JP2014205758A - Cleaning agent composition, cleaning agent comprising the same, and cleaning method using those - Google Patents
Cleaning agent composition, cleaning agent comprising the same, and cleaning method using those Download PDFInfo
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- JP2014205758A JP2014205758A JP2013083473A JP2013083473A JP2014205758A JP 2014205758 A JP2014205758 A JP 2014205758A JP 2013083473 A JP2013083473 A JP 2013083473A JP 2013083473 A JP2013083473 A JP 2013083473A JP 2014205758 A JP2014205758 A JP 2014205758A
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- Prior art keywords
- cleaning
- cyclodextrin
- cleaning composition
- acid
- composition according
- Prior art date
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- 238000004140 cleaning Methods 0.000 title claims abstract description 140
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 87
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000002738 chelating agent Substances 0.000 claims abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 9
- 150000002334 glycols Chemical class 0.000 claims abstract description 6
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 19
- 239000004033 plastic Substances 0.000 claims description 19
- 229920003023 plastic Polymers 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 102000004169 proteins and genes Human genes 0.000 claims description 12
- 108090000623 proteins and genes Proteins 0.000 claims description 12
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229940097362 cyclodextrins Drugs 0.000 claims description 8
- 239000008280 blood Substances 0.000 claims description 7
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
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- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 4
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- 238000003860 storage Methods 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
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Landscapes
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Abstract
Description
本発明は、タール状物質を含む各種スケール及び医療用器具の洗浄剤組成物及びその組成物を含有する洗浄剤並びにそれらを用いた洗浄方法に関し、さらに詳しくは重油を含む化学品貯曹タンク、熱交換器、機械部品、車両部品、ボイラ等の油分接触面及び水乃至は冷媒接触面に付着するタール状物質を含む各種スケールさらには電子材料、加工金属部品、プラスチック部品、液晶パネル部材、光学ガラスレンズ、ハードデスクの表面に生じる各種のスケール乃至は使用済み医療器具に付着するタンパク質、脂肪、血液、油、無機物、錆び等を除去するための洗浄剤組成物及びその組成物を含有する洗浄剤並びにそれらを用いた洗浄方法に関するものである。 The present invention relates to a cleaning composition for various scales and medical instruments containing tar-like substances, a cleaning composition containing the composition, and a cleaning method using the same, and more particularly a chemical storage tank containing heavy oil, Various scales containing tar-like substances adhering to oil contact surfaces and water or refrigerant contact surfaces of heat exchangers, machine parts, vehicle parts, boilers, etc., as well as electronic materials, processed metal parts, plastic parts, liquid crystal panel members, optics Cleaning composition containing glass lens, various scales generated on the surface of hard disk or protein, fat, blood, oil, inorganic substance, rust, etc. adhering to used medical equipment and cleaning containing the composition The present invention relates to an agent and a cleaning method using them.
各種化学プラント、熱交換器、加熱機器付近の反応容器、配管など常時、化学品原料、反応物、冷却水、冷媒に接触する金属材表面乃至はガラス表面に粘質乃至は硬質のスケールが析出して表面に付着して運転に支障を来たすために定期的に運転を止めてこれらのスケールを適時洗浄除去する必要がある。水系の場合は多くの場合、水中に含まれる、カルシウム、マグネシウム，アルミニウム、鉄、シリカが水に難溶の酸化物、水酸化物、塩類となって表面に固着するものである。 Various types of chemical plants, heat exchangers, reaction vessels in the vicinity of heating equipment, piping, etc., always sticky or hard scales are deposited on the surface of metal materials or glass surfaces that come into contact with chemical raw materials, reactants, cooling water, or refrigerant. In order to adhere to the surface and hinder the operation, it is necessary to periodically stop the operation and clean and remove these scales in a timely manner. In many cases, water-based calcium, magnesium, aluminum, iron, and silica contained in water become oxides, hydroxides, and salts that are hardly soluble in water, and are fixed to the surface.
従来これらの洗浄剤として、塩酸、硫酸、硝酸、クエン酸等の酸性物質が使用されるが特に金属表面を腐食や劣化さらには洗浄力の不足と、廃水における酸処理の問題を抱えている。金属表面の腐食と劣化は装置にとって深刻である。又、油系、特に重油分に関わる貯層、熱交換器、化学反応、その他燃焼系に関連する、タール性の粘凋性スケールはより深刻で強酸では対処が出来ず、各種の強アルカリ乃至は極性溶剤が使用される。さらには近年の液晶パネル部材における重要なラビング工程に使用するラビング布（コットン、レーヨン）の毛羽立たせた繊維糸の洗浄が、毛羽布のロール回転により配向膜上に微細な溝を付けることが液晶画面の性能を左右することから、毛羽布に付着する埃、油、樹脂をミクロン単位で取り除くための優れた洗浄剤の開発が待たれていた。 Conventionally, acidic substances such as hydrochloric acid, sulfuric acid, nitric acid, and citric acid are used as these cleaning agents, but they particularly have problems with corrosion and deterioration of metal surfaces, lack of cleaning power, and acid treatment in wastewater. Corrosion and degradation of metal surfaces is serious for equipment. In addition, tar-type viscous scales related to oil systems, particularly reservoirs related to heavy oil, heat exchangers, chemical reactions, and other combustion systems are more serious and cannot be dealt with with strong acids. A polar solvent is used. Furthermore, the cleaning of the lapped fiber yarn of the rubbing cloth (cotton, rayon) used in an important rubbing process in the recent liquid crystal panel members may form fine grooves on the alignment film by rotating the luff roll. Since the performance of the screen is affected, the development of an excellent cleaning agent for removing dust, oil, and resin adhering to the blanket in micron units has been awaited.
一方、従来の機械部品、電子部品、プラスチック部品を始めとする工業用洗浄剤はフッ素系、塩素系、臭素系有機溶剤及び過酸化水素に代表される過酸化物がその溶解性と取り扱いの容易さから多方面で使用されている。 On the other hand, industrial cleaners such as conventional mechanical parts, electronic parts and plastic parts are made of peroxides such as fluorine, chlorine, bromine organic solvents and hydrogen peroxide. It is used in many ways.
しかしながら近年、印刷業の洗浄工程での作業員の胆管ガンの発生が多発し、マスコミで度々報道されるようになった。例えば、２０１２年１０月２５日の日本経済新聞記事は１，２ジクロロプロパン及びジクロロメタンの胆管ガンの関連が指摘されており、これを扱う業種が下記に及ぶことが記載されている。 However, in recent years, there have been frequent occurrences of bile duct cancer among workers in the cleaning process of the printing industry, and it has been reported frequently in the media. For example, the Nihon Keizai Shimbun article dated October 25, 2012 points out the relationship between bile duct cancers of 1,2 dichloropropane and dichloromethane, and states that the following industries are handled.
（１，２ジクロロプロパン）
化学工業、繊維工業、一般機械器具製造業、鉄鋼業
（ジクロロメタン）
プラスチック製品製造業、金属製品製造業、木材・木製品製造業、医薬品製造業、電気機械器具製造業、ゴム製品製造業、窯業・土石製品製造業
(1,2 dichloropropane)
Chemical industry, textile industry, general machinery / equipment manufacturing industry, steel industry (dichloromethane)
Plastic product manufacturing industry, metal product manufacturing industry, wood / wood product manufacturing industry, pharmaceutical manufacturing industry, electrical machinery / equipment manufacturing industry, rubber product manufacturing industry, ceramic industry / debris product manufacturing industry
実に多岐にわたる。印刷業は氷山の一角と言わざるを得ない。一方、近年の環境問題は過酸化物系及びフッ素系、臭素系有機洗浄剤を含めて予断を許さず、安全な洗浄剤の開発は急務である。 It is very diverse. The printing industry is the tip of the iceberg. On the other hand, environmental problems in recent years, including peroxide-based, fluorine-based, and bromine-based organic cleaning agents, are unpredictable, and the development of safe cleaning agents is an urgent task.
現在、環境破壊を伴わない溶剤系洗浄剤としてメタノール、エタノール、プロパノールなどのアルコール系及び油脂系、イオン系界面活性剤が使用されているが洗浄性に限界がある。 Currently, alcohol-based and oil-based and ionic surfactants such as methanol, ethanol, and propanol are used as solvent-based cleaning agents that do not cause environmental destruction, but there are limits to cleaning properties.
更に医療用器具類の洗浄が院内感染の予防のために現場による個別の一次洗浄から中央一括による集中洗浄→消毒・滅菌方式へと移行しており、従って本発明は従来のタンパク質、油、血液、錆び等の洗浄剤に使用されるアルカリ性/酸性/中性洗剤乃至は酵素系洗剤に代わる洗浄力の強い洗浄剤を提供するものである。 Furthermore, the cleaning of medical instruments has shifted from individual primary cleaning in the field to centralized centralized cleaning → disinfection / sterilization to prevent nosocomial infections. Therefore, the present invention is a conventional protein, oil, blood. The present invention provides a detergent having a strong detergency to replace alkaline / acidic / neutral detergents or enzyme detergents used for detergents such as rust.
そこで織物仕上げ処理剤及び洗浄剤として、２−ヒドロキシプロピル−２−ヒドロキシヘキシルーβＣＤのような混成エーテルのＣＤ誘導体水溶液の提案がなされている（例えば特許文献１参照。）。また自動食器洗浄器用にメチル化変性ＣＤ，ＨＰ変性ＣＤとカチオン化グアーガム及びアルキルエーテル硫酸ナトリウムの水溶液の洗浄液の提案がなされている（例えば特許文献２参照。）。また非イオン界面活性剤と天然型ＣＤと２％ＮａＯＨ水溶液及の湯洗によるＣＩＰ洗浄液による食品製造設備の洗浄用に提案されている（例えば特許文献３参照。）。またエーテルカルボン酸、非イオン界面活性剤、水等に各種ＣＤを加えたＣＩＰ洗浄液を食品製造設備の洗浄用に提案されている（例えば特許文献４参照。）。また水酸化テトラメチルアンモニウム水溶液にβＣＤ乃至はＨＰβＣＤを加えたプラスチックレンズ用洗浄剤の提案がなされている（例えば特許文献５参照。）。またアミノ酸型キレート剤、グルコン酸、アルカリビルダー及び陰イオン性界面活性剤の組み合わせによる鋼板の表面清浄剤組成物の提案がなされている（例えば特許文献６参照。）。またフロン代替洗浄剤として炭化水素系溶剤と金属イオンを配位し得る有機化合物の組み合わせによる電子・機械部品、光学・ガラス部品の洗浄剤の提案がなされている（例えば特許文献７参照。）。 Therefore, an aqueous solution of a CD derivative of a hybrid ether such as 2-hydroxypropyl-2-hydroxyhexyl βCD has been proposed as a fabric finishing agent and a cleaning agent (see, for example, Patent Document 1). Further, a washing solution of an aqueous solution of methylated modified CD, HP modified CD, cationized guar gum and sodium alkyl ether sulfate has been proposed for an automatic dishwasher (see, for example, Patent Document 2). It has also been proposed for cleaning food production facilities using a nonionic surfactant, a natural CD, a 2% NaOH aqueous solution and a CIP cleaning solution by hot water washing (see, for example, Patent Document 3). Further, a CIP cleaning solution in which various CDs are added to ether carboxylic acid, nonionic surfactant, water and the like has been proposed for cleaning food production facilities (for example, see Patent Document 4). Also, a plastic lens cleaning agent in which βCD or HPβCD is added to an aqueous tetramethylammonium hydroxide solution has been proposed (see, for example, Patent Document 5). In addition, a steel sheet surface cleaning composition comprising a combination of an amino acid chelating agent, gluconic acid, an alkali builder and an anionic surfactant has been proposed (see, for example, Patent Document 6). In addition, as an alternative cleaning agent for fluorocarbons, a cleaning agent for electronic / mechanical parts and optical / glass parts using a combination of a hydrocarbon solvent and an organic compound capable of coordinating metal ions has been proposed (for example, see Patent Document 7).
しかしながら、強力な無機・有機物への広範な洗浄性を有するＤＭＳＯと様々な化学物質への分散と流動性を促進し洗浄効果を促進するシクロデキストリンはどちらも生分解性を有し環境に最もやさしい物質であることは一般的に認識されていない。すなわちＤＭＳＯは米国、カナダ等では腎臓病及び膀胱炎治療薬として２０％水溶液が溜飲されており、非プロトン性極性溶剤として様々な可能性を有し、その回収方法及び希釈廃液処理は高度化しており、生分解性に優れた、地球環境に配慮された安全な物質である。ＤＭＳＯとシクロデキストリン（ＣＤ）が融合したことにより、飛躍的な洗浄力と消臭機能が発現することを見出し本発明となった。 However, both DMSO, which has a wide range of detergency in strong inorganic and organic substances, and cyclodextrin, which promotes dispersion and fluidity in various chemicals and promotes detergency, are both biodegradable and environmentally friendly. It is not generally recognized that it is a substance. That is, DMSO has been drunk in 20% aqueous solution as a therapeutic agent for kidney disease and cystitis in the United States, Canada, etc., and has various possibilities as an aprotic polar solvent. It is a safe substance with excellent biodegradability and consideration for the global environment. As a result of the fusion of DMSO and cyclodextrin (CD), it has been found that dramatic detergency and deodorizing function are expressed, and the present invention has been achieved.
そこで本発明の目的は上記の従来問題点を解決し、人体により安全で環境に配慮され、しかも効果的な汎用の洗浄剤組成物及び該組成物を含有する洗浄剤並びにそれらを用いた洗浄方法を提供することにある。 Accordingly, an object of the present invention is to solve the above-described conventional problems, and is a general-purpose cleaning composition that is safe and environmentally friendly to the human body, and that is effective, and a cleaning method using the same, and a cleaning method using them. Is to provide.
本発明における洗浄剤組成物は、（Ａ）ジメチルスルホキシド（ＤＭＳＯ）、（Ｂ）シクロデキストリンを含有することを特徴とする。 The cleaning composition in the present invention contains (A) dimethyl sulfoxide (DMSO) and (B) cyclodextrin.
前記洗浄組成物は、更に（Ｃ）キレート剤、（Ｄ）グリコール及びアルコール類、（Ｅ）可溶化剤、（Ｆ）水、（Ｇ）無機アルカリ及び／又は有機アミン、（Ｈ）無機酸及び／又は有機酸を少なくとも１種類以上含有することを特徴とする。 The cleaning composition further comprises (C) a chelating agent, (D) glycol and alcohols, (E) a solubilizer, (F) water, (G) an inorganic alkali and / or organic amine, (H) an inorganic acid, and At least one organic acid is contained.
前記洗浄組成物における前記（Ｂ）シクロデキストリンが、αシクロデキストリン、βシクロデキストリン、γシクロデキストリン、化学修飾型シクロデキストリン、分岐型シクロデキストリンからなる少なくとも１種であることを特徴とする。 The (B) cyclodextrin in the cleaning composition is at least one of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, chemically modified cyclodextrin, and branched cyclodextrin.
前記洗浄組成物における前記（Ｃ）キレート化合物が、エチレンジアミンテトラ酢酸塩（ＥＤＴＡ）、グリコール酸、クエン酸、生分解性キレート剤からなる少なくとも１種であることを特徴とする。 The (C) chelate compound in the cleaning composition is at least one selected from ethylenediaminetetraacetate (EDTA), glycolic acid, citric acid, and a biodegradable chelating agent.
前記洗浄組成物における前記（Ｄ）グリコール類が、１，２エタンジオール、１，２プロパンジオール、１，３プロパンジオール、１，３ブタンジオール、１，４ブタンジオール、２−メチル−１，３−プロパンジオール、ジプロピレングリコール、アルコール、メタノール、エタノール、イソプロパノールからなる少なくとも１種であることを特徴とする。 The (D) glycols in the cleaning composition are 1,2 ethanediol, 1,2 propanediol, 1,3 propanediol, 1,3 butanediol, 1,4 butanediol, 2-methyl-1,3. -It is at least 1 type which consists of propanediol, dipropylene glycol, alcohol, methanol, ethanol, isopropanol, It is characterized by the above-mentioned.
前記洗浄組成物における前記（Ｅ）可溶化剤が、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡＣ）、Ｎメチルピロリドン（ＮＭＰ）、スルホランの非プロトン性極性溶剤からなる少なくとも１種であることを特徴とする。 The solubilizing agent (E) in the cleaning composition is at least one kind of an aprotic polar solvent such as dimethylformamide (DMF), dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), or sulfolane. And
前記洗浄組成物における前記（Ｇ）無機アルカリ及び／又は有機アミンが、水酸化ナトリウム、炭酸水素ナトリウム、炭酸ナトリウム、水酸化カリ、炭酸水素カリウム、炭酸カリの無機アルカリ及びトリエチルアミン、トリメチルアミン、トリエタノールアミンからなる少なくとも１種であることを特徴とする。 The inorganic alkali and / or organic amine (G) in the cleaning composition is sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium hydroxide, potassium hydrogen carbonate, potassium carbonate inorganic alkali and triethylamine, trimethylamine, triethanolamine. It is at least 1 type which consists of.
前記洗浄組成物における前記（Ｈ）無機酸及び／又は有機酸が、塩酸、硫酸、硝酸、酢酸、シュウ酸、クエン酸、グリコール酸（ヒドロキシ酢酸）からなる少なくとも１種であることを特徴とする。 The (H) inorganic acid and / or organic acid in the cleaning composition is at least one selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, citric acid, and glycolic acid (hydroxyacetic acid). .
前記洗浄組成物における前記（Ａ）ジメチルスルホキシドの不純物に由来する臭気物質及び洗浄される物品のスケール（工業用、医療用含む）に由来するか生成する臭気物質を除去する目的で前記（Ｂ）シクロデキストリン類を含有することを特徴とする。 For the purpose of removing (A) the odorous substance derived from the impurities of dimethyl sulfoxide and the odorous substance originating in or generated from the scale (including industrial and medical) of the article to be washed in the cleaning composition. It contains cyclodextrins.
前記洗浄組成物における前記洗浄される物品が、一般機械部品、精密機械部品、車両機械部品、エンジン部品、熱交換器及び配管類、化学品貯蔵タンク、電子部品、電気部品、液晶パネル部材、光学ガラス部品及び部材、プラスチック部品及び部材であることを特徴とする。 The article to be cleaned in the cleaning composition is a general machine part, a precision machine part, a vehicle machine part, an engine part, a heat exchanger and piping, a chemical storage tank, an electronic part, an electric part, a liquid crystal panel member, optical It is characterized by being glass parts and members, plastic parts and members.
前記洗浄組成物における前記洗浄される物品が、使用済み医薬器具等に付着する、人及びペット乃至実験動物由来のタンパク質、脂肪、血液、油、無機物、錆び等を含むことを特徴とする。 The article to be cleaned in the cleaning composition contains protein, fat, blood, oil, inorganic substance, rust, etc. derived from humans and pets or laboratory animals, which adhere to a used medical instrument or the like.
本発明における洗浄剤は、前記洗浄剤組成物を含有することを特徴とする。 The cleaning agent in this invention contains the said cleaning composition, It is characterized by the above-mentioned.
前記洗浄組成物又は前記洗浄剤は、クリーニング用途、輸出用自動車のフィルム剥離用途、又は切削油洗浄用途に使用される。 The cleaning composition or the cleaning agent is used for a cleaning application, an automotive automobile film peeling application, or a cutting oil cleaning application.
本発明における洗浄方法は、前記洗浄剤組成物若しくは前記洗浄剤を含有する水溶液又は当該洗浄剤に、前記洗浄される物品を浸漬して洗浄することを特徴とする。 The cleaning method in the present invention is characterized by immersing and cleaning the article to be cleaned in the cleaning composition, an aqueous solution containing the cleaning agent, or the cleaning agent.
本発明における洗浄方法は、前記洗浄剤組成物若しくは前記洗浄剤を含有する水溶液又は当該洗浄剤を、前記洗浄される物品に高圧洗浄機で噴射して洗浄することを特徴とする。 The cleaning method in the present invention is characterized in that the cleaning composition, the aqueous solution containing the cleaning agent, or the cleaning agent is sprayed onto the article to be cleaned by a high-pressure cleaning machine.
本発明における洗浄方法は、前記洗浄方法における工程の前又は後に、前記洗浄剤組成物若しくは前記洗浄剤を含有する水溶液又は当該洗浄剤を、前記洗浄される物品に循環して洗浄することを特徴とする。 The cleaning method of the present invention is characterized in that the cleaning composition or the aqueous solution containing the cleaning agent or the cleaning agent is circulated and cleaned in the article to be cleaned before or after the step in the cleaning method. And
本発明によれば、（Ａ）ジメチルスルホキシド（ＤＭＳＯ）、（Ｂ）シクロデキストリン（ＣＤ）を含有する洗浄剤組成物を使用する事により、優れた洗浄性、スケール除去及びスケール防止性、脱臭性を持ち、頑固な有機性、無機性固着をＤＭＳＯとＣＤの相乗効果により強力な洗浄効果を有することを特徴とし、更に種々の機器及び金属、ガラス、プラスチック材質表面及びそれに付着乃至は固着する内容物の成分等の状況に応じて、（Ｃ）キレート剤、（Ｄ）グリコール及びアルコール類（Ｅ）可溶化剤及び（Ｆ）水、（Ｇ）無機アルカリ／又は有機アミン、さらに（Ｈ）無機酸／又は有機酸を１種類以上配合して、優れた洗浄効果を発揮することを特徴とする。 According to the present invention, by using a detergent composition containing (A) dimethyl sulfoxide (DMSO) and (B) cyclodextrin (CD), excellent detergency, scale removal and scale prevention, and deodorization It has a strong cleaning effect due to the synergistic effect of DMSO and CD with stubborn organic and inorganic adhesion, and various equipment and metal, glass, plastic material surfaces and the contents that adhere to or adhere to it (C) chelating agent, (D) glycol and alcohols (E) solubilizer and (F) water, (G) inorganic alkali / or organic amine, and (H) inorganic It is characterized by blending one or more acids / or organic acids and exhibiting an excellent cleaning effect.
なおシクロデキストリンを混合する事により、凝固点降下作用があり、他の毒性がある有機化合物より安全に使用できる。 By mixing cyclodextrin, it has a freezing point lowering effect and can be used more safely than other toxic organic compounds.
本発明者らは、鋭意検討の結果、各種無機塩類及び／又は有機タール物質を含む各種スケール及び使用済み医療器具に付着する人に由来するタンパク質、脂肪分、血液、油、錆びの溶解性に優れた非プロトン性極性溶剤で、安全な溶剤として膀胱炎の治療用に使用されている、（Ａ）ジメチルスルホキシド（ＤＭＳＯ）に、相乗的な洗浄効果とスケール分散性及び再付着防止に有効な（Ｂ）シクロデキストリンを組み合わせることにより、飛躍的な洗浄効果を有する洗浄剤組成物及び該組成物を含有する洗浄剤並びにそれらを用いた洗浄方法を本発明の第一の要旨とする。 As a result of intensive studies, the present inventors have found that various scales containing various inorganic salts and / or organic tar substances and the solubility of proteins, fats, blood, oil, and rust derived from people attached to used medical devices. (A) Dimethyl sulfoxide (DMSO), an excellent aprotic polar solvent that is used as a safe solvent for the treatment of cystitis, is effective for synergistic cleaning effect, scale dispersibility and anti-redeposition (B) By combining cyclodextrin, a cleaning composition having a dramatic cleaning effect, a cleaning composition containing the composition, and a cleaning method using them are the first gist of the present invention.
特に上記（Ｂ）成分のシクロデキストリンがαシクロデキストリン、βシクロデキストリン、γシクロデキストリン、分岐型αシクロデキストリン、分岐型βシクロデキストリン、分岐型γシクロデキストリン、化学修飾型シクロデキストリンのうちメチル化αシクロデキストリン、メチル化βシクロデキストリン、メチル化γシクロデキストリン、ヒドロキシプロピルαシクロデキストリン、ヒドロキシプロピルβシクロデキストリン、ヒドロキシプロピルγシクロデキストリン、アセチル化αシクロデキストリン、アセチル化βシクロデキストリン、アセチル化γシクロデキストリン、から選ばれた１種以上の成分を有する洗浄剤組成物及び該組成物を含有する洗浄剤並びにそれらを用いた洗浄方法を第二の要旨とする。 In particular, the cyclodextrin of the above component (B) is α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, branched α-cyclodextrin, branched β-cyclodextrin, branched γ-cyclodextrin, or chemically modified cyclodextrin. Cyclodextrin, methylated beta cyclodextrin, methylated gamma cyclodextrin, hydroxypropyl alpha cyclodextrin, hydroxypropyl beta cyclodextrin, hydroxypropyl gamma cyclodextrin, acetylated alpha cyclodextrin, acetylated beta cyclodextrin, acetylated gamma cyclodextrin The second gist is a detergent composition having one or more components selected from the above, a detergent containing the composition, and a washing method using them.
そして、上記（Ｃ）成分のキレート剤が、エチレンジアミン四酢酸ナトリウム（ＥＤＴＡ），ジエチレントリアミン五酢酸、トリエチレンテトラミン六酢酸、ニトリロ三酢酸、ヒドロキシイミノジコハク酸、ヒドロキシエタンスホスホン酸、３−ヒドロキシ−２，２’−イミノジコハク酸四ナトリウム、クエン酸、グルコン酸、酒石酸、オキシカルボン酸類、Ｌ−アスパラギン酸−Ｎ，Ｎ−２酢酸等があげられ、好ましくはＥＤＴＡ，クエン酸、グルコン酸、酒石酸、３−ヒドロキシ−２，２‘−イミノジコハク酸四ナトリウムから選ばれた１種以上の成分を有する洗浄剤組成物及び該組成物を含有する洗浄剤並びにそれらを用いた洗浄方法を第三の要旨とする。 And the chelating agent of the above component (C) is ethylenediaminetetraacetic acid sodium (EDTA), diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilotriacetic acid, hydroxyiminodisuccinic acid, hydroxyethanesphosphonic acid, 3-hydroxy- 2,2′-iminodisuccinic acid tetrasodium, citric acid, gluconic acid, tartaric acid, oxycarboxylic acids, L-aspartic acid-N, N-2 acetic acid and the like, preferably EDTA, citric acid, gluconic acid, tartaric acid, A detergent composition having one or more components selected from 3-hydroxy-2,2′-iminodisuccinic acid tetrasodium, a detergent containing the composition, and a washing method using them are described in the third aspect. To do.
また、上記の洗浄液組成物と、（Ｄ）グリコール及びアルコール類、（Ｅ）可溶化剤及び（Ｆ）水をから選ばれた１種以上の成分を有する洗浄剤組成物及び該組成物を含有する洗浄剤並びにそれらを用いた洗浄方法を第四の要旨とする。 Further, the cleaning liquid composition, the cleaning composition having one or more components selected from (D) glycol and alcohols, (E) solubilizer and (F) water, and the composition are contained. The fourth gist is a cleaning agent to be used and a cleaning method using them.
さらにまた、（Ｇ）無機アルカリ及び/又は有機アミン、さらに（Ｈ）無機酸及び/又は有機酸から選ばれた１種以上の成分を有する洗浄剤組成物及び該組成物を含有する洗浄剤並びにそれらを用いた洗浄方法を第五の要旨とする。 Furthermore, (G) an inorganic alkali and / or organic amine, (H) a cleaning composition having one or more components selected from inorganic acids and / or organic acids, a cleaning composition containing the composition, and A cleaning method using them is a fifth summary.
すなわち本発明は、（Ａ）ＤＭＳＯ及び（Ｂ）シクロデキストリンを基軸とすることを特徴とする。即ち様々なタール物質を乃至はスケールが付着する各種化学プラント、熱交換器、加熱機器付近の反応容器、配管乃至タンク、熱交換器、機械部品、車両部品、ボイラ及び電子材料、加工金属部品、プラスチック部品、光学ガラスレンズ、ハードデスクの表面に生じる各種のスケール及び使用済み医療器具に付着するタンパク質、脂肪、血液、油、無機物、錆び等の除去に対応するために、（Ｄ）グリコール及びアルコール類、（Ｅ）可溶化剤及び（Ｆ）水、（Ｇ）無機アルカリ/又は有機アミン、さらに（Ｈ）無機酸/又は有機酸を、それぞれの状況に応じて１種類以上配合することで各種製造設備、機械部品乃至は医療用器具等における洗浄工程を集中的に短時間で洗浄することを特徴とする洗浄方法を提供するものである。 That is, the present invention is characterized in that (A) DMSO and (B) cyclodextrin are the basic axes. That is, various chemical substances with various tar substances or scales attached, heat exchangers, reaction vessels near heating equipment, piping or tanks, heat exchangers, machine parts, vehicle parts, boilers and electronic materials, processed metal parts, (D) Glycol and alcohol to cope with the removal of various scales generated on the surface of plastic parts, optical glass lenses, hard desks, and proteins, fats, blood, oil, inorganics, rust, etc. attached to used medical devices Various kinds of (E) solubilizer and (F) water, (G) inorganic alkali / or organic amine, and (H) inorganic acid / or organic acid, depending on the situation. It is an object of the present invention to provide a cleaning method characterized by intensive cleaning in a short time in a manufacturing process, a machine part or a medical instrument.
本発明の特徴である、非プロトン性極性溶剤のジメチルスルホキシド（ＤＭＳＯ）とシクロデキストリン（ＣＤ）をベースに各種の器具、部品、配管、装置、釜容器、熱交換機、機械、医療用器具のスケールの成分に応じて（Ｄ）、（Ｅ）、（Ｆ）、（Ｇ）、（Ｈ）その他を様々に組み合わせて、効率的で強力な洗浄剤を提供できる。これらは本発明の洗浄剤に多様性を与えるものである。当然のことながら本発明における洗浄剤は重油、ダイオキシン、ＰＣＢ、放射性物質を含む重金属の汚染土壌及び植物を含む様々な汚染物質の洗浄に有効であることは類を待たない。 Scales of various instruments, parts, piping, equipment, kettle containers, heat exchangers, machines, and medical instruments based on the characteristics of the present invention, dimethyl sulfoxide (DMSO) and cyclodextrin (CD), which are aprotic polar solvents Depending on the components, (D), (E), (F), (G), (H) and others can be combined in various ways to provide an efficient and powerful cleaning agent. These give diversity to the cleaning agent of the present invention. As a matter of course, the cleaning agent in the present invention is effective for cleaning various pollutants including heavy oil, dioxin, PCB, heavy metal-contaminated soil containing radioactive materials and plants.
本発明の洗浄剤におけるＣＤのＤＭＳＯに対する配合量は２〜４５重量％好ましくは１０〜３０重量％である。更にこのものに水を加えて溶解特性を上げるのが最も好ましい。この場合、上記、ＤＭＳＯとＣＤの全配合量に対して水の割合は、洗浄液全重量の５〜４０重量％が良く、好ましくは１５〜２５重量％である。水とＣＤの添加はスケールの分散と溶解を促し、重要なことだが、スケール物質の再付着乃至は凝集を防止することを見出し本発明にいたった。 The blending amount of CD in DMSO in the cleaning agent of the present invention is 2 to 45% by weight, preferably 10 to 30% by weight. Further, it is most preferable to add water to this to improve the dissolution characteristics. In this case, the ratio of water to the total amount of DMSO and CD is 5 to 40% by weight, preferably 15 to 25% by weight, based on the total weight of the cleaning liquid. It has been found that the addition of water and CD promotes the dispersion and dissolution of the scale and, importantly, prevents the redeposition or aggregation of the scale material.
ＣＤはαシクロデキストリン、βシクロデキストリン、γシクロデキストリン、分岐型αシクロデキストリン、分岐型βシクロデキストリン、分岐型γシクロデキストリン、化学修飾型シクロデキストリンのうちメチル化αシクロデキストリン、メチル化βシクロデキストリン、メチル化γシクロデキストリン、ヒドロキシプロピルαシクロデキストリン、ヒドロキシプロピルβシクロデキストリン、ヒドロキシプロピルγシクロデキストリン、アセチル化αシクロデキストリン、アセチル化βシクロデキストリン、アセチル化γシクロデキストリン、から選ばれた１種以上の成分が選ばれる。 CD is α cyclodextrin, β cyclodextrin, γ cyclodextrin, branched α cyclodextrin, branched β cyclodextrin, branched γ cyclodextrin, chemically modified cyclodextrin, methylated α cyclodextrin, methylated β cyclodextrin One or more selected from methylated gamma cyclodextrin, hydroxypropyl alpha cyclodextrin, hydroxypropyl beta cyclodextrin, hydroxypropyl gamma cyclodextrin, acetylated alpha cyclodextrin, acetylated beta cyclodextrin, acetylated gamma cyclodextrin Are selected.
最も溶解洗浄が難しい最悪の有機性スケール物質は、石炭を乾留して製造するコークス製造工程から発生するタール／ピッチ成分である。即ちコールター／ピッチ留分を分離するコークス炉上部の熱交換器に付着する粘調物のタール／ピッチ物質はナフタレン、クレゾール、フェノール、フェナントレン等の多環性炭化水素を含む芳香族性物質を多く含有しその洗浄は困難を極める。本発明に至った研究は長年のこの難題を解決することであった。その結果、ＤＭＳＯとメチル化βＣＤ及び水の組み合わせが好ましく、ＤＭＳＯ単独乃至はＤＭＳＯ水溶液のみでは洗浄は不完全で且つ時間がかかり、常温洗浄は難しく温度を５０℃以上に上げ且つＫＯＨ等のアルカリを加える必要があり、その洗浄廃液の処理は困難を極め、ＤＭＳＯの回収に複雑な工程処理が必要となる。本発明はＤＭＳＯとＣＤを組み合わせることにより、洗浄性とＤＭＳＯ等の溶剤回収を簡潔にするなどの後処理を簡潔にした。 The worst organic scale material that is most difficult to dissolve and clean is the tar / pitch component generated from the coke production process that produces carbon by carbonization. That is, the thick tar / pitch substance adhering to the heat exchanger at the top of the coke oven that separates the coulter / pitch fraction is rich in aromatic substances containing polycyclic hydrocarbons such as naphthalene, cresol, phenol, and phenanthrene. Containing and cleaning is extremely difficult. The research that led to the present invention was to solve this long-standing problem. As a result, a combination of DMSO, methylated βCD and water is preferable. Cleaning with DMSO alone or with DMSO aqueous solution is incomplete and time-consuming, room temperature cleaning is difficult and the temperature is raised to 50 ° C. or higher, and alkali such as KOH is used. In addition, it is extremely difficult to treat the cleaning waste liquid, and a complicated process is required to recover DMSO. In the present invention, DMSO and CD are combined to simplify post-treatment such as detergency and recovery of solvent such as DMSO.
本発明に使用する各種シクロデキストリンの作用の説明をする。 The action of various cyclodextrins used in the present invention will be described.
そもそもシクロデキストリンは澱粉を酵素分解して直鎖に連なるグルコースを輪切りにして環状に連ねたもので、植木鉢の底が抜けた構造をしており、グルコース６個のものをαシクロデキストリン、７個をβシクロデキストリン、８個をγシクロデキストリンと呼び、様々な物質（分子）を鉢の穴の中に出し入れする。（入るのを“包接”と言い、出すのを“除放”と言う）ドナーとアクセプター（シクロデキストリン）の電子論的分子間力のなせる技である。この機能を利用して、金属、ガラス、プラスチック、木材、繊維、石材表面に付着したスケールの分散剥離作用及びスケールの再付着を防止する作用があることを見出したことが本発明に至った。近年、α型シクロデキストリン、γ型シクロデキストリンが市場に安価に供給が開始されたことにより、その機能を生かした用途開発が進んでいる。生分解性があり最も環境に配慮された物質といえる。 In the first place, cyclodextrin is a structure in which starch is enzymatically decomposed and linearly linked glucose is cut into rings and linked in a ring shape, and the bottom of the flowerpot is removed. Is called β-cyclodextrin and 8 are called γ-cyclodextrin, and various substances (molecules) are put in and out of the bowl holes. (Entering is called “inclusion” and taking out is called “exclusion”) This is a technique in which the electronic intermolecular force of donor and acceptor (cyclodextrin) can be applied. It has been found that the present invention has been found to have the function of dispersing and peeling the scale attached to the surface of metal, glass, plastic, wood, fiber, and stone and preventing the scale from reattaching by utilizing this function. In recent years, since α-type cyclodextrin and γ-type cyclodextrin have been supplied to the market at low cost, application development utilizing the functions has been advanced. It is biodegradable and the most environmentally friendly substance.
本発明における洗浄剤に配合するシクロデキストリンは、αシクロデキストリン（分岐型αシクロデキストリン含む）及びメチル化βシクロデキストリン、分岐型βシクロデキストリン、ヒドロキシプロピルβシクロデキストリン分岐型αシクロデキストリン、分岐型βシクロデキストリン、分岐型γシクロデキストリン、化学修飾型シクロデキストリンのうちメチル化αシクロデキストリン、メチル化βシクロデキストリン、メチル化γシクロデキストリン、ヒドロキシプロピルαシクロデキストリン、ヒドロキシプロピルβシクロデキストリン、ヒドロキシプロピルγシクロデキストリン、アセチル化αシクロデキストリン、アセチル化βシクロデキストリン、アセチル化γシクロデキストリン、及びその混合物である。 The cyclodextrin blended in the cleaning agent of the present invention is α-cyclodextrin (including branched α-cyclodextrin) and methylated β-cyclodextrin, branched β-cyclodextrin, hydroxypropyl β-cyclodextrin branched α-cyclodextrin, branched β Cyclodextrin, branched γ cyclodextrin, chemically modified cyclodextrin methylated α cyclodextrin, methylated β cyclodextrin, methylated γ cyclodextrin, hydroxypropyl α cyclodextrin, hydroxypropyl β cyclodextrin, hydroxypropyl γ cyclodextrin Dextrin, acetylated alpha cyclodextrin, acetylated beta cyclodextrin, acetylated gamma cyclodextrin, and mixtures thereof.
上記シクロデキストリンを１種類以上配合しても良いが、好ましくはαシクロデキストリン、βシクロデキストリン及びメチル化βシクロデキストリン、分岐型βシクロデキストリン、ヒドロキシプロピルβシクロデキストリン、分岐型αシクロデキストリン、分岐型βシクロデキストリンであり、これらのシクロデキストリンを１種類以上配合してもよいが洗浄剤全重量に占める割合は既に上述してある。これらのシクロデキストリンは洗浄剤に由来する乃至はスケール除去乃至は溶解の再に発生する臭気物質を除去する効果があり、本発明を特徴できるものである。 One or more of the above cyclodextrins may be blended, but preferably α cyclodextrin, β cyclodextrin and methylated β cyclodextrin, branched β cyclodextrin, hydroxypropyl β cyclodextrin, branched α cyclodextrin, branched type β cyclodextrin, and one or more of these cyclodextrins may be blended, but the proportion of the total weight of the cleaning agent has already been described above. These cyclodextrins have the effect of removing odorous substances derived from cleaning agents, scale removal or re-dissolution, and can characterize the present invention.
そもそもが、ＤＭＳＯは非プロトン性極性溶剤で、各種の無機塩、有機化合物を溶解する溶剤として様々に利用されている。即ち、ポリアクリロニトリル、トリアセチルセルローズ、エポキシ樹脂ポリビニルピロリドン等の接着性物質に優れた溶解性を持ち、その特質により、電子部品、機械部品、半導体の剥離材として利用されているが、ＤＭＳＯ中に微量含有する不純物のジメチルスルフィド（ＣＨ３）２Ｓ、メチルメルカプタン（ＣＨ３ＳＨ）、硫化水素（Ｈ２Ｓ）は共に悪臭物質であり、ＤＭＳＯ自体が持っている安全性（Ｏｒａｌ ＬＤ５０＝１７４００、Ｄｅｒｍａｌ ＬＤ５０＝４００００）にも拘らず、一部の電子材料の洗浄剤、エッチング後の残渣処理、有機合成溶剤、ＩＰＳ細胞の保存液に限られていた。 In the first place, DMSO is an aprotic polar solvent and is used in various ways as a solvent for dissolving various inorganic salts and organic compounds. In other words, it has excellent solubility in adhesive materials such as polyacrylonitrile, triacetylcellulose, epoxy resin polyvinylpyrrolidone, etc., and due to its characteristics, it is used as a release material for electronic parts, mechanical parts, and semiconductors. The impurities dimethyl sulfide (CH3) 2 S, methyl mercaptan (CH 3 SH), and hydrogen sulfide (H 2 S), which are contained in trace amounts, are both malodorous substances, and the safety of DMSO itself (Oral LD50 = 17400, Dermal) In spite of (LD50 = 40000), it was limited to cleaning agents for some electronic materials, residue treatment after etching, organic synthetic solvents, and IPS cell preservation solution.
本発明における第二の特徴は、シクロデキストリンを加えることにより、上記悪臭物質のジメチルスルフィド（ＣＨ３）２Ｓ、メチルメルカプタン（ＣＨ３ＳＨ）、硫化水素（Ｈ２Ｓ）をシクロデキストリンの包接能を利用して脱臭除去できることが判明し本発明を完成した。 The second feature of the present invention is that cyclodextrin is added to the above malodorous substances such as dimethyl sulfide (CH3) 2 S, methyl mercaptan (CH 3 SH), and hydrogen sulfide (H 2 S). As a result, it was found that deodorization and removal can be performed using this, and the present invention has been completed.
本発明における第三の特徴は医療用の器具洗浄の洗浄剤を提供することにある。既に述べたように、ＤＭＳＯの優れた安全性と溶解性にも拘らず、医療用器具の洗浄剤としての使用が遅れたのはその臭気物質のためである。しかしながら、医療用器具（血液汚染鋼製器具、プラスチック類、金属・ガラス・金属カップ類）の洗浄方法として、浸漬洗浄、ブラッシング洗浄、ジェット式洗浄、超音波洗浄等があり、医療用使用済み汚染器材の一次洗浄の後、殺菌・滅菌工程を得て、検査・組み立てから包装・乾燥工程に進むのであるが、現場での一次洗浄は様々な細菌・ウイルス等の院内感染を誘発することから、厚生労働省は平成１７年に、医政指発第０２０１００４号「医療設備における院内感染の防止について」で消毒・滅菌に先立ち、現場での一次洗浄は行わずに中央部門での一括洗浄を通達した。 The third feature of the present invention is to provide a cleaning agent for cleaning instruments for medical use. As already stated, despite the superior safety and solubility of DMSO, it was because of its odorous substances that its use as a cleaning agent for medical devices was delayed. However, medical equipment (blood-contaminated steel equipment, plastics, metal / glass / metal cups) can be cleaned by immersion, brushing, jet cleaning, ultrasonic cleaning, etc. After the primary cleaning of the equipment, the sterilization and sterilization process is obtained, and the process proceeds from the inspection and assembly to the packaging and drying process, but the primary cleaning in the field induces nosocomial infections such as various bacteria and viruses. In 2005, the Ministry of Health, Labor and Welfare issued a batch cleaning in the central department without primary cleaning at the site prior to disinfection and sterilization in “Direction of nosocomial infection in medical facilities” issued by Medical Administration No. 0201004 .
即ち、本発明は様々な医療器具の中央集中型の一括洗浄に有効であり、ＤＭＳＯとＣＤの相乗効果特性から従来型のアルカリ性／酸性／中性／酵素系洗浄剤に変わる効率的で強力な汎用型洗浄剤として、人及びペット動物乃至は実験動物由来のタンパク質、脂肪、血液、油、無機物、錆び等の集中型洗浄に有効であり本発明の第四の特徴である。 That is, the present invention is effective for centralized batch cleaning of various medical devices, and is an efficient and powerful change from the synergistic characteristics of DMSO and CD to conventional alkaline / acidic / neutral / enzymatic detergents. As a general-purpose cleaning agent, it is effective for intensive cleaning of proteins, fats, blood, oil, inorganic substances, rust, etc. derived from humans and pet animals or laboratory animals, and is the fourth feature of the present invention.
本発明における第五の特徴として近年の液晶パネル製造技術の向上に伴い、ガラスにコートされた配向膜に、起毛布をロールで捲きつけた上部起毛で配向膜表面に一定方向の微細な溝を付け、このものが液晶ポリマーの配向性を左右するのであるが、このコットン、モッケット及びレーヨン、ベルベット、ポリアミド繊維のカットされた起毛布の洗浄は液晶画面の性能を左右し、本発明が有効であることが見出された。 As a fifth feature of the present invention, along with the recent improvement of liquid crystal panel manufacturing technology, a fine groove in a certain direction is formed on the alignment film surface with the upper brushed brushed cloth on the alignment film coated with glass. In addition, this affects the orientation of the liquid crystal polymer, but the cleaning of the cotton, mocket and rayon, velvet, and polyamide fiber cut raised fabric affects the performance of the liquid crystal screen, and the present invention is effective. It was found that there was.
本発明におけるキレート剤としてはエチレンジアミン四酢酸ナトリウム（ＥＤＴＡ），ジエチレントリアミン五酢酸、トリエチレンテトラミン六酢酸、ニトリロ三酢酸、ヒドロキシイミノジコハク酸、ヒドロキシエタンスホスホン酸、３−ヒドロキシ−２，２‘イミノジコハク酸四ナトリウム、クエン酸、グルコン酸、グリコール酸、酒石酸、オキシカルボン酸類、Ｌ−アスパラギン酸−Ｎ，Ｎ−２酢酸等があげられ、好ましくはＥＤＴＡ，クエン酸、グルコン酸、酒石酸である。本発明では、洗浄剤にこれらを洗浄剤全重量の２〜１０重量％加えることにより、機器、配管、医療機器に付着した、Ｃｕ、Ｆｅ、Ｍｎ、Ｃｏ、Ｓｎ等の重金属イオン及び希土類イオンを効果的に除去することができ、ＤＭＳＯとＣＤでのスケール除去後の金属及びプラスチッ乃至はガラス表面の接触外気及び仕上げ用洗浄水等の外部要因による金属イオンの再付着防止に有効であることを見出した。 Examples of the chelating agent in the present invention include sodium ethylenediaminetetraacetate (EDTA), diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilotriacetic acid, hydroxyiminodisuccinic acid, hydroxyethanesphosphonic acid, 3-hydroxy-2,2′iminodisuccinic acid. Examples thereof include tetrasodium acid, citric acid, gluconic acid, glycolic acid, tartaric acid, oxycarboxylic acids, L-aspartic acid-N, N-2 acetic acid and the like, preferably EDTA, citric acid, gluconic acid and tartaric acid. In the present invention, heavy metal ions such as Cu, Fe, Mn, Co, Sn, and rare earth ions adhering to devices, pipes, and medical devices are added to the cleaning agent by adding 2 to 10% by weight of the total amount of the cleaning agent. It can be removed effectively, and is effective in preventing re-deposition of metal ions due to external factors such as metal and plastic after glass scale removal with DMSO and CD, or contact air on the glass surface and cleaning water for finishing. I found it.
更には、本発明は、上記（Ｃ）キレート剤以外に（Ｄ）グリコール類、（Ｅ）可溶化剤及び（Ｆ）水、（Ｇ）無機アルカリ及び／又は有機アミン、さらに（Ｈ）無機酸及び／又は有機酸を１種類以上配合することを特徴とする。グリコール類としては１，２エタンジオール、１，２プロパンジオール、１，３プロパンジオール、１，３ブタンジオール、１，４ブタンジオール、２−メチル−１，３−プロパンジオール、ジプロピレングリコールからからなる少なくとも１種である、グリコール類を洗浄液総重量の５〜１５重量％であり、好ましくは８〜１０重量％である。特に好ましいのは１，３プロパンジオールである。このものは植物由来であり、その安全性と相まって洗浄効果と金属、プラスチック、ガラス等の洗浄表面のスケール再付着に有効である。 Furthermore, the present invention provides (D) glycols, (E) solubilizer and (F) water, (G) inorganic alkali and / or organic amine, and (H) inorganic acid in addition to the above (C) chelating agent. And / or 1 or more types of organic acids are mix | blended. Examples of glycols include 1,2 ethanediol, 1,2 propanediol, 1,3 propanediol, 1,3 butanediol, 1,4 butanediol, 2-methyl-1,3-propanediol, and dipropylene glycol. At least one of the glycols is 5 to 15% by weight, preferably 8 to 10% by weight, based on the total weight of the cleaning liquid. Particularly preferred is 1,3 propanediol. This material is derived from a plant and is effective for cleaning effect and scale reattachment of cleaning surfaces of metals, plastics, glass and the like in combination with safety.
次に、本発明の（Ｅ）可溶化剤としての非プロトン系極性溶剤のジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡＣ）、Ｎメチルピロリドン（ＮＭＰ），スルホランを提供することが出来る。これらはスケールの成分により洗浄剤に配合することにより、用途に応じて、優れた効果を発揮するものである。このものはＤＭＳＯ及びＣＤを基幹とした洗浄剤に配合することにより種々の工程及び機器、器具等に生じるスケール組成に応じて洗浄剤総重量の４〜２０重量％好ましくは８〜１５重量％配合される。スケール組成がＤＭＳＯとＣＤ以外は必要としない場合はその限りではない。 Next, dimethylformamide (DMF), dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) and sulfolane, which are aprotic polar solvents, as the solubilizing agent (E) of the present invention can be provided. By blending these into the cleaning agent with components of the scale, excellent effects are exhibited depending on the application. This blended with DMSO and CD-based cleaning agents, 4 to 20% by weight of the total amount of cleaning agents, preferably 8 to 15% by weight, depending on the scale composition produced in various processes, equipment, instruments, etc. Is done. This is not the case when the scale composition other than DMSO and CD is not required.
また、本発明では、（Ｆ）水、（Ｇ）無機アルカリ及び／又は有機アミン、さらに（Ｈ）無機酸及び／又は有機酸を１種類以上含有することを特徴とするが、これらを洗浄液に加えることで、スケール物質の再凝集の防止とＤＭＳＯ及びＣＤと相まって流動性と消臭性を促し、最終的仕上げ洗浄に有効であり、洗浄コスト削減に必要である。特に洗浄剤に水を加えることは溶剤の静電気等の原因による発火を防止し、重要な要素である。これらの洗浄液総重量に占める割合は全体の３０重量％以下であり好ましくは２９重量％以下である。 In the present invention, (F) water, (G) inorganic alkali and / or organic amine, and (H) one or more kinds of inorganic acid and / or organic acid are contained. In addition, it prevents re-agglomeration of scale material and, in combination with DMSO and CD, promotes fluidity and deodorization, is effective for final finishing cleaning, and is necessary for reducing cleaning costs. In particular, adding water to the cleaning agent is important because it prevents ignition due to static electricity of the solvent. The proportion of these cleaning liquids in the total weight is 30% by weight or less, preferably 29% by weight or less.
また従来、機器類、釜及び配管類、プラスチック機材及び部品類、ガラス基板、光学ガラス、医療用機材の洗浄工程として、水洗浄→溶剤洗浄→水すすぎ→アルカリ洗浄→水すすぎ→酸洗浄→水すすぎ→殺菌→水すすぎの工程で行われるのが一般的である。 Conventionally, as a cleaning process for equipment, kettles and piping, plastic equipment and parts, glass substrates, optical glass, and medical equipment, water washing → solvent washing → water rinsing → alkali washing → water rinsing → acid washing → water Generally, it is performed in the process of rinsing → sterilization → water rinsing.
本発明における、ＤＭＳＯなどの非プロトン性極性溶剤とメチル化βシクロデキストリン、αシクロデキストリン、βシクロデキストリンなどの各種シクロデキストリンを基材とする洗浄剤乃至は水溶液は、汚れの状況及び種類に応じて、洗浄の順序や工程が簡略変更されるか乃至は同じ工程を繰り返し行われる。 In the present invention, cleaning agents or aqueous solutions based on aprotic polar solvents such as DMSO and various cyclodextrins such as methylated β-cyclodextrin, α-cyclodextrin, and β-cyclodextrin depend on the state and type of soil. Thus, the cleaning sequence and process are changed or the same process is repeated.
これらは機器類、釜及び配類管、プラスチック機材及び部品類、ガラス基板、光学ガラス、医療用機材、クロス等の被洗浄物にこれらの洗浄剤組成物乃至は希釈液を浸漬して処理する方法、あるいは被洗浄物内部乃至は外面に希釈液を高圧洗浄機等により噴射して処理する方法がある。 These are treated by immersing these cleaning compositions or diluents in objects to be cleaned such as equipment, kettles and distribution pipes, plastic equipment and parts, glass substrates, optical glass, medical equipment, cloth, etc. There is a method, or a method in which a diluent is sprayed by a high-pressure washing machine or the like inside or outside an object to be cleaned.
本発明の洗浄剤組成物乃至は希釈物による洗浄処理を行う場合、上記記載の工程の前及び／又は後に本発明洗浄剤組成物乃至は希釈物を循環させることにより行うことができる。又本発明では洗浄工程を複数回に分けて繰り返し行うことにより、より高度な洗浄脱臭効果を期待できる。 When performing the cleaning treatment with the detergent composition or the dilution of the present invention, the cleaning composition or the dilution of the present invention can be circulated before and / or after the above-described steps. In the present invention, a higher cleaning and deodorizing effect can be expected by repeatedly performing the cleaning process in a plurality of times.
この場合、洗浄剤組成物乃至は希釈液を５〜１７０℃の温度範囲、好ましくは１５〜１５０℃の温度範囲にて、各種機器類、配管類、プラスチック機材及び部品類、ガラス基板、光学ガラス、医療用機材、クロス等と内部及び外部と接触させながら循環させて行うのが好ましい。勿論、加圧化で行う場合は５０〜１５０℃の温度範囲で機器類の材質等から熱変性を考慮して設定されるべきである。 In this case, the cleaning composition or the diluent is in the temperature range of 5 to 170 ° C., preferably in the temperature range of 15 to 150 ° C., various devices, piping, plastic equipment and parts, glass substrate, optical glass. It is preferable to circulate while making contact with the inside and outside of medical equipment, cloth, etc. Of course, when it is performed by pressurization, it should be set in consideration of heat denaturation in the temperature range of 50 to 150 ° C. from the material of the equipment.
本発明におけるＤＭＳＯ等の非プロトン性極性溶剤に各種シクロデキストリンを加えた洗浄剤組成物を水等で希釈する場合は全洗浄剤組成物の０．１５〜４０．０％好ましくは５．０〜２０．０％の希釈水溶液として用いることが好ましい。 When diluting a detergent composition obtained by adding various cyclodextrins to an aprotic polar solvent such as DMSO in the present invention with water or the like, 0.15 to 40.0% of the total detergent composition, preferably 5.0 to It is preferably used as a 20.0% diluted aqueous solution.
また本発明における洗浄剤組成物乃至は希釈液は前記工程の酸洗浄工程の酸処理剤あるいはアルカリ洗浄工程のアルカリ処理剤と同時に洗浄脱臭工程を行うことが出来、洗浄時間の短縮が可能となる。 In addition, the cleaning composition or dilution liquid in the present invention can be subjected to the cleaning and deodorizing step simultaneously with the acid processing agent in the acid cleaning step or the alkali processing agent in the alkali cleaning step, and the cleaning time can be shortened. .
次に、本発明を実施例等により詳しく説明するが、本発明の範囲はこれらにより制限されるものではない。 EXAMPLES Next, although an Example etc. demonstrate this invention in detail, the scope of the present invention is not restrict | limited by these.
以下の実施例に示す配合組成の洗浄剤を、ジャケット付きミキサーを使用して混合し、均一なスラリーを調製後、冷却を行って表１、表３〜表５に記載の実施例１〜２５の洗浄液を製造した。 The detergents of the composition shown in the following examples are mixed using a mixer with a jacket, and after preparing a uniform slurry, cooling is performed and Examples 1 to 25 shown in Tables 1 and 3 to 5 are performed. A cleaning solution was prepared.
（洗浄性評価法１）
（タールスケール；洗浄評価法）
無水タール（比重１．２、粘度１０００ＣＰ：６０℃、水分０．２，固定炭素３０〜３５％、ＪＦＥケミカル株式会社製）１０グラムをビーカーに取り、予めジメチルスルホキシド（ＤＭＳＯ）にシクロデキストリン（ＣＤ）を溶解させ、実施例に従い添加するキレート剤、グルコース類、水、アルカリ／酸を適量加え、３０分間設定の温度で攪拌し、その後１０分間静置して、タール分の洗浄性を下記により目視で評価する。
（洗浄性評価）
◎；ビーカーガラス壁面及び底面に未溶解残渣を含むタール付着物が全く認められない。
○；ビーカーガラス壁面及び底面に未溶解残渣は無いが底面に微量のタール付着物が認められる。
△；ビーカーガラス壁面及び底面に未溶解残渣は無いが壁面及び底面に微量のタール付着物が認められる。
×；ビーカーガラス壁面及び底面に未溶解残渣を含むタール付着物を認められる。
（◎、○はその後の、水による濯ぎ液洗浄工程を加えて実用性ありと判定される）
(Cleanability evaluation method 1)
(Tar scale; cleaning evaluation method)
Take 10 grams of anhydrous tar (specific gravity 1.2, viscosity 1000 CP: 60 ° C., moisture 0.2, fixed carbon 30-35%, manufactured by JFE Chemical Co., Ltd.) in a beaker, and add dimethyl sulfoxide (DMSO) to cyclodextrin (CD ) And adding appropriate amounts of chelating agent, glucose, water, alkali / acid added according to the examples, stirring at the set temperature for 30 minutes, and then allowing to stand for 10 minutes. Evaluate visually.
(Cleanability evaluation)
A: Tar deposits containing undissolved residues on the wall and bottom surfaces of the beaker glass are not observed at all.
○: There is no undissolved residue on the beaker glass wall and bottom, but a small amount of tar deposits is observed on the bottom.
Δ: There is no undissolved residue on the wall surface and bottom surface of the beaker glass, but a small amount of tar deposits is observed on the wall surface and bottom surface.
X: Tar deposits containing undissolved residue on the beaker glass wall and bottom are observed.
(◎ and ○ are determined to be practical by adding a subsequent washing step with water)
（洗浄性評価法２）
（炭酸カルシウムスケール；洗浄評価法）
炭酸カルシウム（純度９９．９％、純正化学品）１５０ｍｇをビーカーに取り、このものに予めジメチルスルホキシド（ＤＭＳＯ）にシクロデキストリン（ＣＤ）を溶解させ、実施例に従い添加するキレート剤、グルコース類、水、アルカリ／酸を加え、３０分間設定の温度（２０℃）で攪拌し、その後１０分間静置して、ＥＤＴＡで標準溶液、ＮＮ試薬を用いてキレート法にて溶解した炭酸カルシウムを算出して以下の標準基準で洗浄性を評価した。
（洗浄性評価）
◎；洗浄剤溶液１０００ｍｌ当たりの炭酸カルシウム溶解量が１５０ｍｇを超えるもの。
○；洗浄剤溶液１０００ｍｌ当たりの炭酸カルシウム溶解量が１００ｍｇを超えるもの。
△；洗浄剤溶液１０００ｍｌ当たりの炭酸カルシウム溶解量が５０ｍｇを超えるもの。
×；洗浄剤溶液１０００ｍｌ当たりの炭酸カルシウム溶解量が５０ｍｇ未満のもの。
（◎、○はその後の、水による濯ぎ液洗浄工程を加えて実用性ありと判定される）
(Cleanability evaluation method 2)
(Calcium carbonate scale; cleaning evaluation method)
Take 150 mg of calcium carbonate (purity 99.9%, pure chemical) in a beaker, dissolve cyclodextrin (CD) in dimethyl sulfoxide (DMSO) in advance, and add according to the examples, chelating agents, glucoses, water Add the alkali / acid, stir at the set temperature (20 ° C.) for 30 minutes, then let stand for 10 minutes, calculate the calcium carbonate dissolved in the chelate method using the standard solution and NN reagent with EDTA. Detergency was evaluated according to the following standard criteria.
(Cleanability evaluation)
A: The amount of calcium carbonate dissolved per 1000 ml of the detergent solution exceeds 150 mg.
○: The amount of dissolved calcium carbonate per 1000 ml of the detergent solution exceeds 100 mg.
Δ: The amount of calcium carbonate dissolved per 1000 ml of the detergent solution exceeds 50 mg.
X: The amount of dissolved calcium carbonate per 1000 ml of the detergent solution is less than 50 mg.
(◎ and ○ are determined to be practical by adding a subsequent washing step with water)
（洗浄性評価法３）
（プラスチックレンズ及びガラスレンズ表面の洗浄評価法）
レンズ研摩加工後は研摩に伴う、プラスチックのモノマー残渣及び樹脂粉が表面に付着する。一方、ガラスレンズ研摩後にはレアアース等の残存研磨剤残渣及びガラスの削り残渣（ＳｉＯ２等）、その他の酸化物質がガラス表面に残る。本発明では永田製作所株式会社から提供された研摩後（未洗浄）の直径５０ｍｍのガラス凸レンズ及びプラスチック凸レンズを速やかにビーカーに移し、予めジメチルスルホキシド（ＤＭＳＯ）にシクロデキストリン（ＣＤ）を溶解させ、或いは実施例に従い添加するキレート剤、グルコース類、水、アルカリ／酸を加え、３０分間設定の温度（２０℃）で攪拌し、その後１０分間静置し取り出した後、更に純水２００ｍｌに２０分浸漬して研摩液を取り除き、風乾で１昼夜乾燥後、目視にて以下の標準基準で洗浄性を評価した。
（洗浄性評価）
◎；レンズの表面に残渣、樹脂粉乃至はガラス粉、皮脂の汚れが全く認められない。
○；レンズの表面に残渣、樹脂粉乃至はガラス粉、皮脂の汚れが殆んど認められない。
△；レンズの表面に残渣、樹脂粉乃至はガラス粉、皮脂の汚れが若干認められる。
×；レンズの表面に残渣、樹脂粉乃至はガラス粉、皮脂の汚れが相当数認められる。
（◎、○はその後の、水による濯ぎ液洗浄工程を加えて実用性ありと判定される）
(Cleanability evaluation method 3)
(Cleaning evaluation method for plastic lens and glass lens surfaces)
After the lens polishing process, plastic monomer residues and resin powder accompanying the polishing adhere to the surface. On the other hand, after polishing the glass lens, residual abrasive residue such as rare earth, glass shaving residue (SiO 2 etc.), and other oxidizing substances remain on the glass surface. In the present invention, the glass convex lens and plastic convex lens having a diameter of 50 mm after polishing (unwashed) provided by Nagata Seisakusho Co., Ltd. are quickly transferred to a beaker, and cyclodextrin (CD) is dissolved in dimethyl sulfoxide (DMSO) in advance. Add the chelating agent, glucose, water and alkali / acid to be added according to the examples, stir at the set temperature (20 ° C.) for 30 minutes, leave it for 10 minutes and then take it out, and further soak in 200 ml of pure water for 20 minutes. Then, the polishing liquid was removed, and after air-drying for one day and night, the detergency was visually evaluated according to the following standard criteria.
(Cleanability evaluation)
A: Residue, resin powder or glass powder, and sebum are not observed on the lens surface.
◯: Residue, resin powder or glass powder, and sebum are hardly observed on the lens surface.
Δ: Residue, resin powder or glass powder, and sebum stains are slightly observed on the lens surface.
X: A considerable number of residues, resin powder or glass powder, and sebum stains are observed on the lens surface.
(◎ and ○ are determined to be practical by adding a subsequent washing step with water)
（洗浄性評価法４）
（タンパク質；医療器具洗浄評価法）
複数個の鶏卵から卵黄（脂肪２６．５％，タンパク質１５．８％）のみを取り出し、良く攪拌し、このものにアルミニウムの切片（１５ｍｍ×５０ｍｍ厚み３ｍｍ）を３０分間浸漬し、取り出した後、１昼夜放置して卵黄タンパク質が固着乃至は付着したものをビーカーに移し、予めジメチルスルホキシド（ＤＭＳＯ）にシクロデキストリン（ＣＤ）を溶解させ、或いは実施例に従い添加するキレート剤、グルコース類、水、アルカリ／酸を加え、３０分間設定の温度（２０℃）で攪拌し、その後１０分間静置し、取り出した後、更に水２００ｍｌに２０分浸漬して研摩液を取り除き、風乾で１昼夜乾燥後、アルミニウム切片重量変化にて以下の標準基準で洗浄性を評価した。
（洗浄性評価）
○；アルミニウム切片の重量変化が無く、アミドブラック染色法でもタンパク質残留が全く認められない。
△；アルミニウム切片の重量変化が無いが、アミドブラック染色法でタンパク質残留が痕跡が認められる。
×；アルミニウム切片の重量変化が認められ、タンパク質付着物が認められる。
（○はその後の、水による濯ぎ液洗浄工程を加えて実用性ありと判定される）
(Cleanability evaluation method 4)
(Protein; Evaluation method for cleaning medical equipment)
After removing only egg yolk (26.5% fat, 15.8% protein) from a plurality of chicken eggs and stirring well, an aluminum slice (15 mm × 50 mm thickness 3 mm) was immersed in this for 30 minutes, and then removed. Leave the egg yolk protein adhering or adhering to the beaker for 1 day and night, dissolve cyclodextrin (CD) in dimethyl sulfoxide (DMSO) in advance, or add according to the embodiment chelating agent, glucose, water, alkali / Add acid, stir at the set temperature (20 ° C.) for 30 minutes, then let stand for 10 minutes, take out, further soak in 200 ml of water for 20 minutes to remove the polishing liquid, air-dry for one day and night, Detergency was evaluated according to the following standard criteria by changing the weight of the aluminum section.
(Cleanability evaluation)
◯: There is no change in the weight of the aluminum section, and no protein residue is observed even with the amide black staining method.
Δ: There is no change in the weight of the aluminum section, but traces of protein residue are observed by the amide black staining method.
X: A change in weight of the aluminum piece is observed, and protein deposits are observed.
(○ is determined to be practical by adding a subsequent washing step with water)
（総合洗浄性）
上記洗浄評価法１，２，４に従い、下記の消臭性評価を含め、総合的に判断して評価基準の多いものを総合洗浄基準とした。洗浄評価法３のプラスチック及びレンズの洗浄効果は特に光学レンズのサンプルの特殊性からそれのみでの評価とした。
(Total cleanability)
In accordance with the cleaning evaluation methods 1, 2, and 4, the comprehensive cleaning standard was determined based on the comprehensive evaluation including the following deodorant evaluation. The cleaning effect of the plastic and lens of the cleaning evaluation method 3 was evaluated based on the particularity of the optical lens sample.
（脱臭性評価）
洗浄液の洗浄前及び洗浄後の臭気の判定は５人のパネラーによる官能テストにより行われた。臭気の度合いを以下の４段階での評価基準で評価した。
（臭気評価基準）
◎；臭気なし
○；僅かにメルカプタン乃至は硫黄臭あり。
△；ややメルカプタン乃至は硫黄臭あり。
×；メルカプタン乃至は硫黄臭が強い。
（◎、○はその後の、水による濯ぎ液洗浄工程を加えて実用性ありと判定される）
(Deodorization evaluation)
The determination of the odor before and after cleaning of the cleaning liquid was performed by a sensory test with five panelists. The degree of odor was evaluated according to the following four evaluation criteria.
(Odor evaluation criteria)
A: No odor B: Slightly mercaptan or sulfur odor.
Δ: Slightly mercaptan or sulfur odor.
X: Mercaptan or sulfur odor is strong.
(◎ and ○ are determined to be practical by adding a subsequent washing step with water)
（ラビングクロス洗浄性）
液晶パネルの配向膜に溝を付ける、カット済みラビングクロス（トリコット起毛布；パイル太さ；４０番双糸、長さ；１．７ｍｍ、本数；２７５．５本／ｃｍ２，ベース厚み；０．５ｍｍ）の切片；５０ｍｍ×２０ｍｍを、予めビーカー内にジメチルスルホキシド（ＤＭＳＯ）にシクロデキストリン（ＣＤ）を溶解させ、或いは実施例に従い添加するキレート剤、グルコース類、水を加え、３０分間設定の温度（２０℃）で攪拌し、その後１０分間静置し取り出した後、更に純水２００ｍｌに２０分浸漬して研摩液を取り除き、風乾で１昼夜乾燥後拡大鏡を使用する目視にて以下の標準基準で洗浄性を評価した。
（洗浄性評価）
◎；起毛布の立毛起毛に起毛の絡みが無く、表面に埃、有機物乃至は油の汚れが全く認められない。
○；起毛布の立毛起毛に起毛の絡みが僅かにあるが、表面に埃、有機物乃至は油の汚れが全く認められない。
△；起毛布の立毛起毛に起毛の絡みが僅かにあり、表面に微量の埃が認められ、有機物乃至は油の汚れが全く認められない。
×；起毛布の立毛起毛に起毛の絡みが僅かにあり、表面に微量の埃が認められ、有機物乃至は油の汚れが認められる。
（◎、○はその後の、水による濯ぎ液洗浄工程を加えて実用性ありと判定される）
(Rubbing cloth washability)
Cut rubbing cloth (tricot brushed cloth; pile thickness; No. 40 twine, length: 1.7 mm, number: 275.5 / cm2, base thickness: 0.5 mm ); 50 mm × 20 mm, in which a cyclodextrin (CD) is dissolved in dimethyl sulfoxide (DMSO) in a beaker in advance, or a chelating agent, glucose, and water added according to the examples are added, and the temperature (set for 30 minutes) (20 ° C), and then left to stand for 10 minutes and then taken out, and then immersed in 200 ml of pure water for 20 minutes to remove the polishing liquid. The detergency was evaluated.
(Cleanability evaluation)
A: The raised nap of the raised cloth has no entanglement, and no dust, organic matter or oil stains are observed on the surface.
○: There is a slight entanglement in the raised nap of the raised cloth, but no dust, organic matter or oil stains are observed on the surface.
Δ: Raised napping of the raised cloth has slight entanglement, a minute amount of dust is observed on the surface, and no organic matter or oil stains are observed.
X: The raised napping of the raised cloth has a slight entanglement of the raised hair, a minute amount of dust is observed on the surface, and organic matter or oil stains are observed.
(◎ and ○ are determined to be practical by adding a subsequent washing step with water)
以下の実施例（表１、３〜１０の１〜６３）及び比較例（表２の１〜７）において、各成分の割合は質量％で示す。試験結果及び評価法は既に説明済みの方法による。なお実施例及び比較例において記載した（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分、（Ｅ）成分、（Ｆ）成分、（Ｇ）成分、（Ｈ）成分は以下の通りである。 In the following Examples (Tables 1, 3 to 10 to 1 to 63) and Comparative Examples (Table 2 to 1 to 7), the ratio of each component is indicated by mass%. Test results and evaluation methods are as described above. In addition, (A) component, (B) component, (C) component, (D) component, (E) component, (F) component, (G) component, (H) component described in the Example and the comparative example are the following. It is as follows.
（Ａ）成分
ジメチルスルホキシド（ＤＭＳＯ）
（Ｂ）成分
α−シクロデキストリン（αＣＤ）
β−シクロデキストリン（βＣＤ）
γ−シクロデキストリン（γＣＤ）
メチル化βシクロデキストリン（ＭｅβＣＤ）
ヒドロキシプロピルβシクロデキストリン（ＨＰβＣＤ）
分岐型βシクロデキストリン（分岐型βＣＤ）
（Ｃ）成分
エチレンジアミン四酢酸ナトリウム（ＥＤＴＡ）
グルコン酸
クエン酸
エチレンジアミン
（Ｄ）成分
１，３プロパンジオール
メタノール
エタノール
イソプロパノール
（Ｅ）成分
ジメチルホルムアミド（ＤＭＦ）
ジメチルアセトアミド（ＤＭＡＣ）
Ｎメチルピロリドン（ＮＭＰ）
スルホラン
（Ｆ）成分
水
（Ｇ）成分
炭酸ソーダ
炭酸水素ナトリウム
トリエチルアミン
（Ｈ）成分
硫酸
塩酸（純分換算）
酢酸
(A) Component dimethyl sulfoxide (DMSO)
(B) Component α-cyclodextrin (αCD)
β-cyclodextrin (βCD)
γ-cyclodextrin (γCD)
Methylated β cyclodextrin (MeβCD)
Hydroxypropyl β cyclodextrin (HPβCD)
Branched β-cyclodextrin (Branched βCD)
Component (C) Sodium ethylenediaminetetraacetate (EDTA)
Gluconic acid citrate ethylenediamine (D) component 1,3 propanediol methanol ethanol isopropanol (E) component dimethylformamide (DMF)
Dimethylacetamide (DMAC)
N-methylpyrrolidone (NMP)
Sulfolane (F) component water (G) component sodium carbonate sodium hydrogen carbonate triethylamine (H) component sulfuric acid hydrochloric acid (pure equivalent)
Acetic acid
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