JP4549965B2 - Rinsing agent composition for steel strip - Google Patents
Rinsing agent composition for steel strip Download PDFInfo
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- JP4549965B2 JP4549965B2 JP2005349001A JP2005349001A JP4549965B2 JP 4549965 B2 JP4549965 B2 JP 4549965B2 JP 2005349001 A JP2005349001 A JP 2005349001A JP 2005349001 A JP2005349001 A JP 2005349001A JP 4549965 B2 JP4549965 B2 JP 4549965B2
- Authority
- JP
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- Prior art keywords
- rinsing
- steel strip
- composition
- weight
- rinse
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- 229910000831 Steel Inorganic materials 0.000 title claims description 46
- 239000010959 steel Substances 0.000 title claims description 46
- 239000000203 mixture Substances 0.000 title claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 15
- 239000011976 maleic acid Substances 0.000 claims description 15
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 15
- 229920003169 water-soluble polymer Polymers 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000000129 anionic group Chemical group 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- -1 halogen ion Chemical class 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000000693 micelle Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002891 organic anions Chemical class 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 24
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000005238 degreasing Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000012459 cleaning agent Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 125000006353 oxyethylene group Chemical group 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000010960 cold rolled steel Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000010731 rolling oil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003669 anti-smudge Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 229920001778 nylon Polymers 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
- 125000000913 palmityl 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])[H] 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 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
- 238000004381 surface treatment Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/16—Metals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Electrochemistry (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Cleaning In General (AREA)
- Cleaning By Liquid Or Steam (AREA)
Description
本発明は、鋼帯の製造工程における鋼帯の洗浄後、好ましくはｐＨが５以上、更に好ましくはアルカリ洗浄後のリンス工程において使用されるリンス剤組成物、リンス方法及び該リンス工程を含む鋼帯の製造方法に関する。 The present invention relates to a rinsing agent composition, a rinsing method and a steel including the rinsing step used in the rinsing step after washing the steel strip in the steel strip production process, preferably at a pH of 5 or more, more preferably after alkaline washing. The present invention relates to a method for manufacturing a belt.
冷間圧延鋼板のような鋼帯の製造には、圧延後の鋼帯を洗浄する工程及び洗浄後の鋼帯をさらにリンスする工程を含む。洗浄工程は、例えば、ｐＨが１２以上のアルカリ洗浄液を用い鋼板表面上に付着する圧延油や鉄粉等の汚れ成分の除去を目的とし、リンス工程では、水又は温水を使用して、アルカリ洗浄処理で付着したアルカリ洗浄剤や除去しきれなかった鉄粉除去を目的とする。アルカリ洗浄液による洗浄工程は浸漬洗浄、電解洗浄、ブラシ洗浄、スプレー洗浄等の組み合わせにより構成され、リンス工程は浸漬リンス、ブラシリンス、スプレーリンス等の組み合わせにより構成されている。 Manufacturing a steel strip such as a cold rolled steel sheet includes a step of cleaning the steel strip after rolling and a step of further rinsing the steel strip after cleaning. The cleaning process is for the purpose of removing dirt components such as rolling oil and iron powder adhering to the steel sheet surface using an alkaline cleaning liquid having a pH of 12 or more. In the rinsing process, water or hot water is used to perform alkaline cleaning. The purpose is to remove the alkaline detergent adhering to the treatment and iron powder that could not be removed. The cleaning process using the alkaline cleaning liquid is configured by a combination of immersion cleaning, electrolytic cleaning, brush cleaning, spray cleaning, and the like, and the rinsing process is configured by a combination of immersion rinse, brush rinse, spray rinse, and the like.
鋼帯は、リンス工程後さらにはその後の焼鈍工程後に化成処理やメッキ処理等の表面処理がなされるため、リンス工程後の鋼帯表面の清浄性を確保することが非常に重要である。 Since the steel strip is subjected to a surface treatment such as a chemical conversion treatment or a plating treatment after the rinsing step and after the subsequent annealing step, it is very important to ensure the cleanliness of the steel strip surface after the rinsing step.
一方、近年、生産性向上のため、鋼帯の製造スピードの増大や、洗浄・リンス工程の水温低減の検討がなされている。 On the other hand, in recent years, studies have been made to increase the production speed of steel strips and to reduce the water temperature in the washing and rinsing process in order to improve productivity.
このような生産性向上措置に伴い、洗浄時間が短縮したり、洗浄効率が低下して、鋼帯の洗浄、なかでもｐＨが５以上、更にはアルカリ洗浄が不十分になれば、鋼帯は、その表面に油分、鉄粉等の汚れ成分を残存させたまま、リンス工程に進む。リンス工程では、ブラシやバクアップロールあるいはリンガーロールにその汚れが付着し、蓄積すると、鋼帯表面に汚れが再付着する場合がある。再付着した汚れを取り除くために、製造ラインを止めてブラシやロールを洗浄したり、交換する必要が生じたりしては、生産性の低下を招くため、当初の生産性向上を十分に達成できないことになる。 With such productivity improvement measures, if the cleaning time is shortened or the cleaning efficiency is reduced, the steel strip is washed, in particular, the pH is 5 or more, and further the alkaline cleaning is insufficient, the steel strip is Then, the rinsing process is proceeded with the oily components, iron powder and other dirt components remaining on the surface. In the rinsing step, dirt may adhere to the surface of the steel strip when the dirt adheres to and accumulates on the brush, the back-up roll, or the ringer roll. If it is necessary to stop the production line to clean or replace the brushes or rolls in order to remove the reattached dirt, the productivity will be reduced and the initial productivity improvement will not be sufficiently achieved. It will be.
特許文献１には、リンス処理時にアニオン性水溶性高分子を添加するスカム堆積防止方法が開示されている。 Patent Document 1 discloses a scum deposition preventing method in which an anionic water-soluble polymer is added during rinsing.
特許文献２には、界面活性剤と特定分子量の水溶性ポリカルボン酸を含有する金属洗浄用水溶液組成物が開示されている。
本発明の課題は、冷間圧延鋼板等の鋼帯の製造工程における洗浄工程、好ましくはｐＨが５以上、更に好ましくはアルカリ洗浄工程後のリンス工程において、汚れ成分の残留・蓄積を抑止し、低温でもリンス性に優れたリンス剤組成物、リンス方法及びそのリンス方法を含む鋼帯の製造方法を提供することである。 The problem of the present invention is to suppress the residual / accumulation of dirt components in the washing step in the production process of steel strips such as cold rolled steel sheets, preferably at a pH of 5 or more, more preferably in the rinsing step after the alkali washing step, It is providing the rinse agent composition excellent in the rinse property also at low temperature, the rinse method, and the manufacturing method of the steel strip containing the rinse method.
本発明は、（ａ）臨界ミセル濃度（２５℃）が０．０７％以下の界面活性剤〔以下、（ａ）成分という〕、（ｂ）アニオン性水溶性高分子〔以下、（ｂ）成分という〕及び（ｃ）水とを含有する鋼帯用リンス剤組成物であって、組成物中、（ａ）及び（ｂ）の合計量が０．００１〜７０重量％であり、（ａ）及び（ｂ）を合計で０．００１〜０．１重量％含有するリンス剤として用いるための鋼帯用リンス剤組成物に関する。 The present invention includes (a) a surfactant having a critical micelle concentration (25 ° C.) of 0.07% or less (hereinafter referred to as “component (a)”), (b) an anionic water-soluble polymer [hereinafter referred to as component (b). And (c) a rinsing agent composition for steel strips containing water, in which the total amount of (a) and (b) is 0.001 to 70% by weight, (a) And (b) a rinsing agent composition for a steel strip for use as a rinsing agent containing 0.001 to 0.1% by weight in total.
また、本発明は、（ａ）臨界ミセル濃度（２５℃）が０．０７％以下の界面活性剤、（ｂ）アニオン性水溶性高分子及び（ｃ）水のうち、１つ又は２つを含む組成物（イ）、
（ａ）、（ｂ）及び（ｃ）のうち、組成物（イ）に含まれない残りの１つ又は２つを含む組成物（ロ）、並びに
（ａ）、（ｂ）及び（ｃ）のうち、（イ）及び（ロ）に含まれないものがある場合、それを含む組成物（ハ）を含んでなるキットであって、（ａ）及び（ｂ）を合計で０．００１〜０．１重量％含有するリンス剤を得るための、鋼帯用リンス剤用キットに関する。
Further, the present invention provides one or two of (a) a surfactant having a critical micelle concentration (25 ° C.) of 0.07% or less, (b) an anionic water-soluble polymer, and (c) water. Containing composition (I),
(A), (b) and (c) a composition (b) containing the remaining one or two not included in the composition (a), and (a), (b) and (c) Among them, when there is something not included in (a) and (b), it is a kit comprising a composition (c) containing it, and (a) and (b) are added in a total of 0.001 to 0.001. The present invention relates to a steel strip rinse agent kit for obtaining a rinse agent containing 0.1% by weight.
また、本発明は、上記本発明の鋼帯用リンス剤組成物を、（ａ）及び（ｂ）の合計が０．００１〜０．１重量％となるように含有するリンス剤で、鋼帯を洗浄する、鋼帯のリンス方法に関する。 Moreover, this invention is a rinse agent which contains the rinse agent composition for steel strips of the said invention so that the sum total of (a) and (b) may be 0.001 to 0.1 weight%, The present invention relates to a method for rinsing a steel strip.
また、本発明は、上記本発明のリンス方法で鋼帯を洗浄する工程を含む、鋼帯の製造方法に関する。 Moreover, this invention relates to the manufacturing method of a steel strip including the process of wash | cleaning a steel strip with the rinse method of the said invention.
本発明によると、冷間圧延鋼板製造のアルカリ洗浄工程におけるリンス処理時において、アルカリ洗浄剤、圧延油や鉄粉などの汚れ成分の残留をなくして、リンス処理のブラシ、バックアップロールやリンガーロールへの汚れの蓄積を低減し、ブラシやロールの洗浄や交換頻度を減らし生産性を向上させる効果がある。また、リンス性を向上させるために60〜80℃に昇温しているリンス水の温度を低温化して、蒸気コストを削減できる効果がある。 According to the present invention, at the time of rinsing in the alkali cleaning step of cold rolled steel sheet production, residual alkaline components such as an alkaline cleaning agent, rolling oil and iron powder are eliminated, and a rinsing brush, backup roll and ringer roll are obtained. This reduces the accumulation of dirt and reduces the frequency of cleaning and replacement of brushes and rolls, thereby improving productivity. Moreover, in order to improve rinse property, there exists an effect which can lower | hang the temperature of the rinse water currently heated up to 60-80 degreeC, and can reduce vapor | steam cost.
本発明者等は、特定の界面活性剤〔（ａ）成分〕とアニオン性水溶性高分子の組合せが、リンス工程、好ましくはｐＨが５〜１２、さらに好ましくはｐＨが７〜１２のリンス工程での本発明の課題を解決できることを見出し、本発明を完成するに至った。 The inventors of the present invention have found that a combination of a specific surfactant [component (a)] and an anionic water-soluble polymer is a rinsing step, preferably a rinsing step having a pH of 5 to 12, more preferably a pH of 7 to 12. The inventors have found that the problems of the present invention can be solved, and have completed the present invention.
［（ａ）成分］
本発明の（ａ）成分は、油成分の洗浄性を確保する観点から、臨界ミセル濃度（２５℃）が０．０７％以下、好ましくは０．０５％以下、更に好ましくは０．０３％以下、好ましくは０．０００１％以上、より好ましくは０．００１％以上、更に好ましくは０．００３％以上の界面活性剤であり、中でも、下記一般式（１）で表わされる化合物が好ましい。
[(A) component]
The component (a) of the present invention has a critical micelle concentration (25 ° C.) of 0.07% or less, preferably 0.05% or less, more preferably 0.03% or less, from the viewpoint of ensuring the detergency of the oil component. The surfactant is preferably 0.0001% or more, more preferably 0.001% or more, and still more preferably 0.003% or more. Among them, the compound represented by the following general formula (1) is preferable.
Ｒ1Ｘ （１）
（式中、Ｒ1は炭素数８〜２０の直鎖若しくは分岐鎖のアルキル基又はアルケニル基、Ｘは−Ｏ−(ＡＯ)vＨ、
−ＣＯＯ−Ｍ、−ＳＯ3−Ｍ、−ＯＳＯ3−Ｍ、−Ｏ(ＡＯ)wＳＯ3−Ｍ、−Ｎ+Ｈ3・Ｂ-、−Ｎ+(ＣＨ3)3・Ｂ-、−Ｎ+(ＣＨ3)2(ＣＨ2)−ＣＯＯ-、−Ｎ(ＣＨ3)2Ｏ、ＡＯは炭素数２〜４のオキシアルキレン基、ｖ、ｗは平均付加モル数を示し、それぞれ１〜１００の数であり、ｖ、ｗ個のＡＯは同一でも異なっていても良い。Ｍはアルカリ金属、炭素数１〜４の脂肪族アミン、アンモニウム、またはアルカノールアミンを示し、Ｂ-はハロゲンイオン、無機または有機アニオンを示す。）
R 1 X (1)
(Wherein R 1 is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, X is —O— (AO) v H,
-COO-M, -SO 3 -M, -OSO 3 -M, -O (AO) w SO 3 -M, -N + H 3 · B -, -N + (CH 3) 3 · B -, - N + (CH 3 ) 2 (CH 2 ) —COO − , —N (CH 3 ) 2 O, AO is an oxyalkylene group having 2 to 4 carbon atoms, v and w are the average number of moles added, The number is 100, and v and w AOs may be the same or different. M represents an alkali metal, an aliphatic amine having 1 to 4 carbon atoms, ammonium or alkanolamine, and B − represents a halogen ion, an inorganic or organic anion. )
式（１）において、Ｒ1は炭素数８〜２０の直鎖若しくは分岐鎖のアルキル基又はアルケニル基であり、好ましくは炭素数８〜１８、更に好ましくは炭素数１０〜１８、特に好ましくは炭素数１２〜１８の直鎖若しくは分岐鎖のアルキル基又はアルケニル基である。アルキル基としては例えばオクチル基、２−エチルへキシル基、デシル基、ｓｅｃ−デシル基、ラウリル（ドデシル）基、ｓｅｃ−ラウリル基、ミリスチル基、セチル基、ステアリル基等が挙げられる。式（１）中、Ｒ1の炭素数は水への溶解性の点で２０以下であり、脱脂性の点で８以上である。 In the formula (1), R 1 is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 10 to 18 carbon atoms, particularly preferably carbon. It is a linear or branched alkyl group or alkenyl group of formula 12-18. Examples of the alkyl group include octyl group, 2-ethylhexyl group, decyl group, sec-decyl group, lauryl (dodecyl) group, sec-lauryl group, myristyl group, cetyl group, stearyl group and the like. In the formula (1), the carbon number of R 1 is 20 or less in terms of solubility in water and 8 or more in terms of degreasing properties.
また、式（１）中のｖ、ｗは、平均付加モル数を示し、それぞれ１〜１００の数であり、２〜５０の数が好ましく、２〜４０がより好ましい。ｖ、ｗは脱脂性の点で１以上であり、工業的な実用性の点で１００以下である。 Moreover, v and w in Formula (1) show an average addition mole number, are the numbers of 1-100, respectively, the number of 2-50 is preferable, and 2-40 are more preferable. v and w are 1 or more in terms of degreasing properties and 100 or less in terms of industrial practicality.
一般式（１）において、ＡＯは、オキシエチレン基、オキシプロピレン基、テトラメチレン基等の炭素数２〜４のオキシアルキレン基を意味する。これらのうち、オキシエチレン基、オキシプロピレン基が好ましい。ＡＯが複数種あってもよく、その場合はブロック結合、ランダム結合、交互結合など、いずれでもよい。ＡＯの炭素数は工業的な実用性から２〜４である。 In the general formula (1), AO means an oxyalkylene group having 2 to 4 carbon atoms such as an oxyethylene group, an oxypropylene group, and a tetramethylene group. Of these, oxyethylene groups and oxypropylene groups are preferred. There may be a plurality of types of AO. In that case, any of block coupling, random coupling, alternating coupling, and the like may be used. The carbon number of AO is 2 to 4 due to industrial practicality.
一般式（１）の化合物としては、以下の化合物が挙げられる。 Examples of the compound of the general formula (1) include the following compounds.
ＣjＨ2j+1−ＣＯＯＮａ（特にｊ＝１１の化合物）
ＣjＨ2j+1−ＯＳＯ3Ｎａ（特にｊ＝１８の化合物）
ＣjＨ2j+1−Ｎ+Ｈ3・ＣＨ3ＣＯＯ-（特にｊ＝１２の化合物）
ＣjＨ2j+1−Ｎ(ＣＨ3)2Ｏ（特にｊ＝１２の化合物）
（式中、ＥＯはオキシエチレン基、ｊは８〜２０の数、ｐは平均付加モル数であり１〜４０の数、ｑは平均付加モル数であり１〜２０の数である。）
C j H 2j + 1 -COONa (especially a compound with j = 11)
C j H 2j + 1 -OSO 3 Na ( especially compounds of j = 18)
C j H 2j + 1 -N + H 3 · CH 3 COO - ( in particular the compounds of j = 12)
C j H 2j + 1 —N (CH 3 ) 2 O (especially j = 12 compound)
(In the formula, EO is an oxyethylene group, j is a number of 8 to 20, p is an average added mole number and a number of 1 to 40, and q is an average added mole number and a number of 1 to 20.)
中でも一般式（２）の化合物が好ましい。
Ｒ1−Ｏ−(ＡＯ)xＨ （２）
（式中、Ｒ1は炭素数８〜２０の直鎖若しくは分岐鎖のアルキル基又はアルケニル基、ＡＯは炭素数２〜４のオキシアルキレン基、ｘは平均付加モル数を示し、１〜１００の数であり、ｘ個のＡＯは同一でも異なっていても良い。）
Among these, the compound of the general formula (2) is preferable.
R 1 —O— (AO) x H (2)
(In the formula, R 1 is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, x is an average added mole number, And the x AOs may be the same or different.)
一般式（２）中のＲ1、ＡＯの好ましいものは一般式（１）と同じであり、ｘの好ましい範囲もｖ、ｗと同じである。 Preferable R 1 and AO in the general formula (2) are the same as those in the general formula (1), and the preferable range of x is also the same as v and w.
一般式（２）で表される化合物として具体的には、以下のものが挙げられる。
ＣjＨ2j+1−Ｏ(ＥＯ)pＨ
ＣjＨ2j+1−Ｏ(ＥＯ)q(ＰＯ)rＨ、（但し、ＥＯとＰＯがブロック付加したもの）
ＣjＨ2j+1−Ｏ(ＰＯ)q(ＥＯ)rＨ、（但し、ＥＯとＰＯがブロック付加したもの）
ＣjＨ2j+1−Ｏ(ＥＯ)s(ＰＯ)t(ＥＯ)uＨ、（但し、ＥＯとＰＯがブロック付加したもの）
ＣjＨ2j+1−Ｏ(ＥＯ)q(ＰＯ)rＨ（但し、ＥＯとＰＯがランダム付加したもの）
（式中、ＥＯはオキシエチレン基（Ｃ2Ｈ4Ｏ）、ＰＯはオキシプロピレン基（Ｃ3Ｈ6Ｏ）、ｊは８〜２０の数、ｐ、ｑ、ｒ、ｓ、ｔ、ｕは、それぞれ平均付加モル数であり、ｐは３〜４０の数、ｑは１〜４０の数、ｒは１〜４０の数、ｓは１〜３０の数、ｔは１〜３０の数、ｕは１〜３０の数である。）
Specific examples of the compound represented by the general formula (2) include the following.
C j H 2j + 1 −O (EO) pH
C j H 2j + 1 −O (EO) q (PO) r H (however, EO and PO are added as a block)
C j H 2j + 1 -O (PO) q (EO) r H, (however, EO and PO added as a block)
C j H 2j + 1 -O (EO) s (PO) t (EO) u H (however, EO and PO are added as a block)
C j H 2j + 1 -O (EO) q (PO) r H (however, EO and PO are randomly added)
(Wherein EO is an oxyethylene group (C 2 H 4 O), PO is an oxypropylene group (C 3 H 6 O), j is a number from 8 to 20, p, q, r, s, t, u are , P is a number of 3-40, q is a number of 1-40, r is a number of 1-40, s is a number of 1-30, t is a number of 1-30, u Is a number from 1 to 30.)
本発明のリンス剤組成物には、１種又はそれ以上の（ａ）を用いることができる。 One or more types of (a) can be used in the rinse agent composition of the present invention.
（ａ）成分の臨界ミセル濃度は次の方法により測定されたものである。０．０００１重量％、０．００１重量％、０．０１重量％、０．１重量％、１重量％、１０重量％の界面活性剤水溶液の表面張力をＷｉｌｈｅｌｍｙ法により２５℃で測定する。いずれかの濃度を十倍したときの表面張力の低下率が５％以下となった場合、当該濃度とその１／１０の濃度の間を９等分した濃度の界面活性剤水溶液の表面張力をＷｉｌｈｅｌｍｙ法により２５℃で測定する。当該９等分した濃度の表面張力を対比し、隣り合う濃度の組み合わせにおいて表面張力の低下率が５％以下となるものの中から、最も低い濃度を選定し、これを臨界ミセル濃度（重量基準）とする。 The critical micelle concentration of component (a) is measured by the following method. The surface tension of 0.0001% by weight, 0.001% by weight, 0.01% by weight, 0.1% by weight, 1% by weight, and 10% by weight of a surfactant aqueous solution is measured at 25 ° C. by the Wilhelmy method. When the reduction rate of the surface tension when any concentration is multiplied by 10 becomes 5% or less, the surface tension of the surfactant aqueous solution having a concentration obtained by dividing the concentration between the concentration and 1/10 of the concentration into 9 equal parts is obtained. It is measured at 25 ° C. by the Wilhelmy method. Contrast the surface tension of the concentration divided into nine equal parts, and select the lowest concentration from those where the rate of decrease in surface tension is 5% or less in the combination of adjacent concentrations. This is the critical micelle concentration (weight basis) And
［（ｂ）成分］
本発明で、アニオン性水溶性高分子とは、イオン交換水で、解離して負電荷のイオン雰囲気を形成し、２５℃において水１００ｇに対して１０ｇ以上溶解するものをいう。
[Component (b)]
In the present invention, the anionic water-soluble polymer means a substance that is dissociated with ion-exchanged water to form a negatively charged ion atmosphere and is dissolved in 100 g of water at 25 ° C. in an amount of 10 g or more.
本発明に用いるアニオン性水溶性高分子としては、脱スマッジ性の観点から、ポリカルボン酸系、ポリスルホン酸系が好ましく、中でも、ポリカルボン酸系が好ましい。 The anionic water-soluble polymer used in the present invention is preferably a polycarboxylic acid type or a polysulfonic acid type from the viewpoint of de-smudge property, and among them, a polycarboxylic acid type is preferable.
ポリカルボン酸系水溶性高分子としては、ポリ（メタ）アクリル酸、ポリヒドロキシ（メタ）アクリル酸、（メタ）アクリル酸とマレイン酸とのコポリマー等の（メタ）アクリル酸コポリマー、オレフィンとマレイン酸とのコポリマー、マレイン酸とアリルアルコールのエチレンオキサイド（ＥＯ）、プロピレンオキサイド（ＰＯ）等のアルキレンオキサイド付加物とのコポリマー、アリルスルホン酸とマレイン酸とのコポリマー等が挙げられる。ここで「（メタ）アクリル酸」とは、アクリル酸又はメタクリル酸を意味する。これらのアニオン性水溶性高分子のうち、ポリアクリル酸、ポリヒドロキシアクリル酸、アクリル酸／マレイン酸コポリマー、オレフィン／マレイン酸コポリマー、マレイン酸／アリルアルコールアルキレンオキサイド付加物コポリマー、アリルスルホン酸／マレイン酸コポリマーが好ましく、より好ましくはポリヒドロキシアクリル酸、アクリル酸／マレイン酸コポリマー、オレフィン／マレイン酸コポリマーであり、特に好ましくは、オレフィン／マレイン酸コポリマーである。 Polycarboxylic acid-based water-soluble polymers include poly (meth) acrylic acid, polyhydroxy (meth) acrylic acid, (meth) acrylic acid copolymers such as copolymers of (meth) acrylic acid and maleic acid, olefins and maleic acid A copolymer of maleic acid and allyl alcohol with an alkylene oxide adduct such as ethylene oxide (EO) and propylene oxide (PO), a copolymer of allyl sulfonic acid and maleic acid, and the like. Here, “(meth) acrylic acid” means acrylic acid or methacrylic acid. Among these anionic water-soluble polymers, polyacrylic acid, polyhydroxyacrylic acid, acrylic acid / maleic acid copolymer, olefin / maleic acid copolymer, maleic acid / allyl alcohol alkylene oxide adduct copolymer, allyl sulfonic acid / maleic acid Preferred are copolymers, more preferred are polyhydroxyacrylic acid, acrylic acid / maleic acid copolymers, olefin / maleic acid copolymers, and particularly preferred are olefin / maleic acid copolymers.
アニオン性水溶性高分子の分子量（重量平均）は、リンス性及び鉄粉除去性の観点から、１０００以上が好ましく、水への溶解速度の低下による、鋼板表面への残留を抑止する観点から、５００００以下が更に好ましい。特に好ましくは１０００以上２００００以下である。この分子量は、後述の実施例記載の方法により測定されたものである。 The molecular weight (weight average) of the anionic water-soluble polymer is preferably 1000 or more from the viewpoint of rinsing properties and iron powder removability, and from the viewpoint of suppressing the residual on the steel sheet surface due to a decrease in the dissolution rate in water, More preferably, it is 50000 or less. Most preferably, it is 1000 or more and 20000 or less. This molecular weight is measured by the method described in the examples below.
本発明の組成物は、（ａ）成分の油洗浄性と（ｂ）成分の汚れ分散性を適切に確保する観点から、（ａ）成分と（ｂ）成分とを合計で０．００１〜７０重量％、好ましくは０．０１〜５０重量％、より好ましくは１〜３０重量％含有する。この合計量は、組成物の用途、形態などに応じて変更できる。また、本発明の組成物は、（ａ）成分及び（ｂ）成分を合計で０．００１〜０．１重量％、好ましくは０．００５〜０．０５重量％含有するリンス剤として用いるための組成物である。 The composition of the present invention comprises (a) component and (b) component in total from 0.001 to 70 from the viewpoint of appropriately securing the oil detergency of component (a) and soil dispersibility of component (b). % By weight, preferably 0.01 to 50% by weight, more preferably 1 to 30% by weight. This total amount can be changed according to the use and form of the composition. Moreover, the composition of the present invention is used as a rinse agent containing (a) component and (b) component in a total amount of 0.001 to 0.1% by weight, preferably 0.005 to 0.05% by weight. It is a composition.
本発明のリンス剤組成物では、（ａ）成分と（ｂ）成分の重量比は、（ａ）／（ｂ）＝７０／３０〜３０／７０、更に６０／４０〜４０／６０であることが、脱脂性と脱スマッジ性を両立し、最小添加量で効率よくブラシへの汚れ付着を防止する点で好ましい。 In the rinse agent composition of the present invention, the weight ratio of the component (a) to the component (b) is (a) / (b) = 70/30 to 30/70, more preferably 60/40 to 40/60. However, it is preferable in terms of achieving both the degreasing property and the de-smudge property and efficiently preventing the adhesion of dirt to the brush with the minimum addition amount.
本発明のリンス剤組成物は、そのまま、あるいは適当な濃度に水等で希釈したリンス剤、特に、（ａ）成分及び（ｂ）成分を合計で０．００１〜０．１重量％、好ましくは０．００５〜０．０５重量％含有するリンス剤として、リンス工程、好ましくはｐＨが５〜１２、更に好ましくはｐＨが７〜１２のリンス工程で好適に用いられる。従って、本発明のリンス剤組成物から調製されるリンス剤のｐＨも、好ましくはｐＨが５〜１２、更に好ましくはｐＨが７〜１２である。このようなリンス剤は本発明のキットから調製できる。 The rinse agent composition of the present invention is a rinse agent which is diluted as it is or with an appropriate concentration with water or the like, and in particular, the total amount of the component (a) and the component (b) is 0.001 to 0.1% by weight, preferably As a rinse agent containing 0.005 to 0.05 weight%, it is used suitably at the rinse process, Preferably pH is 5-12, More preferably, the rinse process is pH 7-12. Therefore, the pH of the rinse agent prepared from the rinse agent composition of the present invention is preferably 5 to 12, more preferably 7 to 12. Such a rinse agent can be prepared from the kit of the present invention.
本発明のリンス剤組成物を用いたリンス方法は、鋼帯の製造方法の工程に組み込むことができる。鋼帯の製造方法は、洗浄工程を含むことができ、この洗浄工程では、例えば特開平１０−２８０１７９号公報、特開平１０−３２４９００号公報に記載されているアルカリ洗浄剤を好ましく用いることができる。具体的には、下記の洗浄剤（１）、（２）、（３）が挙げられる。 The rinsing method using the rinsing agent composition of the present invention can be incorporated in the steps of the steel strip manufacturing method. The manufacturing method of the steel strip can include a cleaning step. In this cleaning step, for example, an alkaline cleaner described in JP-A-10-280179 and JP-A-10-324900 can be preferably used. . Specifically, the following cleaning agents (1), (2), and (3) may be mentioned.
＜洗浄剤（１）＞
(A)下記一般式（Ｉ）〜(III)で表される非イオン界面活性剤の１種以上、及び(B)アルカリ剤を含有する洗浄剤。
R1O-(EO)x1-(PO)y1-(EO)x2-H （Ｉ）
R2O-[EOx3/POy2]-(EO)x4-H (II)
R3O-(EO)x5-[EOx6/POy3]-(PO)y4-[EOx7/POy5]-(EO)x8-H (III)
〔式中、R1, R2及びR3は炭素数６〜24の直鎖又は分岐鎖のアルキル基又はアルケニル基を示し、EOはオキシエチレン基、POはオキシプロピレン基を示す。x1, x2, x3, x4, x5, x6, x7及びx8はエチレンオキサイドの平均付加モル数を示す数で、x1, x2, x3, x4, x5及びx8はそれぞれ１以上の数、x1＋x2≧４、x3＋x4≧４、x5＋x6＋x7＋x8≧４、x6＋x7≧１である。y1, y2, y3, y4及びy5はプロピレンオキサイドの平均付加モル数を示す数で、０＜y1＜x1＋x2、０＜y2＜x3＋x4、y3＋y5≧１、y3≧０、y4≧０、y5≧０、y3＋y4＋y5＜x5＋x6＋x7＋x8である。また、[ ]で囲まれた部分はランダム付加、（ ）で囲まれた部分はブロック付加であることを示す。〕
<Cleaning agent (1)>
(A) A cleaning agent containing at least one nonionic surfactant represented by the following general formulas (I) to (III) and (B) an alkaline agent.
R 1 O- (EO) x1- (PO) y1- (EO) x2 -H (I)
R 2 O- [EO x3 / PO y2 ]-(EO) x4 -H (II)
R 3 O- (EO) x5- [EO x6 / PO y3 ]-(PO) y4- [EO x7 / PO y5 ]-(EO) x8 -H (III)
[Wherein R 1 , R 2 and R 3 represent a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. x1, x2, x3, x4, x5, x6, x7 and x8 are numbers indicating the average added mole number of ethylene oxide, and x1, x2, x3, x4, x5 and x8 are each a number of 1 or more, x1 + x2 ≧ 4, x3 + x4 ≧ 4, x5 + x6 + x7 + x8 ≧ 4, and x6 + x7 ≧ 1. y1, y2, y3, y4 and y5 are numbers indicating the average added mole number of propylene oxide, 0 <y1 <x1 + x2, 0 <y2 <x3 + x4, y3 + y5 ≧ 1, y3 ≧ 0, y4 ≧ 0, y5 ≧ 0, y3 + y4 + y5 <x5 + x6 + x7 + x8. In addition, a portion surrounded by [] indicates random addition, and a portion surrounded by () indicates block addition. ]
＜洗浄剤（２）＞
アルカリ剤と、下記一般式（Ａ）に示すポリオキシエチレンアルキルエーテルの少なくとも１種とを含む洗浄剤。
Ｒ−Ｏ−(ＣＨ2ＣＨ2Ｏ)nＨ （Ａ）
（式中、Ｒは炭素数５〜12の直鎖又は分岐鎖のアルキル基又はアルケニル基、ｎはオキシエチレン基の平均付加モル数を表し、Ｒが炭素数５〜10である場合にはｎは１〜20、Ｒが炭素数11〜12の場合にはｎは６〜20である）
<Cleaning agent (2)>
A cleaning agent comprising an alkali agent and at least one polyoxyethylene alkyl ether represented by the following general formula (A).
R—O— (CH 2 CH 2 O) n H (A)
(In the formula, R represents a linear or branched alkyl group or alkenyl group having 5 to 12 carbon atoms, n represents the average number of added moles of the oxyethylene group, and when R is 5 to 10 carbon atoms, n represents Is 1 to 20, and when R is 11 to 12 carbon atoms, n is 6 to 20)
＜洗浄剤（３）＞
アルカリ剤と、一般式（Ａ）に示すポリオキシエチレンアルキルエーテルの少なくとも１種と、下式（Ｂ）に示す水溶性高分子カルボン酸類の少なくとも１種とを含む洗浄剤。
Ｒ−Ｏ−(ＣＨ2ＣＨ2Ｏ)nＨ （Ａ）
（式中、Ｒは炭素数５〜12の直鎖又は分岐鎖のアルキル基又はアルケニル基、ｎはオキシエチレン基の平均付加モル数を表し、Ｒが炭素数５〜10である場合にはｎは１〜20、Ｒが炭素数11〜12の場合にはｎは６〜20である）
<Cleaning agent (3)>
A cleaning agent comprising an alkali agent, at least one polyoxyethylene alkyl ether represented by the general formula (A), and at least one water-soluble polymer carboxylic acid represented by the following formula (B).
R—O— (CH 2 CH 2 O) n H (A)
(In the formula, R represents a linear or branched alkyl group or alkenyl group having 5 to 12 carbon atoms, n represents the average number of added moles of the oxyethylene group, and when R is 5 to 10 carbon atoms, n represents Is 1 to 20, and when R is 11 to 12 carbon atoms, n is 6 to 20)
（式中、
Ｒ1b〜Ｒ6b：水素原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシル基、ＣＯＯＭ、又はＯＨ
Ｍ：水素原子、アルカリ金属、炭素数１〜４のアルキルアミン、又は炭素数１〜６のアルカノールアミン
ｍ／ｎ（共重合モル比）：０／10〜10／１
重量平均分子量（Ｍｗ）：1,000〜100,000）
(Where
R 1b to R 6b : a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, COOM, or OH
M: a hydrogen atom, an alkali metal, an alkylamine having 1 to 4 carbon atoms, or an alkanolamine having 1 to 6 carbon atoms (copolymerization molar ratio): 0/10 to 10/1
Weight average molecular weight (Mw): 1,000-100,000)
実施例１〜１８及び比較例１〜１５
下記の表１〜２に示す組成のリンス剤組成物をそれぞれ調製し、脱脂性、脱スマッジ性、及びブラシへの汚れ付着防止性を次のように評価した。結果を表１〜２に示す。
Examples 1-18 and Comparative Examples 1-15
Rinse agent compositions having the compositions shown in Tables 1 and 2 below were prepared, and degreasing properties, de-smudge properties, and anti-smudge properties on brushes were evaluated as follows. The results are shown in Tables 1-2.
（１）試験鋼帯用鋼板
洗浄前残存炭素量が170ｍｇ/ｍ2、残存鉄粉量が170ｍｇ/ｍ2の冷間圧延鋼板を使用した。
(1) Steel plate for test steel strip A cold-rolled steel plate having a residual carbon amount before cleaning of 170 mg / m 2 and a residual iron powder amount of 170 mg / m 2 was used.
（２）洗浄条件
上記冷間圧延鋼板を縦７ｃｍ、横１０ｃｍにカットした厚さ０．７ｍｍの試験鋼帯を以下の条件でアルカリ洗浄剤にて浸漬洗浄し、さらに電解洗浄した。
・アルカリ洗浄剤：ＮａＯＨ２重量％と添加剤１重量％と水９７重量％からなる水溶液（添加剤組成：ＮａＯＨ１重量％、グルコン酸ナトリウム１５重量％、エチレンジアミン４酢酸ナトリウム５重量％、ポリオキシアルキレンノニルフェニルエーテル（ＥＯの平均付加モル数：１３モル）１０重量％、ポリアクリル酸ナトリウム５重量％、水６４重量％）
・浸漬洗浄：７０℃ 浸漬時間２秒
・電解洗浄：７０℃ 電解時間０．８秒 電流密度１４Ａ／ｄｍ2
(2) Washing conditions A test steel strip having a thickness of 0.7 mm obtained by cutting the cold-rolled steel sheet into a length of 7 cm and a width of 10 cm was immersed and washed with an alkaline detergent under the following conditions, and further electrolytically washed.
-Alkaline detergent: aqueous solution consisting of 2% by weight NaOH, 1% by weight additive and 97% by weight water (additive composition: 1% by weight NaOH, 15% by weight sodium gluconate, 5% by weight ethylenediaminetetraacetate, polyoxyalkylene nonyl) Phenyl ether (average number of moles of EO added: 13 moles) 10% by weight, sodium polyacrylate 5% by weight, water 64% by weight)
・ Immersion cleaning: 70 ° C. Immersion time 2 seconds • Electrolytic cleaning: 70 ° C. Electrolysis time 0.8 seconds Current density 14 A / dm 2
（３）リンス条件
試験鋼帯を、電解洗浄槽から引き上げた後、ヒーターで所定の温度に加温したリンス剤組成物をスプレーしながら、ブラシ試験機によるブラシリンスを行った。その後、７０℃の温水に２秒浸漬し、仕上げリンスを行い、試験鋼帯の表面が乾燥するまで、ドライヤーで温風乾燥した。
・スプレーリンス：流量4.5Ｌ／ｍｉｎ（所定の温度に加温）
・ブラシリンス：ブラシ試験機（昭和工業（株）製）ナイロンブラシ、３００回転／分、圧下量１ｍｍ、鋼板送り速度70ｍ／ｍｉｎ、１パス
(3) Rinsing conditions After the test steel strip was pulled up from the electrolytic cleaning tank, brush rinsing with a brush tester was performed while spraying a rinse agent composition heated to a predetermined temperature with a heater. Then, it was immersed in warm water at 70 ° C. for 2 seconds, finished rinsing, and dried with warm air until the surface of the test steel strip was dried.
-Spray rinsing: Flow rate 4.5L / min (warming to a predetermined temperature)
・ Brush rinse: Brush tester (made by Showa Kogyo Co., Ltd.) nylon brush, 300 rotations / minute, reduction amount 1 mm, steel sheet feed speed 70 m / min, 1 pass
（４）脱脂性
温風乾燥後の試験鋼板を、25ｍｍ×50ｍｍにカットしてカーボンメーター（EMIA−111 CARBON ANALYZER（堀場製作所（株）製））で残存炭素量を測定した。
(4) Degreasing property The test steel sheet after drying with hot air was cut into 25 mm × 50 mm, and the residual carbon content was measured with a carbon meter (EMIA-111 CARBON ANALYZER (manufactured by Horiba, Ltd.)).
（５）脱スマッジ性
温風乾燥後の試験鋼帯の表面に残る鉄粉を脱脂綿により拭き取り、その脱脂綿を湿式分解した後、プラズマ発光分析により鉄分濃度を測定し、鉄分量を求めた。そして単位面積あたりの鉄粉残留量を脱スマッジ性の指標とした。
(5) Desmudge property The iron powder remaining on the surface of the test steel strip after hot air drying was wiped off with absorbent cotton, the absorbent cotton was wet-decomposed, and then the iron concentration was measured by plasma emission analysis to determine the iron content. The residual amount of iron powder per unit area was used as an indicator of desmudgeability.
（６）ブラシへの汚れの付着防止性
（２）と同様の条件で洗浄した３０枚の試験鋼板を、（３）と同様にリンスした後のブラシの汚れ具合を目視で評価した。
ブラシ汚れ評価基準
○；ほとんど汚れがない。
△；少し汚れている。
×；かなり汚れている。
(6) Preventing adhesion of dirt to the brush The brush dirt condition after rinsing the 30 test steel plates washed under the same conditions as in (2) in the same manner as in (3) was visually evaluated.
Brush dirt evaluation standard ○: There is almost no dirt.
Δ: Slightly dirty
X: It is quite dirty.
表中、界面活性剤について、Ｃの次の数字は一般式（１）の化合物におけるアルキル基の炭素数であり、ＥＯ、ＰＯの次の（ ）内の数字は平均付加モル数である。また、高分子化合物について、ＡＡはアクリル酸、ＭＡＮは無水マレイン酸を示し、（ ）内はコポリマーの共重合モル比である。また、Ｍｗは重量平均分子量であり、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、以下の条件で求めた。 In the table, for the surfactant, the number next to C is the number of carbon atoms of the alkyl group in the compound of the general formula (1), and the number in parentheses next to EO and PO is the average number of moles added. Moreover, about a high molecular compound, AA shows acrylic acid, MAN shows maleic anhydride, The inside of () is a copolymerization molar ratio of a copolymer. Moreover, Mw is a weight average molecular weight, and it calculated | required on condition of the following by gel permeation chromatography (GPC).
＜ＧＰＣ条件＞
・カラム：ＴＳＫ ＰＷＸＬ＋Ｇ４０００ＰＷＸＬ＋Ｇ２５００ＰＷＸＬ（いずれも東ソー株式会社製）
・カラム温度：４０℃
・検出器：ＲＩ又はＵＶ（２１０ｎｍ）
・溶離液：０．２ｍｏｌ／Ｌ リン酸緩衝液／アセトニトリル（９／１）
・流速：１．０ｍＬ／ｍｉｎ
・注入量：０．１ｍＬ
・標準：ポリエチレングリコール
<GPC conditions>
Column: TSK PWXL + G4000PWXL + G2500PWXL (both manufactured by Tosoh Corporation)
-Column temperature: 40 ° C
Detector: RI or UV (210 nm)
Eluent: 0.2 mol / L phosphate buffer / acetonitrile (9/1)
・ Flow rate: 1.0 mL / min
・ Injection volume: 0.1 mL
・ Standard: Polyethylene glycol
表１〜２から明らかなように、本発明のリンス剤組成物を使用した実施例１〜１３では、脱脂性、脱スマッジ性、ブラシへの付着性性のいずれも優れていた。また、リンス温度を５０℃にした実施例１４、２５℃にした実施例１５〜１８も脱脂性、脱スマッジ性、ブラシへの付着性性のいずれも優れていた。これに対して、水のみでリンスした比較例１〜３は脱脂性、脱スマッジ性、ブラシの汚れ付着性のいずれの性能も不十分であった。また、リンス温度を低温化するほど性能は低下した。界面活性剤のみ添加した比較例４、５、１０では脱脂性は比較的優れていたが脱スマッジ性が不十分であり、ブラシの汚れ付着性も劣っていた。また、水溶性高分子のみを添加した比較例６、７、１１は脱スマッジ性は向上したが脱脂性は不十分であり、ブラシ付着性も劣っていた。（ａ）成分でない界面活性剤と、（ｂ）成分との組合せである比較例８、１２、１４、１５では脱スマッジ性は向上したが脱脂性は不十分であり、ブラシ付着性も劣っていた。また、（ａ）成分と、（ｂ）成分でない水溶性高分子との組合せである比較例９、１３では脱脂性は比較的優れていたが脱スマッジ性が不十分であり、ブラシの汚れ付着性も劣っていた。 As is clear from Tables 1 and 2, in Examples 1 to 13 using the rinse agent composition of the present invention, all of the degreasing property, the de-smudge property, and the adhesion property to the brush were excellent. In addition, Example 14 in which the rinse temperature was set to 50 ° C. and Examples 15 to 18 in which the rinse temperature was set to 25 ° C. were all excellent in degreasing property, de-smudge property, and adhesion property to the brush. On the other hand, Comparative Examples 1 to 3 rinsed only with water were insufficient in all of the performances of degreasing property, de-smudge property, and brush dirt adhesion. Moreover, the performance decreased as the rinse temperature was lowered. In Comparative Examples 4, 5, and 10 in which only the surfactant was added, the degreasing property was relatively excellent, but the de-smudge property was insufficient, and the dirt adhesion of the brush was also inferior. In Comparative Examples 6, 7, and 11 to which only the water-soluble polymer was added, the de-smudge property was improved, but the degreasing property was insufficient and the brush adhesion property was inferior. In Comparative Examples 8, 12, 14, and 15, which are combinations of a surfactant that is not the component (a) and the component (b), the de-smudge property is improved, but the degreasing property is insufficient, and the brush adhesion is also inferior. It was. In Comparative Examples 9 and 13, which are a combination of the component (a) and the water-soluble polymer that is not the component (b), the degreasing property was relatively excellent, but the de-smudge property was insufficient, and the dirt on the brush was adhered. The property was also inferior.
Claims (8)
Ｒ1Ｘ （１）
（式中、Ｒ1は炭素数８〜２０の直鎖若しくは分岐鎖のアルキル基又はアルケニル基、Ｘは−Ｏ−(ＡＯ)vＨ、
−ＣＯＯ−Ｍ、−ＳＯ3−Ｍ、−ＯＳＯ3−Ｍ、−Ｏ(ＡＯ)wＳＯ3−Ｍ、−Ｎ+Ｈ3・Ｂ-、−Ｎ+(ＣＨ3)3・Ｂ-、−Ｎ+(ＣＨ3)2(ＣＨ2)−ＣＯＯ-、−Ｎ(ＣＨ3)2Ｏ、ＡＯは炭素数２〜４のオキシアルキレン基、ｖ、ｗは平均付加モル数を示し、それぞれ１〜１００の数であり、ｖ、ｗ個のＡＯは同一でも異なっていても良い。Ｍはアルカリ金属、炭素数１〜４の脂肪族アミン、アンモニウム、またはアルカノールアミンを示し、Ｂ-はハロゲンイオン、無機または有機アニオンを示す。） The rinsing agent composition for steel strip according to claim 1, wherein (a) the surfactant is represented by the following general formula (1).
R 1 X (1)
(Wherein R 1 is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, X is —O— (AO) v H,
-COO-M, -SO 3 -M, -OSO 3 -M, -O (AO) w SO 3 -M, -N + H 3 · B -, -N + (CH 3) 3 · B -, - N + (CH 3 ) 2 (CH 2 ) —COO − , —N (CH 3 ) 2 O, AO is an oxyalkylene group having 2 to 4 carbon atoms, v and w are the average number of moles added, The number is 100, and v and w AOs may be the same or different. M represents an alkali metal, an aliphatic amine having 1 to 4 carbon atoms, ammonium or alkanolamine, and B − represents a halogen ion, an inorganic or organic anion. )
（ａ）、（ｂ）及び（ｃ）のうち、組成物（イ）に含まれない残りの１つ又は２つを含む組成物（ロ）、並びに
（ａ）、（ｂ）及び（ｃ）のうち、（イ）及び（ロ）に含まれないものがある場合、それを含む組成物（ハ）を含んでなるキットであって、（ａ）及び（ｂ）を合計で０．００１〜０．１重量％含有するリンス剤を得るための、鋼帯用リンス剤用キット。 A composition comprising (a) one or two of a surfactant having a critical micelle concentration (25 ° C.) of 0.07% or less, (b) an anionic water-soluble polymer, and (c) water (A) ,
(A), (b) and (c) a composition (b) containing the remaining one or two not included in the composition (a), and (a), (b) and (c) Among them, when there is something not included in (a) and (b), it is a kit comprising a composition (c) containing it, and (a) and (b) are added in a total of 0.001 to 0.001. A steel strip rinse agent kit for obtaining a rinse agent containing 0.1% by weight.
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| US20130085093A1 (en) * | 2010-05-14 | 2013-04-04 | Yuken Industry Co., Ltd. | Aqueous cleaning agent composition |
| JP5843355B2 (en) * | 2011-12-27 | 2016-01-13 | 花王株式会社 | Steel sheet cleaner |
| JP5851323B2 (en) * | 2012-04-20 | 2016-02-03 | ライオン株式会社 | Liquid cleaning agent |
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| JPH0450393B2 (en) * | 1987-10-26 | 1992-08-14 | Kao Corp | |
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| JP2005126553A (en) * | 2003-10-23 | 2005-05-19 | Kao Corp | Hard surface cleanser composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0450393B2 (en) * | 1987-10-26 | 1992-08-14 | Kao Corp | |
| JPH06299200A (en) * | 1993-04-13 | 1994-10-25 | Lion Corp | Rinsing agent and method for finish-washing |
| JPH10292195A (en) * | 1997-04-17 | 1998-11-04 | Lion Corp | Acidic cleaner composition |
| JP2003145193A (en) * | 2001-11-15 | 2003-05-20 | Kao Corp | Method for preventing scum deposition |
| JP2004091686A (en) * | 2002-08-30 | 2004-03-25 | Dai Ichi Kogyo Seiyaku Co Ltd | Nonionic surfactant composition |
| JP2005126553A (en) * | 2003-10-23 | 2005-05-19 | Kao Corp | Hard surface cleanser composition |
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