度が１０〜１００ｍｍ2／ｓの高粘度基油を混合することが必要である。こうした手法をとることによって、容易に所望の粘度範囲を有する基油を得ることができるとともに脱脂性の優れた加工兼用防錆油組成物を得ることができる。より具体的には、上記（ａ）成分と（ｂ）成分を、（ａ）成分:（ｂ）成分の質量比で１：２〜１：１５の範囲で混合したものが脱脂性の点から好ましい。
さらに、本発明で用いる（Ａ）基油は、環分析により測定した分子量が７００未満であることが好ましい。環分析による分子量が７００未満であると脱脂されやすい。
The processing and rust preventive oil composition of the present invention is based on (A) a mineral oil and / or a synthetic oil having a kinematic viscosity at 40 ° C. of 4 to 50 mm 2 / s. When the kinematic viscosity at 40 ° C. is 4 mm 2 / s or more, the surface of the steel sheet is difficult to dry, and when it is 50 mm 2 / s or less, there is an advantage that the coating is easy to spread and the coating property is high. There is an advantage that it is easy to carry without. From the above points, the kinematic viscosity at 40 ° C. is more preferably in the range of 10-20 mm 2 / s.
In preparing a base oil having a kinematic viscosity at 40 ° C. within the above range, (a) a low-viscosity base oil having a kinematic viscosity at 40 ° C. of 1.5 to 10 mm 2 / s and (b) a kinematic viscosity at 40 ° C. It is necessary to mix a high viscosity base oil having a viscosity of 10 to 100 mm 2 / s. By taking such a method, it is possible to easily obtain a base oil having a desired viscosity range, and it is possible to obtain a processing and rust preventive oil composition having excellent degreasing properties. More specifically, the above component (a) and component (b) are mixed in a mass ratio of component (a): component (b) in the range of 1: 2 to 1:15 from the point of degreasing properties. preferable.
Furthermore, the base oil (A) used in the present invention preferably has a molecular weight measured by ring analysis of less than 700. It is easy to degrease when the molecular weight by ring analysis is less than 700.
本発明で用いる鉱油としては、通常潤滑油の基油として用いられるものであれば特に限定されるものではなく、パラフィン基系原油、中間基系原油、又はナフテン基系原油を常圧蒸留した残渣油、又は常圧蒸留の残渣油を減圧蒸留して得られる留出油、さらにはこれらを常法に従って精製することによって得られる精製油、例えば溶剤精製油、水添精製油、脱ロウ処理油、白土処理油などを挙げることができる。
また、合成油としては、例えば、ポリ−α−オレフィン、α−オレフィンコポリマー、ポリブテン、アルキルベンゼン、ポリオールエステル、二塩基酸エステル、ポリオキシアルキレングリコール、ポリオキシアルキレングリコールエステル、ポリオキシアルキレングリコールエーテル、ヒンダードエステル、シリコーンオイルなどを挙げることができる。
これらの潤滑油基油は、一種単独で、又は二種以上を混合して、さらには鉱油と合成油を組み合わせて使用することができる。
The mineral oil used in the present invention is not particularly limited as long as it is usually used as a base oil for lubricating oil, and is a residue obtained by atmospheric distillation of paraffin-based crude oil, intermediate-based crude oil, or naphthene-based crude oil. Oil, or distillate obtained by distillation under reduced pressure of residual oil from atmospheric distillation, and further refined oil obtained by refining them according to a conventional method, for example, solvent refined oil, hydrogenated refined oil, dewaxed oil And white clay treated oil.
Synthetic oils include, for example, poly-α-olefin, α-olefin copolymer, polybutene, alkylbenzene, polyol ester, dibasic acid ester, polyoxyalkylene glycol, polyoxyalkylene glycol ester, polyoxyalkylene glycol ether, hinder. Examples include polyesters and silicone oils.
These lubricating base oils can be used singly or in combination of two or more, and a combination of mineral oil and synthetic oil can be used.
本発明の加工兼用防錆油組成物は、（Ｂ）多価アルコールの脂肪酸エステルを配合することを特徴とする。該（Ｂ）成分としては部分エステルを含有していてもよいが、（Ｂ）多価アルコールの脂肪酸エステルの分子中の平均の水酸基（ＯＨ基）の数が１未満であることが必要であり、フルエステルであることが好ましい。また、ＯＨ基が残存する多価アルコールの脂肪酸エステルが、エーテル結合により二量体を作る場合も、本発明の（Ｂ）多価アルコールの脂肪酸エステルに含有される。
ここで多価アルコールとは水酸基を２個以上有するアルコールであり、特に炭素数２〜４の多価アルコールが好ましい。具体的には、エチレングリコール、プロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトールなどが挙げられ、これらのうち特に、グリセリン、トリメチロールプロパン及びペンタエリスリトールが好ましい。また、脂肪酸としては、炭素数１４以上の脂肪酸であることが重要であり、直鎖状、分岐状又は環状であってもよく、飽和又は不飽和であってもよい。より好ましくは、炭素数１４〜１８の脂肪酸が好ましく、具体的には、ミリスチン酸、パルミチン酸、オレイン酸、ステアリン酸などが挙げられる。すなわち、本発明の（Ｂ）成分としては、脂肪酸エステルを構成する脂肪酸残基の炭素数が１４以上、さらには脂肪酸残基の炭素数が１４〜１８であり、分子中のＯＨ基の数が１未満であることが好ましく、最も好ましい脂肪酸エステルとしてはトリメチロールプロパントリオレエート及びペンタエリスリトールテトラオレエートが挙げられる。
また、（Ｂ）成分の配合量は、組成物全量基準で１〜２０質量％の範囲であることが好ましく、さらには１〜１０質量％の範囲、特には２〜１０質量％の範囲が好ましい。
The processing and rust preventive oil composition of the present invention is characterized by blending (B) a fatty acid ester of a polyhydric alcohol. The component (B) may contain a partial ester, but the average number of hydroxyl groups (OH groups) in the molecule of the fatty acid ester of the (B) polyhydric alcohol must be less than 1. A full ester is preferred. Further, the fatty acid ester of a polyhydric alcohol in which an OH group remains is also contained in the fatty acid ester of (B) the polyhydric alcohol of the present invention when a dimer is formed by an ether bond.
Here, the polyhydric alcohol is an alcohol having two or more hydroxyl groups, and a polyhydric alcohol having 2 to 4 carbon atoms is particularly preferable. Specific examples include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol. Among these, glycerin, trimethylolpropane, and pentaerythritol are particularly preferable. Moreover, it is important that the fatty acid is a fatty acid having 14 or more carbon atoms, and may be linear, branched or cyclic, and may be saturated or unsaturated. More preferably, a fatty acid having 14 to 18 carbon atoms is preferable, and specific examples include myristic acid, palmitic acid, oleic acid, stearic acid and the like. That is, as the component (B) of the present invention, the fatty acid residue constituting the fatty acid ester has 14 or more carbon atoms, further the fatty acid residue has 14 to 18 carbon atoms, and the number of OH groups in the molecule is Preferably less than 1, and most preferred fatty acid esters include trimethylolpropane trioleate and pentaerythritol tetraoleate.
The amount of component (B) is preferably in the range of 1 to 20% by mass, more preferably in the range of 1 to 10% by mass, and particularly preferably in the range of 2 to 10% by mass based on the total amount of the composition. .
次に、本発明の加工兼用防錆油組成物は、（Ｃ）過塩基性金属スルホネート及び（Ｄ）中性金属スルホネートを配合することを特徴とする。ここで、金属スルホネートとは各種スルホン酸の金属塩をいう。スルホン酸としては、芳香族石油スルホン酸、アルキルスルホン酸、アリールスルホン酸、アルキルアリールスルホン酸等があり、より具体的には、ドデシルベンゼンスルホン酸、ジラウリルセチルベンゼンスルホン酸、パラフィンワックス置換ベンゼンスルホン酸、ポリオレフィン置換ベンゼンスルホン酸、ポリイソブチレン置換ベンゼンスルホン酸、ナフタレンスルホン酸などが挙げられる。また、金属としては、カルシウム、ナトリウム、マグネシウム、亜鉛など種々のものが挙げられ、これらのうち特にカルシウムが好ましい。
また、（Ｃ）成分中のカルシウムの含有量は、組成物全量を基準として２．５質量％以下であることが好ましい。カルシウムの含有量が２．５質量％以下であると、油が付着しても自動車用マスチックシーラントなどの塩化ビニル含有接着剤の接着性を阻害しない。
本発明の加工兼用防錆油組成物における（Ｃ）過塩基性金属スルホネート及び（Ｄ）中性金属スルホネートには、環境上の観点から、バリウムを含有しないことが好ましく、より具体的にはバリウムの含有量がそれぞれ５質量ｐｐｍ以下であることが好ましい。
Next, the processing and rust preventive oil composition of the present invention is characterized by blending (C) an overbased metal sulfonate and (D) a neutral metal sulfonate. Here, the metal sulfonate refers to metal salts of various sulfonic acids. Examples of the sulfonic acid include aromatic petroleum sulfonic acid, alkyl sulfonic acid, aryl sulfonic acid, alkyl aryl sulfonic acid, and the like. More specifically, dodecylbenzene sulfonic acid, dilauryl cetyl benzene sulfonic acid, paraffin wax-substituted benzene sulfone. Examples include acids, polyolefin-substituted benzene sulfonic acids, polyisobutylene-substituted benzene sulfonic acids, and naphthalene sulfonic acids. Examples of the metal include various metals such as calcium, sodium, magnesium, and zinc. Of these, calcium is particularly preferable.
Moreover, it is preferable that content of the calcium in (C) component is 2.5 mass% or less on the basis of the composition whole quantity. When the calcium content is 2.5% by mass or less, even if oil adheres, the adhesiveness of a vinyl chloride-containing adhesive such as an automotive mastic sealant is not inhibited.
The (C) overbased metal sulfonate and (D) neutral metal sulfonate in the combined anti-rust oil composition for processing of the present invention preferably contain no barium from the environmental viewpoint, and more specifically, barium. It is preferable that content of each is 5 mass ppm or less.
上記（Ｃ）過塩基性金属スルホネートは、添加量を少なくすることができる点から、ＪＩＳ Ｋ−２５０１に準拠した過塩素酸法による全塩基価が、３００ｍｇＫＯＨ／ｇ以上であることが好ましく、さらには４００ｍｇＫＯＨ／ｇ以上であることが好ましい。（Ｃ）過塩基性金属スルホネートは、一種を単独で、又は二種以上を組み合わせて使用してもよい。また、（Ｃ）過塩基性金属スルホネートの配合量は、組成物全量基準で、１〜２０質量％の範囲が好ましく、さらに好ましくは２〜２０質量％の範囲、特に好ましくは３〜１２質量％の範囲である。金属分として換算した場合には、０．２〜４質量％の範囲が好ましく、さらに好ましくは０．４〜４質量％の範囲、特に好ましくは０．６〜２．２質量％の範囲である。 The (C) overbased metal sulfonate is preferably such that the total base number by the perchloric acid method in accordance with JIS K-2501 is 300 mgKOH / g or more from the viewpoint that the addition amount can be reduced. Is preferably 400 mgKOH / g or more. (C) You may use an overbased metal sulfonate individually by 1 type or in combination of 2 or more types. In addition, the amount of (C) the overbased metal sulfonate is preferably in the range of 1 to 20% by mass, more preferably in the range of 2 to 20% by mass, particularly preferably 3 to 12% by mass, based on the total amount of the composition. Range. When converted as a metal content, the range is preferably 0.2 to 4% by mass, more preferably 0.4 to 4% by mass, and particularly preferably 0.6 to 2.2% by mass. .
次に、（Ｄ）中性金属スルホネートは、具体的にはＪＩＳ Ｋ−２５０１に準拠した過塩素酸法による全塩基価が０〜５０ｍｇＫＯＨ／ｇ程度のものをいう。（Ｄ）中性金属スルホネートを含有することにより、防錆性、耐ステイン性が向上する。
（Ｄ）中性金属スルホネートの配合量は、組成物全量基準で、１〜１０質量％の範囲が好ましく、さらに好ましくは２〜１０質量％の範囲、特に好ましくは３〜５質量％の範囲である。金属分として換算した場合には、０．０２〜０．２質量％の範囲が好ましく、さらに好ましくは０．０４〜０．２質量％の範囲、特に好ましくは０．０４〜０．１質量％の範囲である。
また、（Ｃ）成分と（Ｄ）成分の配合比率については、（Ｃ）成分：（Ｄ）成分として、１：４〜４：１の範囲が好ましく、さらには、１：２〜２：１の範囲が好ましい。
Next, (D) neutral metal sulfonate specifically refers to those having a total base number of about 0 to 50 mgKOH / g according to the perchloric acid method in accordance with JIS K-2501. (D) By containing a neutral metal sulfonate, rust prevention and stain resistance are improved.
(D) The compounding amount of the neutral metal sulfonate is preferably in the range of 1 to 10% by mass, more preferably in the range of 2 to 10% by mass, particularly preferably in the range of 3 to 5% by mass, based on the total amount of the composition. is there. When converted as a metal content, the range of 0.02 to 0.2% by mass is preferable, more preferably 0.04 to 0.2% by mass, and particularly preferably 0.04 to 0.1% by mass. Range.
Moreover, about the mixture ratio of (C) component and (D) component, the range of 1: 4-4: 1 is preferable as (C) component: (D) component, Furthermore, 1: 2-2: 1 The range of is preferable.
本発明の加工兼用防錆油組成物は、（Ａ）基油に、（Ｂ）〜（Ｄ）成分を配合して調製することができる。その際に、組成物の４０℃における動粘度が４〜５０ｍｍ2／ｓ、好ましくは５〜２０ｍｍ2／ｓ、さらに好ましくは１０〜２０ｍｍ2／ｓとなるように、各成分の種類、性状、配合割合を選択することが望ましい。
（Ｂ）〜（Ｄ）成分の配合量は上述のようであるが、また、（Ｂ）多価アルコールの脂肪酸エステルと金属スルホネート（（Ｃ）成分と（Ｄ）成分の合計量）との質量比（Ｂ）：［（Ｃ）＋（Ｄ）］が、１：１〜１：２の範囲であることが好ましい。
The processing and rust preventive oil composition of the present invention can be prepared by blending the components (B) to (D) in the (A) base oil. At that time, the type, properties, and properties of each component so that the kinematic viscosity at 40 ° C. of the composition is 4 to 50 mm 2 / s, preferably 5 to 20 mm 2 / s, more preferably 10 to 20 mm 2 / s. It is desirable to select a blending ratio.
The blending amounts of the components (B) to (D) are as described above, and the mass of the fatty acid ester of the polyhydric alcohol and the metal sulfonate (the total amount of the components (C) and (D)). The ratio (B): [(C) + (D)] is preferably in the range of 1: 1 to 1: 2.
本発明の加工兼用防錆油組成物は実質的にバリウムを含有しないことを特徴とする。実質的にバリウムを含有しないことにより、環境への負荷を低減することができる。ここで実質的にというのは、積極的にバリウムを添加するものではないことを意味し、微量に混入される不純物のバリウムまでを積極的に除去することを意図するものではない。通常、本発明の加工兼用防錆油組成物において、バリウムの含有量は、不純物のバリウムを考慮しても、５質量ｐｐｍ以下であり、さらには１質量ｐｐｍ以下である。 The processing and rust preventive oil composition of the present invention is characterized by containing substantially no barium. By containing substantially no barium, the burden on the environment can be reduced. Here, “substantially” means that barium is not actively added, and it is not intended to actively remove even barium, which is an impurity mixed in a trace amount. Usually, in the processing and rust preventive oil composition of the present invention, the content of barium is 5 ppm by mass or less, and further 1 ppm by mass or less even when the barium impurity is taken into consideration.
また、本発明の加工兼用防錆油組成物には、所望に応じ、本発明の目的を損なわない範囲で、酸化防止剤、金属不活性化剤等の各種添加剤を配合することができる。
酸化防止剤としては、２，６−ジ−ｔ−ブチルフェノール、２，６−ジ−ｔ−ブチル−ｐ−クレゾール等のフェノール系酸化防止剤、アルキル化ジフェニルアミン、フェニル−α−ナフチルアミンなどのアミン系酸化防止剤を用いることができる。
金属不活性剤としては、例えばベンゾトリアゾール、チアジアゾール、アルケニルコハク酸エステルやその誘導体等が挙げられる。
これらの添加剤の配合量は、通常、組成物基準で０．１〜１０質量％の範囲である。
Moreover, the processing combined rust preventive oil composition of the present invention can be blended with various additives such as an antioxidant and a metal deactivator as long as the purpose of the present invention is not impaired.
Antioxidants include phenolic antioxidants such as 2,6-di-t-butylphenol and 2,6-di-t-butyl-p-cresol, amines such as alkylated diphenylamine and phenyl-α-naphthylamine Antioxidants can be used.
Examples of the metal deactivator include benzotriazole, thiadiazole, alkenyl succinate and derivatives thereof.
The compounding amount of these additives is usually in the range of 0.1 to 10% by mass based on the composition.
本発明の加工兼用防錆油組成物を金属材料等に塗布する方法としては特に限定はなく、浸漬法、シャワー法、静電塗装法などの一般的な手法を用いることができる。 The method for applying the processing and rust preventive oil composition of the present invention to a metal material or the like is not particularly limited, and general methods such as an immersion method, a shower method, and an electrostatic coating method can be used.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
評価方法
（１）防錆性１（軒下曝露試験）；供試材として、ＪＩＳ Ｇ３１４１に準拠して、ＳＰＣＣ−ＳＤ（厚さ０．８ｍｍ）を用い、これに各実施例及び比較例にて調製した加工兼用防錆油組成物を塗油した。２４時間油きりをし、雨のかからない軒下に吊り下げて放置した。評価基準は以下のとおりである。
◎；６０日以上経過後でもさびは全く見られなかった。
○；３０〜６０日経過後にわずかにさびが発生した。
△；１４〜３０日経過後にさびが発生した。
×；１３日以内にさびが発生した。
（２）防錆性２（スタック試験）
上記と同様の供試材を６０×８０ｍｍに裁断し、各実施例及び比較例にて調製した加工兼用防錆油組成物を浸漬法により塗油した。２４時間油きりをし、５Ｃのφ１８５ｍｍのろ紙で梱包した。温度５０℃、相対湿度９５％で６０日間放置した後、さび及びステインの有無を目視にて観察した。評価基準は以下のとおりである。
○；さび及びステインが見られなかった。
×；さびあるいはステインが発生した。
（３）脱脂性
上記（２）と同様の供試材を各実施例及び比較例にて調製した加工兼用防錆油組成物に浸漬し、室内にて油きりをした後７日間放置した。脱脂液として「パーカーＦＣＥ２００１（２％）」を用い、これに各実施例及び比較例にて調製した加工兼用防錆油組成物を３０００質量ｐｐｍ添加して脱脂老化液を調製した。該脱脂老化液に試験片を４０℃で、３０秒浸漬し、１５秒間水洗して脱脂状態を確認した。脱脂の程度は脱脂後の鋼板の水濡れ面積（％）にて評価した。
（４）深絞り性
上記と同様の供試材（φ７０ｍｍ）に、各実施例及び比較例にて調製した加工兼用防錆油組成物を１．５〜２ｇ／ｍ2塗油し、ポンチとしてＳＫＤ１１硬質クロムメッキ（鏡面仕上げ、径３２φ、肩半径５Ｒ）、ダイスとしてＳＫＤ１１硬質クロムメッキ（鏡面仕上げ、径３４．４φ、肩半径５Ｒ）を用い、ポンチ速度１ｍｍ／ｓの条件で深絞り加工を行った。各しわ押さえ荷重での最大ポンチ荷重（ｔｆ）と破断時の絞り高さ（ｍｍ）を測定し、限界しわ押さえ荷重を算出した。評価基準は以下のとおりである。
◎；４ｔｆ以上
○；３〜４ｔｆ
△；２〜３ｔｆ
×；２ｔｆ以下
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Evaluation method (1) Rust prevention property 1 (Under eaves exposure test); SPCC-SD (thickness 0.8 mm) is used as a test material in accordance with JIS G3141, and in each of the examples and comparative examples, The prepared combined rust preventive oil composition was applied. Oiled for 24 hours and hung under the eaves where it doesn't rain. The evaluation criteria are as follows.
A: No rust was observed even after 60 days.
A: Rust slightly occurred after 30 to 60 days.
Δ: Rust occurred after 14 to 30 days.
X: Rust occurred within 13 days.
(2) Rust prevention 2 (stack test)
A test material similar to the above was cut into 60 × 80 mm, and the processing and rust preventive oil composition prepared in each of the Examples and Comparative Examples was applied by an immersion method. Oiled for 24 hours and packed with 5C φ185 mm filter paper. After leaving at a temperature of 50 ° C. and a relative humidity of 95% for 60 days, the presence or absence of rust and stain was visually observed. The evaluation criteria are as follows.
○: Rust and stain were not observed.
X: Rust or stain occurred.
(3) Degreasing property The test material similar to the above (2) was immersed in a processing and rust preventive oil composition prepared in each of the examples and comparative examples, drained indoors, and left for 7 days. “Parker FCE2001 (2%)” was used as the degreasing liquid, and 3000 mass ppm of the combined processing and rust preventive oil composition prepared in each Example and Comparative Example was added thereto to prepare a degreasing aging liquid. The test piece was immersed in the degreasing aging solution at 40 ° C. for 30 seconds and washed with water for 15 seconds to confirm the degreasing state. The degree of degreasing was evaluated by the water wetted area (%) of the steel sheet after degreasing.
(4) Deep drawability To the same test material (φ70 mm) as above, the processing and rust preventive oil composition prepared in each example and comparative example was applied in an amount of 1.5 to 2 g / m 2 , as a punch. SKD11 hard chrome plating (mirror finish, diameter 32φ, shoulder radius 5R), SKD11 hard chrome plating (mirror finish, diameter 34.4φ, shoulder radius 5R) as dies, deep drawing under conditions of punch speed 1mm / s went. The maximum punch load (tf) at each wrinkle holding load and the drawing height (mm) at break were measured, and the limit wrinkle holding load was calculated. The evaluation criteria are as follows.
◎; 4tf or more ○; 3-4tf
Δ: 2 to 3 tf
×: 2 tf or less
実施例１〜８及び比較例１〜８
第１表に示すように、（Ａ）基油に（Ｂ）〜（Ｄ）成分及び添加剤を配合し、加工兼用防錆油組成物を得、上記方法によって評価した。その結果を第１表に示す。
Examples 1-8 and Comparative Examples 1-8
As shown in Table 1, components (B) to (D) and additives were blended with (A) base oil to obtain a combined processing rust preventive oil composition, which was evaluated by the above method. The results are shown in Table 1.
（注）
＊１ 基油Ａ；パラフィン系鉱油、４０℃における動粘度５．０２５ｍｍ2／ｓ、環分析による分子量２２５、硫黄含有量０．０１質量％
＊２ 基油Ｂ；パラフィン系鉱油、４０℃における動粘度２０．５４ｍｍ2／ｓ、環分析による分子量３６３、硫黄含有量０．１５質量％
＊３ 基油Ｃ；ナフテン系鉱油、４０℃における動粘度１０１．４ｍｍ2／ｓ、環分析による分子量４０４、硫黄含有量０．０５４質量％
＊４ 基油Ｄ；パラフィン系鉱油、４０℃における動粘度４８０．２ｍｍ2／ｓ、環分析による分子量７０７、硫黄含有量０．９４質量％
(note)
* 1 Base oil A: paraffinic mineral oil, kinematic viscosity at 40 ° C. 5.025 mm 2 / s, molecular weight 225 by ring analysis, sulfur content 0.01% by mass
* 2 Base oil B: paraffinic mineral oil, kinematic viscosity at 40 ° C. 20.54 mm 2 / s, molecular weight 363 by ring analysis, sulfur content 0.15% by mass
* 3 Base oil C: naphthenic mineral oil, kinematic viscosity at 40 ° C. 101.4 mm 2 / s, molecular weight 404 by ring analysis, sulfur content 0.054% by mass
* 4 Base oil D: paraffinic mineral oil, kinematic viscosity at 40 ° C. 480.2 mm 2 / s, molecular weight 707 by ring analysis, sulfur content 0.94% by mass
＊５ トリメチロールプロパンエステルＡ（トリメチロールプロパントリオクチレート）；脂肪酸残基の炭素数 ８、分子中のＯＨ基なし、硫黄含有量 検出限界以下
＊６ トリメチロールプロパンエステルＢ（トリメチロールプロパントリラウリレート）；脂肪酸残基の炭素数 １２、分子中のＯＨ基なし、硫黄含有量 検出限界以下
＊７ トリメチロールプロパンエステルＣ（トリメチロールプロパントリオレエート）；脂肪酸残基の炭素数 １８、分子中のＯＨ基なし、硫黄含有量 検出限界以下
＊８ トリメチロールプロパンエステルＤ（トリメチロールプロパンジオレエート）；脂肪酸残基の炭素数 １８、分子中のＯＨ基 １個、硫黄含有量 検出限界以下
＊９ トリメチロールプロパンエステルＥ（トリメチロールプロパンモノオレエート）；脂肪酸残基の炭素数 １８、分子中のＯＨ基 ２個、硫黄含有量 検出限界以下
＊１０ 過塩基性カルシウムスルホネート；塩基価４０５ｍｇＫＯＨ／ｇ、バリウム含有量 検出限界以下、カルシウム含有量；２質量％
＊１１ 中性カルシウムスルホネート；塩基価２１．７ｍｇＫＯＨ／ｇ、バリウム含有量 検出限界以下、カルシウム含有量；１５質量％
＊１２ 酸化防止剤；２，６−ジ−ｔ−ブチル−ｐ−クレゾール（ＤＢＰＣ）
* 5 Trimethylolpropane ester A (trimethylolpropane trioctylate); carbon number of fatty acid residue 8, no OH group in molecule, sulfur content below detection limit * 6 Trimethylolpropane ester B (trimethylolpropane trilaurate) Rate); carbon number of fatty acid residue 12, no OH group in molecule, sulfur content below detection limit * 7 Trimethylolpropane ester C (trimethylolpropane trioleate); carbon number of fatty acid residue 18, in molecule No OH group, sulfur content below detection limit * 8 Trimethylolpropane ester D (trimethylolpropanediolate); 18 carbon atoms in fatty acid residue, 1 OH group in molecule, sulfur content below detection limit * 9 Trimethylolpropane ester E (trimethylolpropane monooleate); fat Carbon atoms of acid residues 18, two OH groups in the molecule, a sulfur content below the detection limit * 10 overbased calcium sulfonate; base number 405mgKOH / g, barium content undetectable, calcium content; 2 wt%
* 11 Neutral calcium sulfonate; base number 21.7 mgKOH / g, barium content Below detection limit, calcium content; 15% by mass
* 12 Antioxidant; 2,6-di-t-butyl-p-cresol (DBPC)
本発明の加工兼用防錆油組成物は、熱延鋼板、冷延鋼板、亜鉛メッキ鋼板に塗布して有効であり、防錆性、アルカリ脱脂剤等による脱脂性に優れる。また、潤滑性にも優れ、特に、亜鉛メッキ鋼板においては、亜鉛メッキの剥離を抑制して摩擦係数を低減し、かつ、現状の防錆油塗布ラインでそのままトラブルなく塗布することが可能である。さらには、防錆油が多量に混入したアルカリ脱脂液においても、優れた脱脂性を保つことができる上、バリウムをほとんど含有しないため環境負荷が小さい。 The processing and rust preventive oil composition of the present invention is effective when applied to a hot-rolled steel sheet, a cold-rolled steel sheet, and a galvanized steel sheet, and is excellent in rust prevention and degreasing properties with an alkaline degreasing agent or the like. In addition, it has excellent lubricity, especially in the case of galvanized steel sheets, it is possible to suppress galvanization peeling and reduce the coefficient of friction, and it can be applied without any trouble with the current rust preventive oil application line. . Furthermore, even in an alkaline degreasing solution mixed with a large amount of rust-preventing oil, excellent degreasing properties can be maintained, and the environmental load is small because it hardly contains barium.
Claims (6)
（Ａ）基油が（ａ）４０℃における動粘度が１．５〜１０ｍｍ2／ｓの低粘度基油と（ｂ）４０℃における動粘度が１０〜１００ｍｍ2／ｓの高粘度基油を、（ａ）成分：（ｂ）成分の質量比で１：２〜１：１５の範囲で混合したものであり、
（Ｂ）成分及び（Ｃ）成分が、組成物全量を基準として、それぞれ１〜２０質量％配合され、（Ｄ）成分が組成物全量を基準として金属分として０．０２〜０．１質量％配合され、かつ、（Ｂ）成分と、（Ｃ）成分及び（Ｄ）成分との質量比（Ｂ）：［（Ｃ）＋（Ｄ）］が、１：１〜１：２の範囲である加工兼用防錆油組成物。 (A) Mineral oil and / or synthetic oil having a kinematic viscosity at 40 ° C. of 4 to 50 mm 2 / s is used as the base oil, and (B) the number of carbon atoms of the fatty acid residue is 14 or more, and the number of OH groups in the molecule Is a fatty acid ester of a polyhydric alcohol having a ratio of less than 1, (C) an overbased metal sulfonate, and (D) a neutral metal sulfonate, and the barium content is 5 mass ppm or less based on the total amount of the composition. A rust preventive oil composition for processing and use,
(A) The base oil is (a) a low-viscosity base oil having a kinematic viscosity at 40 ° C. of 1.5 to 10 mm 2 / s and (b) a high-viscosity base oil having a kinematic viscosity at 40 ° C. of 10 to 100 mm 2 / s. , (A) component: (b) component is mixed at a mass ratio of 1: 2 to 1:15,
(B) component and (C) component are respectively mix | blended 1-20 mass% on the basis of the composition whole quantity, (D) component is 0.02-0.1 mass% as a metal part on the basis of the composition whole quantity. And the mass ratio (B): [(C) + (D)] of the component (B), the component (C) and the component (D) is in the range of 1: 1 to 1: 2. Anti-rust oil composition for processing.
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| JP7465765B2 (en) | 2019-10-16 | 2024-04-11 | Ｅｎｅｏｓ株式会社 | Rust-preventive oil composition |
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