JP2006249114A - Cleaning agent composition and cleaning method - Google Patents

Cleaning agent composition and cleaning method Download PDF

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JP2006249114A
JP2006249114A JP2005063234A JP2005063234A JP2006249114A JP 2006249114 A JP2006249114 A JP 2006249114A JP 2005063234 A JP2005063234 A JP 2005063234A JP 2005063234 A JP2005063234 A JP 2005063234A JP 2006249114 A JP2006249114 A JP 2006249114A
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cleaning
cleaned
cleaning agent
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parts
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JP4761293B2 (en
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Isao Aoyanagi
功 青柳
Keita Matsushita
景太 松下
Tomomi Okada
知巳 岡田
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Eneos Corp
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Japan Energy Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleaning agent composition and a cleaning method for cleaning stains such as flux, wax, processing oil, and particularly a mixture thereof adhered to parts such as electric/electronic parts, optical parts, auto-parts, and precision machine parts. <P>SOLUTION: The cleaning agent composition comprises 60-20 wt% of a saturated hydrocarbon having a boiling point of 200-350°C and 40-80 wt% of an acetate. Preferably, the saturated hydrocarbon has 12-19 carbon atoms; the acetate is 3-methyl-3-methoxybutyl acetate; and the cleaning agent composition has a flash point of 70°C or higher. Further, various stains can be sufficiently cleaned by a cleaning method in which a material to be cleaned is subjected to immersion cleaning using the cleaning agent and then immersed in a hydrofluorocarbon or a hydrofluoroether for rinsing. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、電気・電子部品、光学部品、自動車部品、精密機械部品などの部品に付着したフラックス、ワックス、加工油などの、特には、これらが複合して付着した汚れを洗浄するための洗浄剤組成物及び洗浄方法に関する。   The present invention is a cleaning for cleaning dirt, such as flux, wax, processing oil, etc. adhering to parts such as electric / electronic parts, optical parts, automobile parts, precision machine parts, etc. The present invention relates to an agent composition and a cleaning method.

従来、フラックス、ワックス、加工油、植物油などが付着した精密部品の洗浄には、トリフロロトリクロロエタンなどのフロン系溶剤あるいは1,1,1−トリクロロエタン、トリクロロエチレン、塩化メチレンなどの塩素系溶剤が洗浄剤として使用されてきた。しかし、トリフロロトリクロロエタンや1,1,1−トリクロロエタンはオゾン層を破壊する物質として、1995年末にその製造が禁止された。また、トリクロロエチレンや塩化メチレンは毒性が強く、放出された場合に大気汚染、水質汚染を起こすため、その法規制が厳しい。   Conventionally, fluorocarbon solvents such as trifluorotrichloroethane or chlorinated solvents such as 1,1,1-trichloroethane, trichloroethylene, and methylene chloride are used as cleaning agents for cleaning precision parts to which flux, wax, processing oil, vegetable oil, etc. are attached. Has been used as. However, the production of trifluorotrichloroethane and 1,1,1-trichloroethane was prohibited at the end of 1995 as substances that destroy the ozone layer. Also, trichlorethylene and methylene chloride are highly toxic, and if released, cause air pollution and water pollution, so the laws and regulations are strict.

また、界面活性剤や無機アルカリを添加した水系洗浄剤、リン酸塩類等の水溶性洗浄剤の利用も検討されるが、洗浄力が乏しく、かつ排水処理設備に大きなスペースを必要とするため経済性の面からも好ましくない。そのため、オゾン層破壊がなく、高脱脂力で低毒性、かつ常温で引火性のない、比較的安全な炭化水素系洗浄剤が見直されているが、フロン系溶剤や塩素系溶剤と異なり引火性の液体であるため、消防法により危険物の指定数量の制約がある。   In addition, the use of water-based detergents containing surfactants and inorganic alkalis, and water-soluble detergents such as phosphates is also considered, but it is economical because it has poor detergency and requires a large space for wastewater treatment facilities. It is not preferable from the viewpoint of sex. Therefore, a relatively safe hydrocarbon-based cleaning agent that has no ozone depletion, high degreasing power, low toxicity, and no flammability at room temperature has been reviewed. Unlike chlorofluorocarbon and chlorinated solvents, flammable Because of this liquid, there are restrictions on the number of dangerous goods specified by the Fire Service Act.

消防法危険物第三石油類に分類される炭化水素は、危険物の指定数量としての制約が少ない反面、蒸発速度が遅いために洗浄処理後の乾燥に時間がかかるという問題があった。また、ハイドロフルオロカーボン又はハイドロフルオロエーテル(HFC/E)は炭化水素洗浄剤で洗浄後のすすぎ剤や蒸気洗浄剤として使用されるが、炭化水素洗浄剤は、HFC/Eに難溶であるため、被洗浄物表面上で、炭化水素洗浄剤からHFC/Eへの置換が十分に行われず、汚れ成分を含む炭化水素洗浄剤の一部が被洗浄物表面に付着したまま残留し、洗浄不良を起こす恐れがあった。   Hydrocarbons classified as dangerous oil third petroleums of the Fire Service Act have few restrictions on the designated quantity of dangerous goods, but have a problem that it takes time to dry after washing because of the slow evaporation rate. Hydrofluorocarbon or hydrofluoroether (HFC / E) is used as a rinsing agent or a steam cleaning agent after cleaning with a hydrocarbon cleaner, but the hydrocarbon cleaner is hardly soluble in HFC / E. The hydrocarbon cleaning agent is not sufficiently replaced with HFC / E on the surface of the object to be cleaned, and a part of the hydrocarbon cleaning agent including the soil component remains on the surface of the object to be cleaned, resulting in poor cleaning. There was a risk of waking up.

HFC/Eと相溶性のあるグリコールエーテルやエステル等の有機化合物とHFC/Eとの混合物の温浴を用いた洗浄工程と引き続いて該HFC/E単体によるすすぎ工程からなる洗浄方法が提案されている(特許文献1参照)。また、HFC/Eと有機化合物(グリコールエーテル類、グリコールエーテルアセテート類、ヒドロキシカルボン酸エステル類等)から成る均一な洗浄剤で被洗浄物を洗浄した後に該HFC/Eですすぐ工程で、汚染されたすすぎ剤を静置することにより、混入した汚れ成分及び/または洗浄剤成分を分離し、洗浄剤及びすすぎ剤を再利用する方法も提案されている(特許文献2参照)。しかし、これら文献に記載のグリコールエーテル類は、炭化水素と比較すると鉱物油に対する洗浄性が必ずしも高いとはいえない。   There has been proposed a cleaning method comprising a cleaning step using a warm bath of a mixture of an organic compound such as glycol ether or ester compatible with HFC / E and HFC / E and a rinsing step using the HFC / E alone. (See Patent Document 1). In addition, after washing the object to be cleaned with a uniform cleaning agent composed of HFC / E and organic compounds (glycol ethers, glycol ether acetates, hydroxycarboxylic acid esters, etc.), the HFC / E is contaminated in the rinsing process. There has also been proposed a method of separating the contaminated dirt component and / or cleaning agent component by allowing the rinsing agent to stand, and reusing the cleaning agent and the rinsing agent (see Patent Document 2). However, the glycol ethers described in these documents do not necessarily have a high detergency for mineral oil as compared with hydrocarbons.

また、炭化水素系溶剤を主成分とする一次洗浄液で被洗浄物を洗浄処理した後、HFCを主成分とする二次洗浄液ですすぎ洗浄する洗浄装置(特許文献3参照)や、HFC/Eに難溶性の炭化水素等の有機化合物とHFC/Eを洗浄槽に二層分離させて充填し、被洗浄物を主として有機化合物を含む上層液体により洗浄した後、これを主として該HFC/Eを含む下層液体によりシャワー洗浄し、次いで該HFC/Eですすぎ、更にこれを該HFC/Eの飽和蒸気により蒸気洗浄することからなる洗浄方法が提案されている(特許文献4参照)。さらに、炭化水素系溶剤で被洗浄物を洗浄後にHFC/Eですすぎ洗浄する洗浄装置が提案されている(特許文献5参照)。ここでは、炭化水素系溶剤とHFC/Eが相溶しないことで両者を容易に比重分離できることが特徴として挙げられている。これらの特許は、HFC/Eに難溶性の溶剤を用いていることを特徴としており、HFC/Eによるすすぎ工程において溶剤が被洗浄物表面に残存して、溶剤に溶解された汚れ成分が被洗浄物表面にシミを作って洗浄不良を起こす恐れがある。
特開平10−36894号公報 特開2001−334104号公報 特開平6−328052号公報 特開平10−192797号公報 特開平10−202209号公報
In addition, a cleaning apparatus (see Patent Document 3) for cleaning an object to be cleaned with a primary cleaning liquid mainly composed of a hydrocarbon solvent and then rinsing with a secondary cleaning liquid mainly composed of HFC, or HFC / E An organic compound such as a hardly soluble hydrocarbon and HFC / E are separated into two layers in a washing tank and filled, and the object to be washed is washed mainly with an upper liquid containing the organic compound, and then this mainly contains the HFC / E. There has been proposed a cleaning method comprising shower cleaning with a lower layer liquid, then rinsing with the HFC / E, and further steam cleaning with a saturated vapor of the HFC / E (see Patent Document 4). Furthermore, a cleaning apparatus has been proposed in which an object to be cleaned is cleaned with a hydrocarbon solvent and then rinsed with HFC / E (see Patent Document 5). Here, it is mentioned as a feature that the hydrocarbon solvent and HFC / E are not compatible with each other so that both can be easily separated by specific gravity. These patents are characterized by using a solvent that is hardly soluble in HFC / E. In the rinsing process by HFC / E, the solvent remains on the surface of the object to be cleaned, and the soil component dissolved in the solvent is covered. There is a risk of creating stains on the surface of the cleaning object, resulting in poor cleaning.
JP 10-36894 A JP 2001-334104 A JP-A-6-328052 Japanese Patent Laid-Open No. 10-192797 JP-A-10-202209

本発明は、前述のような洗浄不良を起こさず、オゾン層破壊等の環境上の問題が無く、危険物の指定数量としての制約が少なく、揮発によるロスが少なく、加熱洗浄ができ、十分な乾燥性能を有し、回収が容易で、かつ、フラックス、ワックス、加工油などが複合して付着した汚れに対して十分な洗浄特性を有する洗浄剤組成物及び洗浄方法を提供するものである。   The present invention does not cause poor cleaning as described above, has no environmental problems such as ozone layer destruction, has few restrictions on the designated quantity of dangerous materials, has little loss due to volatilization, can be heated and cleaned, and is sufficient It is an object of the present invention to provide a cleaning composition and a cleaning method that have a drying performance, are easy to recover, and have sufficient cleaning properties against dirt adhered by combining flux, wax, processing oil, and the like.

本発明者等は、鋭意研究を重ねた結果、飽和炭化水素と酢酸エステルとの混合物が、各種汚れの洗浄に適し、また、ハイドロフルオロカーボン又はハイドロフルオロエーテルと特有の溶解特性があることを見出し、本発明に到達した。   As a result of extensive research, the present inventors have found that a mixture of a saturated hydrocarbon and an acetate ester is suitable for cleaning various types of dirt, and has a characteristic solubility characteristic with hydrofluorocarbon or hydrofluoroether, The present invention has been reached.

すなわち、本発明の洗浄剤組成物は、沸点が200〜350℃の飽和炭化水素を60〜20重量%、酢酸エステルを40〜80重量%含有する。また、飽和炭化水素の炭素数は12〜19であり、酢酸エステルが3−メチル−3−メトキシブチルアセテートであり、洗浄剤組成物の引火点が70℃以上であることが好ましい。引火点が70℃未満であると、通常、洗浄で使用する温度範囲において、引火性蒸気の発生が多くなり、安全上の危険性が増大するため、引火点70℃以上のものが好ましい。   That is, the cleaning composition of the present invention contains 60 to 20% by weight of saturated hydrocarbon having a boiling point of 200 to 350 ° C. and 40 to 80% by weight of acetate. Moreover, it is preferable that carbon number of a saturated hydrocarbon is 12-19, an acetic ester is 3-methyl-3-methoxybutyl acetate, and the flash point of a cleaning composition is 70 degreeC or more. When the flash point is less than 70 ° C., the generation of flammable vapor is usually increased in the temperature range used for cleaning, and the safety risk increases. Therefore, the flash point is preferably 70 ° C. or higher.

また、この洗浄剤を用いて被洗浄物を浸漬洗浄後、ハイドロフルオロカーボン又はハイドロフルオロエーテルに浸漬してすすぎを行う洗浄方法により、さまざまな汚れに対し、十分な洗浄を行うことができる。
さらに、上記の洗浄方法を行った後、ハイドロフルオロカーボン又はハイドロフルオロエーテルの蒸気と被洗浄物を接触させて蒸気洗浄を行い、その後、被洗浄物を乾燥する洗浄方法であって、蒸気洗浄の際に、前記洗浄剤組成物とハイドロフルオロカーボン又はハイドロフルオロエーテルが相溶することにより、被洗浄物表面上の洗浄剤組成物とハイドロフルオロカーボン又はハイドロフルオロエーテルを置換させ、かつ、すすぎや蒸気洗浄を行った後の洗浄剤組成物を含むハイドロフルオロカーボン又はハイドロフルオロエーテルを冷却することにより二層分離させることにより、各々を容易に回収することができる。このときのハイドロフルオロカーボン又はハイドロフルオロエーテルの沸点は30〜150℃であることが好ましい。
Further, after the object to be cleaned is immersed and cleaned using this cleaning agent, various cleanings can be sufficiently cleaned by a cleaning method in which the object is rinsed by being immersed in hydrofluorocarbon or hydrofluoroether.
Further, after performing the above-described cleaning method, the cleaning is performed by bringing the hydrofluorocarbon or hydrofluoroether vapor into contact with the object to be cleaned, followed by steam cleaning, and then drying the object to be cleaned. In addition, the cleaning composition and the hydrofluorocarbon or hydrofluoroether are compatible with each other, so that the cleaning composition on the surface of the object to be cleaned and the hydrofluorocarbon or hydrofluoroether are replaced, and rinsing or steam cleaning is performed. Each can be easily recovered by separating the two layers by cooling the hydrofluorocarbon or hydrofluoroether containing the subsequent cleaning composition. The boiling point of the hydrofluorocarbon or hydrofluoroether at this time is preferably 30 to 150 ° C.

本発明による洗浄剤組成物は、オゾン層破壊等の環境上の問題が無く、第3石油類に属することから危険物の指定数量としての制約が少なく、高沸点がゆえに揮発によるロスが少なくて加熱洗浄ができ、かつ、フラックス、ワックス、加工油などが複合して付着した汚れに対して十分な洗浄特性を有している。そして、HFC/Eの沸点温度近傍において相溶し、低温になるに連れて溶解度が大きく低下する本発明の洗浄剤組成物の特性を活用した洗浄方法により、該HFC/Eによる被洗浄物のすすぎの健全性、被洗浄物の速い蒸発速度及び洗浄剤と蒸気洗浄剤の容易な分離回収方法が提供される。   The cleaning composition according to the present invention has no environmental problems such as ozone layer destruction, and since it belongs to the third petroleum, there are few restrictions on the designated quantity of dangerous goods, and because of its high boiling point, there is little loss due to volatilization. It can be cleaned by heating, and has sufficient cleaning properties against dirt adhered by a combination of flux, wax, processing oil, and the like. And, by the cleaning method utilizing the characteristics of the cleaning composition of the present invention, which is compatible in the vicinity of the boiling point temperature of HFC / E, and the solubility greatly decreases as the temperature becomes lower, the object to be cleaned by the HFC / E A rinsing soundness, a fast evaporation rate of an object to be cleaned, and an easy separation and recovery method of a cleaning agent and a steam cleaning agent are provided.

本発明の洗浄剤組成物は、沸点が200〜350℃の範囲にある飽和炭化水素を60〜20重量%含む。飽和炭化水素は、直鎖状、分岐鎖状、環状であっても、これらを単独で用いても複数を混合して用いても構わない。飽和脂肪族炭化水素が好ましく、特には、直鎖飽和脂肪族炭化水素が好ましい。沸点が200℃未満の飽和炭化水素は消防法危険物の第二石油類、または、第一石油類に属するため、安全上好ましくない。また、沸点が350℃を超えると、飽和炭化水素が高粘度になるため、洗浄効率が低下したり、洗浄後の乾燥がしにくくなるため好ましくない。飽和炭化水素は炭素数12〜19、特に炭素数12が、特には、ノルマルドデカンが好ましく用いられる。
本発明の洗浄剤組成物は、上記飽和炭化水素を60〜20重量%含有するものであり、40〜30重量%含有することが好ましい。飽和炭化水素が20重量%未満であると、鉱物油に対する洗浄性が低下するため好ましくない。また、60重量%を超えると、HFC/Eとの相溶性が低くなるため、HFC/Eでのすすぎや蒸気洗浄を行う際、洗浄剤の置換が行われにくくなるため好ましくない。
The cleaning composition of the present invention contains 60 to 20% by weight of a saturated hydrocarbon having a boiling point in the range of 200 to 350 ° C. The saturated hydrocarbon may be linear, branched, or cyclic, and these may be used alone or in combination. Saturated aliphatic hydrocarbons are preferred, and straight chain saturated aliphatic hydrocarbons are particularly preferred. Saturated hydrocarbons having a boiling point of less than 200 ° C. are not preferable for safety because they belong to the second petroleum or the first petroleum, which is a dangerous material of the Fire Service Act. On the other hand, if the boiling point exceeds 350 ° C., the saturated hydrocarbon has a high viscosity, which is not preferable because the cleaning efficiency is lowered and drying after the cleaning becomes difficult. The saturated hydrocarbon preferably has 12 to 19 carbon atoms, particularly 12 carbon atoms, and particularly normal decane.
The cleaning composition of the present invention contains 60 to 20% by weight of the saturated hydrocarbon, and preferably 40 to 30% by weight. A saturated hydrocarbon content of less than 20% by weight is not preferable because the cleaning performance for mineral oil is reduced. On the other hand, if it exceeds 60% by weight, the compatibility with HFC / E is lowered, and therefore, it is difficult to replace the cleaning agent when rinsing with HFC / E or steam cleaning.

本発明の洗浄剤組成物は、酢酸エステルを40〜80重量%含有するものであり、60〜70重量%含有することが好ましい。酢酸エステルとしては、ヒドロキシル基を有する脂肪族炭化水素誘導体と酢酸のエステル、特には、ジアルキルエーテルの水素元素の一つをヒドロキシル基で置換したアルコールと酢酸のエステルが好ましく用いられる。酢酸エステルの炭素数は5〜10、特に6〜8が好ましい。
酢酸エステルが40重量%未満であると、フラックス、ワックスといった極性物質を含む汚れに対する洗浄性が低下するとともに、HFC/Eとの溶解性が低下するため、HFC/Eでのすすぎや蒸気洗浄を行う際、洗浄剤の置換がされにくくなるため好ましくない。また、80重量%を超えると鉱物油に対する洗浄性が低下するため好ましくない。
The cleaning composition of the present invention contains 40 to 80% by weight of acetate and preferably 60 to 70% by weight. As the acetic acid ester, an aliphatic hydrocarbon derivative having a hydroxyl group and an acetic acid ester, in particular, an alcohol and acetic acid ester in which one of hydrogen elements of a dialkyl ether is substituted with a hydroxyl group are preferably used. The number of carbon atoms of the acetate ester is preferably 5 to 10, particularly 6 to 8.
If the acetic acid ester is less than 40% by weight, the cleaning performance with respect to dirt containing polar substances such as flux and wax is reduced, and the solubility with HFC / E is reduced. When performing, it is not preferable because the cleaning agent is hardly replaced. On the other hand, if it exceeds 80% by weight, it is not preferable because the detergency to mineral oil is lowered.

酢酸エステルとしては、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノプロピルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールジアセテート、ブチレングリコールモノエチルエーテルアセテート、ブチレングリコールモノプロピルエーテルアセテート、ブチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノプロピルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテートが挙げられる。入手の容易性、引火点の高さから、ブチレングリコールモノメチルエーテルアセテートの一種である3−メチル−3−メトキシブチルアセテートが好ましく用いられる。   As the acetate ester, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol diacetate, Butylene glycol monoethyl ether acetate, butylene glycol monopropyl ether acetate, butylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monomethyl ether acetate, dipropylene glycol Monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monomethyl ether acetate. In view of availability and high flash point, 3-methyl-3-methoxybutyl acetate, which is a kind of butylene glycol monomethyl ether acetate, is preferably used.

本発明の洗浄剤組成物には、本発明の目的を損なわない範囲で、他の炭化水素類、エステル類、アルコール類、ケトン類、ラクタム類などの配合成分や、界面活性剤、酸化防止剤、紫外線吸収剤、防錆剤などの慣用の添加剤を含めることができる。これら成分の含有量は、合計で10重量%未満、特には2重量%未満であることが好ましい。また、通常、水は配合されないことが好ましい。   The cleaning composition of the present invention includes other components such as hydrocarbons, esters, alcohols, ketones, lactams, surfactants, antioxidants and the like as long as the object of the present invention is not impaired. Conventional additives such as UV absorbers and rust inhibitors can be included. The total content of these components is preferably less than 10% by weight, particularly less than 2% by weight. Moreover, it is preferable that water is not normally mix | blended.

界面活性剤としては非イオン性界面活性剤が好ましく、例えば高級アルコールエチレンオキサイド付加物、アルキルフェノールエチレンオキサイド付加物、脂肪酸エチレンオキサイド付加物、高級アルキルアミンエチレンオキサイド付加物、ソルビトール及びソルビタンの脂肪酸エステル、ショ糖脂肪酸エステル、シリコン系、フッ素系などいずれのものも使用できる。   The surfactant is preferably a nonionic surfactant. For example, a higher alcohol ethylene oxide adduct, an alkylphenol ethylene oxide adduct, a fatty acid ethylene oxide adduct, a higher alkylamine ethylene oxide adduct, sorbitol and a fatty acid ester of sorbitan, Any of sugar fatty acid ester, silicon type, fluorine type and the like can be used.

また、紫外線吸収剤及び酸化防止剤としては、洗浄液の長期保存などにおける安定性の向上に役立ち、紫外線吸収剤としては例えばベンゾトリアゾール系、ベンゾフェノン系、ヒンダードアミン系などを使用でき、酸化防止剤としては例えばフェノール系、アミン系、硫黄系、リン系など、本発明の洗浄剤組成物に溶解するものはいずれも使用できる。フェノール系酸化防止剤を、50〜1000ppm添加することが特に好ましい。   In addition, UV absorbers and antioxidants help improve stability during long-term storage of cleaning liquids, and UV absorbers such as benzotriazoles, benzophenones, and hindered amines can be used. Any of those that dissolve in the cleaning composition of the present invention, such as phenol, amine, sulfur, and phosphorus, can be used. It is particularly preferable to add 50 to 1000 ppm of a phenolic antioxidant.

本発明の洗浄剤組成物は引火点が高い反面、蒸発速度が遅いという問題があるため、速乾性を持たせるためにHFC/Eを蒸気洗浄剤とする蒸気洗浄を用いるのが好ましい。すなわち、HFC/Eを満たしたすすぎ槽で被洗浄物に付着した洗浄剤をすすいで除去した後に、被洗浄物を該HFC/Eの飽和蒸気層に静置することで蒸発速度が格段に改善される。ここで、HFC/Eの沸点は30〜150℃の範囲にあり、ハンドリングのしやすさ、洗浄剤との相溶性及び洗浄剤との沸点差を考慮して、沸点が40〜110℃のハイドロフルオロエーテル(HFE)が特に好ましく用いられる。HFEの例としては、1,2,2,2−テトラフルオロエチル−ヘプタフルオロプロピルエーテル(沸点40℃)、1,1,1,2,3,3−ヘキサフルオロ−2−ヘプタフルオロプロピロキシ−3−(1,2,2,2−テトラフルオロエトキシ)−プロパン(沸点104℃)、1,1,2,2−テトラフルオロエチル−2,2,2−トリフルオロエチルエーテル(沸点56℃)、ノナフルオロブチルメチルエーテル(沸点61℃)、ノナフルオロブチルエチルエーテル(沸点76℃)が挙げられる。   Although the cleaning composition of the present invention has a high flash point, it has a problem that the evaporation rate is slow. Therefore, it is preferable to use steam cleaning using HFC / E as a steam cleaning agent in order to provide quick drying. That is, after rinsing and removing the cleaning agent adhering to the object to be cleaned in a rinsing tank filled with HFC / E, the evaporation rate is remarkably improved by leaving the object to be cleaned in the saturated vapor layer of the HFC / E. Is done. Here, the boiling point of HFC / E is in the range of 30 to 150 ° C. Considering the ease of handling, compatibility with the cleaning agent and the difference in boiling point with the cleaning agent, Fluoroether (HFE) is particularly preferably used. Examples of HFE include 1,2,2,2-tetrafluoroethyl-heptafluoropropyl ether (boiling point 40 ° C.), 1,1,1,2,3,3-hexafluoro-2-heptafluoropropyloxy- 3- (1,2,2,2-tetrafluoroethoxy) -propane (boiling point 104 ° C.), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (boiling point 56 ° C.) , Nonafluorobutyl methyl ether (boiling point 61 ° C.) and nonafluorobutyl ethyl ether (boiling point 76 ° C.).

一般に蒸気洗浄では蒸気洗浄剤の沸点近傍において洗浄剤と蒸気洗浄剤は相溶するのが好ましいとされている。本発明の洗浄剤組成物であるノルマルドデカンと3−メチル−3−メトキシブチルアセテートの混合物と、蒸気洗浄剤としてのHFEの一種である1,1,2,2−テトラフルオロエチル−2,2,2−トリフルオロエチルエーテル(HFE−1)(実施例1〜5、及び比較例1〜3)の溶解度を図1に示す。本発明の洗浄剤組成物は、50℃でHFE−1に相溶することから、良好な蒸気洗浄が達成される。また、本発明の洗浄剤組成物のHFE−1への溶解度は温度が下がるに連れて急激に低下する。したがって、蒸気洗浄剤の沸点近傍で均一な本発明の洗浄剤組成物と蒸気洗浄剤の混合物は、冷却すると二層に分離して、容易に各々を回収し、再利用することができる。   In general, in the case of steam cleaning, it is preferable that the cleaning agent and the steam cleaning agent are compatible in the vicinity of the boiling point of the steam cleaning agent. A mixture of normal dodecane and 3-methyl-3-methoxybutyl acetate, which is a cleaning composition of the present invention, and 1,1,2,2-tetrafluoroethyl-2,2 which is a kind of HFE as a steam cleaning agent , 2-trifluoroethyl ether (HFE-1) (Examples 1-5 and Comparative Examples 1-3) is shown in FIG. Since the cleaning composition of the present invention is compatible with HFE-1 at 50 ° C., good steam cleaning is achieved. Further, the solubility of the cleaning composition of the present invention in HFE-1 rapidly decreases as the temperature decreases. Accordingly, the mixture of the cleaning composition of the present invention and the steam cleaning agent that is uniform near the boiling point of the steam cleaning agent is separated into two layers when cooled, and each can be easily recovered and reused.

本発明の洗浄方法において、被洗浄物を洗浄剤組成物と接触させる方法は特に制限されるものでなく、公知のいずれの方法も使用できる。例えば、洗浄剤組成物を含浸したスポンジなどによる拭き取り、洗浄剤組成物への浸漬、スプレーなどにより接触させることが好ましい。浸漬による洗浄においては、洗浄効果を高めるために、同時に攪拌、揺動、超音波、エアバブリングなどを組み合せることが更に好ましい。この場合、超音波の使用条件は、例えば発振周波数20〜100kHz、洗浄剤1L当りの発振出力10〜200Wが好ましい。エアバブリングでは、微細な気泡を、好ましくはガス:洗浄剤の体積比を1:1〜5:1で通気することにより、洗浄剤組成物に溶解しない汚れを気泡と共に上昇させ、分離できる。スプレーによる洗浄においては、その圧力は、例えば0.05〜1MPaが好ましい。いずれの場合も洗浄時間は、15秒間〜2時間、特には30秒間〜20分間が好ましい。この範囲未満では洗浄が不十分で、汚れを十分に除去できない。一方、この範囲を超えても洗浄効果は格別に向上しない。洗浄温度は、20〜130℃が好ましく、50〜130℃で加熱処理することにより洗浄効果を著しく上昇させることができる。   In the cleaning method of the present invention, the method of bringing the article to be cleaned into contact with the cleaning composition is not particularly limited, and any known method can be used. For example, it is preferable to make contact by wiping with a sponge impregnated with the cleaning composition, immersion in the cleaning composition, spraying, or the like. In cleaning by dipping, it is more preferable to combine stirring, shaking, ultrasonic waves, air bubbling, etc. at the same time in order to enhance the cleaning effect. In this case, the use conditions of the ultrasonic waves are preferably, for example, an oscillation frequency of 20 to 100 kHz and an oscillation output of 10 to 200 W per 1 L of the cleaning agent. In the air bubbling, fine bubbles are preferably aerated with a volume ratio of gas: cleaning agent of 1: 1 to 5: 1, whereby dirt that does not dissolve in the cleaning composition can be raised together with the bubbles and separated. In cleaning by spraying, the pressure is preferably 0.05 to 1 MPa, for example. In any case, the washing time is preferably 15 seconds to 2 hours, particularly 30 seconds to 20 minutes. If it is less than this range, washing is insufficient and the dirt cannot be removed sufficiently. On the other hand, even if it exceeds this range, the cleaning effect is not improved significantly. The washing temperature is preferably 20 to 130 ° C, and the washing effect can be remarkably increased by heat treatment at 50 to 130 ° C.

本発明の洗浄方法において、被洗浄物に付着した洗浄剤の除去は、HFC/Eを用いたすすぎ及び蒸気洗浄により行う。その方法は特に制限されるものでなく、公知のいずれの方法も使用できる。例えば、HFC/Eを満たしたすすぎ槽で洗浄剤の付着した被洗浄物をすすいだ後に、該HFC/Eの飽和蒸気層に静置して蒸気洗浄することにより清浄な物品が得られる。すすぎ槽は、沸騰浴または冷浴のいずれか一方、または、両方でもよく、また、すすぎ効果を高めるために攪拌機または超音波発生機を取り付けることもできる。沸騰浴ですすいだ後に超音波発生機の付いた冷浴ですすぐのが最も効果的である。被洗浄物はすすぎ槽でHFC/Eの沸点よりも低い温度に冷却された後に引き上げられて、該HFC/Eの飽和蒸気層に導入されると、被洗浄物表面で該HFC/Eは凝縮・液化して、すすぎ槽では除去できなかった汚れを含む洗浄剤と置換され、すすぎが完了する。この際、該HFC/Eと洗浄剤の相溶性が低いと、置換が不十分となり、被洗浄剤表面に洗浄剤が残留して、シミが発生する恐れがあるが、本発明の洗浄剤組成物は該HFC/Eの沸点近傍で該HFC/Eと相溶するため、洗浄不良は起こらない。すすぎを終了した被洗浄物の表面は、該HFC/Eのみで濡れている状態にあるため、速やかに乾燥される。   In the cleaning method of the present invention, the cleaning agent adhering to the object to be cleaned is removed by rinsing and steam cleaning using HFC / E. The method is not particularly limited, and any known method can be used. For example, after rinsing an object to which the cleaning agent is adhered in a rinsing tank filled with HFC / E, a clean article can be obtained by standing in a saturated vapor layer of the HFC / E and performing steam cleaning. The rinsing tank may be either a boiling bath or a cold bath, or both, and a stirrer or an ultrasonic generator may be attached to enhance the rinsing effect. It is most effective to rinse in a boiling bath and then in a cold bath with an ultrasonic generator. When the object to be cleaned is cooled to a temperature lower than the boiling point of HFC / E in the rinsing tank and then pulled up and introduced into the saturated vapor layer of HFC / E, the HFC / E is condensed on the surface of the object to be cleaned. -Liquefaction is replaced with a cleaning agent containing dirt that could not be removed in the rinsing tank, and rinsing is completed. At this time, if the compatibility between the HFC / E and the cleaning agent is low, the substitution may be insufficient, and the cleaning agent may remain on the surface of the cleaning agent, causing stains. Since the product is compatible with the HFC / E in the vicinity of the boiling point of the HFC / E, poor cleaning does not occur. Since the surface of the object to be cleaned that has been rinsed is wet only by the HFC / E, it is quickly dried.

蒸気洗浄剤から洗浄剤成分や汚れ成分を分離するには、しばしば蒸留法が適用される。本発明の洗浄剤組成物においても蒸気洗浄剤との分離に蒸留法を用いることが可能であるが、一般に蒸留法には多大な時間や費用を要するという問題点がある。図1に示したように、本発明の洗浄剤組成物と蒸気洗浄剤の相溶性には顕著な温度依存性があることから、本発明の洗浄方法では、洗浄剤を含有するすすぎ槽や蒸気洗浄剤の凝縮液を冷却して2層分離させて、各々を回収して再利用する分離方法も含まれている。ここで、回収された汚れ成分を含む洗浄剤は、蒸留法等により洗浄剤組成物と汚れ成分に分離された後に再利用される。   Distillation methods are often applied to separate detergent and soil components from steam cleaners. Even in the cleaning composition of the present invention, it is possible to use a distillation method for separation from the vapor cleaning agent, but the distillation method generally has a problem of requiring a great deal of time and cost. As shown in FIG. 1, the compatibility between the cleaning composition of the present invention and the steam cleaning agent has a remarkable temperature dependence. Therefore, in the cleaning method of the present invention, the rinsing tank or steam containing the cleaning agent is used. A separation method is also included in which the condensate of the cleaning agent is cooled and separated into two layers, and each is recovered and reused. Here, the cleaning agent containing the collected soil component is reused after being separated into the cleaning composition and the soil component by a distillation method or the like.

洗浄対象物としては、電子・電気部品、光学部品、精密機械部品、自動車部品などの部品を例示することができる。対象となる電気・電子部品としては、プリント配線基板、セラミック配線基板などの配線基板、リードフレームなどの半導体パッケージ部材、リレー、コネクターなどの接点部材、液晶、プラズマディスプレイなどの表示部品、ハードディスク記憶媒体、磁気ヘッドなどの磁気記憶部品、水晶振動子などの圧電部品、モータ、ソレノイドなどの電動機部品、センサー部品が挙げられる。光学部品としては、眼鏡、カメラ用などのレンズ、その筐体が挙げられる。精密機械部品としては、VTRなどに用いられる精密ベアリングなどの部品が挙げられる。   Examples of the object to be cleaned include parts such as electronic / electrical parts, optical parts, precision machine parts, and automobile parts. Target electrical / electronic components include printed circuit boards, wiring boards such as ceramic wiring boards, semiconductor package members such as lead frames, contact members such as relays and connectors, display parts such as liquid crystals and plasma displays, and hard disk storage media. And magnetic storage parts such as magnetic heads, piezoelectric parts such as crystal oscillators, motor parts such as motors and solenoids, and sensor parts. Examples of the optical component include glasses, a lens for a camera, and a housing thereof. Examples of precision machine parts include parts such as precision bearings used in VTRs and the like.

洗浄対象物に付着している汚れとしては、アスファルトピッチ、ワックス、松脂、油脂、鉱油などからなる機械油、植物油、グリース、フラックス、フォトレジスト、接着剤が挙げられる。本発明の洗浄剤組成物は、特に、フラックス、ワックスに対して優れた洗浄力を有する。   Examples of dirt adhering to the object to be cleaned include machine oils such as asphalt pitch, wax, pine oil, fats and oils, vegetable oils, greases, fluxes, photoresists, and adhesives. The cleaning composition of the present invention has an excellent cleaning power especially for fluxes and waxes.

以下、本発明を実施例、比較例により更に詳細に説明するが、本発明は実施例により限定して解釈されるものではない。   EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is limited to an Example and is not interpreted.

実施例1〜5、比較例1〜10
[洗浄剤の調製]
ノルマルウンデカン(n−C11)(沸点171℃)、ノルマルドデカン(n−C12)(沸点209℃)及び3−メトキシ−3−メチルブチルアセテート(MMBAC)(沸点188℃)を用い、表1の配合量で配合して、実施例1〜5と比較例1〜10の洗浄剤を調製した。
Examples 1-5, Comparative Examples 1-10
[Preparation of detergent]
Formulation of Table 1 using normal undecane (n-C11) (boiling point 171 ° C.), normal dodecane (n-C12) (boiling point 209 ° C.) and 3-methoxy-3-methylbutyl acetate (MMBAC) (boiling point 188 ° C.) The cleaning agents of Examples 1 to 5 and Comparative Examples 1 to 10 were prepared by mixing in amounts.

Figure 2006249114
Figure 2006249114

[引火点]
実施例1〜5と比較例1〜10の洗浄剤のタグ密閉式引火点(JIS K2265)を表1に併せて示した。実施例1〜5と比較例1〜4の洗浄剤は第三石油類(引火点70℃以上200℃未満)、比較例5〜10の洗浄剤は第二石油類である。(引火点21℃以上70℃未満)。
[Flash point]
Table 1 also shows tag sealed flash points (JIS K2265) of the cleaning agents of Examples 1 to 5 and Comparative Examples 1 to 10. The cleaning agents in Examples 1 to 5 and Comparative Examples 1 to 4 are third petroleums (flash point 70 ° C. or higher and lower than 200 ° C.), and the cleaning agents in Comparative Examples 5 to 10 are second petroleums. (Flash point 21 ° C. or higher and lower than 70 ° C.).

[蒸気洗浄剤への溶解度]
第三石油類に分類される実施例1〜5と比較例1〜4の洗浄剤について、1,1,2,2−テトラフルオロエチル−2,2,2−トリフルオロエチルエーテル(HFE−1)への溶解度を測定した。結果を表2と図1に示す。ここで、溶解度の測定の上限は100g/100gHFE−1とした。実施例1〜5の洗浄剤は50℃でHFE−1と相溶し、冷却するに従い相溶性は大きく低下した。一方、比較例1〜3の洗浄剤は50℃においてもHFE−1への溶解度が低く、部品上に残存付着している洗浄剤との置換が行われにくい。したがって、実施例1〜5と同じ条件で蒸気洗浄した場合は、すすぎ不良となる。また、比較例4の洗浄剤は−10℃においてもHFE−1に完全に相溶するため、冷却しながら洗浄剤と蒸気洗浄剤(HFE−1)を分離して各々を回収することはできない。50℃においてHFE−1に溶解している各洗浄剤(100g/100gHFE−1を上限とする)の−10℃における回収率を分離回収率として表2に付記する。
[Solubility in steam cleaner]
For the cleaning agents of Examples 1 to 5 and Comparative Examples 1 to 4 classified as third petroleums, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (HFE-1 ) Was measured. The results are shown in Table 2 and FIG. Here, the upper limit of the measurement of solubility was 100 g / 100 g HFE-1. The cleaning agents of Examples 1 to 5 were compatible with HFE-1 at 50 ° C., and the compatibility was greatly reduced as the cooling was performed. On the other hand, the cleaning agents of Comparative Examples 1 to 3 have low solubility in HFE-1 even at 50 ° C., and are not easily replaced with the cleaning agent remaining on the parts. Therefore, when steam cleaning is performed under the same conditions as in Examples 1 to 5, rinsing failure occurs. Moreover, since the cleaning agent of Comparative Example 4 is completely compatible with HFE-1 even at −10 ° C., it is not possible to separate the cleaning agent and the steam cleaning agent (HFE-1) while cooling and recover each of them. . The recovery rate at −10 ° C. of each cleaning agent (up to 100 g / 100 g HFE-1) dissolved in HFE-1 at 50 ° C. is shown in Table 2 as the separation recovery rate.

Figure 2006249114
Figure 2006249114

[松脂溶解性]
第三石油類に分類される実施例1〜5と比較例1〜4の洗浄剤について松脂(関東化学)の溶解性試験を実施した。各洗浄剤40重量%と松脂60重量%を混合し、室温で超音波照射(出力100W、周波数28kHz)を5分間行い、目視により不溶解分の有無を観察した。完全に相溶したものを○、微かにでも不溶解分の有るものを×として評価し、表2に併せて示した。この結果から、実施例1〜5の洗浄剤は高い松脂溶解性を示すことがわかる。一方、比較例1〜2の洗浄剤の松脂溶解性は劣っていることがわかる。
[Solid solubility]
For the cleaning agents of Examples 1 to 5 and Comparative Examples 1 to 4 classified as third petroleums, a solubility test of pine resin (Kanto Chemical) was conducted. 40% by weight of each cleaning agent and 60% by weight of pine resin were mixed, and ultrasonic irradiation (output 100 W, frequency 28 kHz) was performed at room temperature for 5 minutes, and the presence or absence of insoluble matter was visually observed. The completely compatible materials were evaluated as ◯, and even the slightly insoluble components were evaluated as ×, and are also shown in Table 2. From this result, it can be seen that the cleaning agents of Examples 1 to 5 exhibit high pine resin solubility. On the other hand, it turns out that the pine resin solubility of the cleaning agent of Comparative Examples 1-2 is inferior.

[フラックス洗浄性]
フラックス洗浄性の評価は、金属板(銅板50×50mm、厚さ0.03mm)上にロジン系フラックス入りハンダペースト(タムラ化研製、SQ−1030SZM−1)各1mgを9箇所に塗布し、250℃で30秒間リフローしたものを洗浄した。この洗浄対象物を200cmの洗浄液が充填された洗浄槽において液温20℃で超音波照射(出力100W、周波数28kHz)し、10秒間洗浄した。洗浄後、金属板上にフラックスの痕跡が認められなくなったものを○、微かにでも痕跡のあるものを×として評価し、表2に併せて示した。この結果から、実施例1〜5の洗浄剤は高いフラックス洗浄性を示すことがわかる。
[Flux cleaning properties]
Evaluation of the flux cleaning property was carried out by applying 1 mg each of rosin-based flux-containing solder paste (Tamura Chemical Research, SQ-1030SZM-1) on a metal plate (copper plate 50 × 50 mm, thickness 0.03 mm), 250 What was reflowed at 30 ° C. for 30 seconds was washed. This object to be cleaned was irradiated with ultrasonic waves (output: 100 W, frequency: 28 kHz) at a liquid temperature of 20 ° C. in a cleaning tank filled with 200 cm 3 of cleaning liquid and cleaned for 10 seconds. After cleaning, evaluation was made on the metal plate where no trace of the flux was observed, and evaluation was made on the case where the trace of the flux was slightly observed as x. From this result, it can be seen that the cleaning agents of Examples 1 to 5 exhibit high flux cleaning properties.

[ワックス洗浄性]
ワックスの洗浄性評価は、金属板(銅板50×50mm、厚さ0.03mm)上にテルペンフェノール樹脂系ワックス(日化精工製、アルコワックス542M)100mgを塗布し、室温で30秒間超音波照射(出力100W、周波数28kHz)して洗浄を行った。評価はワックスの残存率(残存するワックス重量の初期塗布量に対する割合(%))を求め、残存率15%未満を○、15%以上を×とした。この結果から、実施例1〜5の洗浄剤は高いワックス洗浄性を示すことがわかる。
[Wax detergency]
Wax cleanability evaluation was performed by applying 100 mg of terpene phenol resin wax (Nikko Seiko, Alcowax 542M) on a metal plate (copper plate 50 × 50 mm, thickness 0.03 mm) and ultrasonically irradiating it at room temperature for 30 seconds. Cleaning was performed at an output of 100 W and a frequency of 28 kHz. In the evaluation, the residual ratio of wax (the ratio (%) of the residual wax weight to the initial coating amount) was obtained. From this result, it can be seen that the cleaning agents of Examples 1 to 5 exhibit high wax detergency.

[植物油洗浄性]
植物油の洗浄性評価は、積層メッシュ板(SUS製30mmφ、厚さ1.0mm)上にひまし油(関東化学)300〜400mgを付着させ、室温で60秒間超音波照射(出力100W、周波数28kHz)して洗浄を行った。評価は植物油残存率(残存する植物油重量の初期の付着量に対する割合(%))を求め、残存率15%未満を○、15%以上を×とした。この結果から、実施例1〜5の洗浄剤は高い植物油洗浄性を示すことがわかる。
[Vegetable oil washability]
Evaluation of the cleanability of vegetable oil was performed by attaching 300 to 400 mg of castor oil (Kanto Chemical) on a laminated mesh plate (SUS 30 mmφ, thickness 1.0 mm), and irradiating with ultrasonic waves (output 100 W, frequency 28 kHz) for 60 seconds at room temperature. And washed. In the evaluation, the residual ratio of vegetable oil (ratio (%) of the amount of residual vegetable oil with respect to the initial amount of adhesion) was determined. From this result, it can be seen that the detergents of Examples 1 to 5 exhibit high vegetable oil detergency.

本発明の洗浄剤組成物は、オゾン層破壊等の環境上の問題が無く、危険物の指定数量としての制約が少なく、揮発によるロスが少なく、加熱洗浄ができ、十分な乾燥性能を有し、かつ、回収が容易であることから、本発明の洗浄剤組成物及び洗浄方法は、電気・電子部品、光学部品、自動車部品、精密機械部品などの部品に付着したフラックス、ワックス、加工油などの、特には、これらが複合して付着した汚れの洗浄に有用である。   The cleaning composition of the present invention has no environmental problems such as ozone layer destruction, has few restrictions on the designated quantity of hazardous materials, has little loss due to volatilization, can be heated and cleaned, and has sufficient drying performance. In addition, since the cleaning composition and the cleaning method of the present invention are easy to collect, the flux, wax, processing oil, etc. attached to parts such as electric / electronic parts, optical parts, automobile parts, precision machine parts, etc. In particular, it is useful for cleaning soils in which these are combined and adhered.

HFEの一種である1,1,2,2−テトラフルオロエチル−2,2,2−トリフルオロエチルエーテルに対する、本発明の洗浄剤組成物の溶解度を示す図である。It is a figure which shows the solubility of the cleaning composition of this invention with respect to 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether which is 1 type of HFE.

Claims (7)

沸点が200〜350℃の飽和炭化水素を60〜20重量%、酢酸エステルを40〜80重量%含有することを特徴とする洗浄剤組成物。   A detergent composition comprising 60 to 20% by weight of saturated hydrocarbon having a boiling point of 200 to 350 ° C. and 40 to 80% by weight of acetate. 飽和炭化水素の炭素数が12〜19である請求項1記載の洗浄剤組成物。   The cleaning composition according to claim 1, wherein the saturated hydrocarbon has 12 to 19 carbon atoms. 酢酸エステルが3−メチル−3−メトキシブチルアセテートである請求項1又は2記載の洗浄剤組成物。   The cleaning composition according to claim 1 or 2, wherein the acetate is 3-methyl-3-methoxybutyl acetate. 洗浄剤組成物の引火点が70℃以上である請求項1乃至3のいずれか一項に記載の洗浄剤組成物。   The cleaning composition according to any one of claims 1 to 3, wherein the cleaning composition has a flash point of 70 ° C or higher. 被洗浄物を請求項1乃至4のいずれか一項に記載の洗浄剤組成物を用いて浸漬洗浄後、ハイドロフルオロカーボン又はハイドロフルオロエーテルに浸漬してすすぎを行うことを特徴とする洗浄方法。   A cleaning method comprising rinsing by immersing an object to be cleaned in a hydrofluorocarbon or hydrofluoroether after immersion cleaning using the cleaning composition according to any one of claims 1 to 4. 請求項5に記載の洗浄方法を行った後、ハイドロフルオロカーボン又はハイドロフルオロエーテルの蒸気と被洗浄物を接触させて蒸気洗浄を行い、その後、被洗浄物を乾燥する洗浄方法であって、蒸気洗浄の際に、前記洗浄剤組成物とハイドロフルオロカーボン又はハイドロフルオロエーテルが相溶することにより、被洗浄物表面上の洗浄剤組成物とハイドロフルオロカーボン又はハイドロフルオロエーテルを置換させ、かつ、すすぎや蒸気洗浄を行った後の洗浄剤組成物を含むハイドロフルオロカーボン又はハイドロフルオロエーテルを冷却することにより二層分離させ、各々を回収することを特徴とする洗浄方法。   A cleaning method for performing steam cleaning by bringing a hydrofluorocarbon or hydrofluoroether vapor into contact with an object to be cleaned after performing the cleaning method according to claim 5, and then drying the object to be cleaned. In this case, the cleaning composition and the hydrofluorocarbon or hydrofluoroether are compatible with each other, thereby replacing the cleaning composition on the surface of the object to be cleaned with the hydrofluorocarbon or hydrofluoroether, and rinsing or steam cleaning. A cleaning method, wherein the hydrofluorocarbon or hydrofluoroether containing the cleaning composition after the step is separated into two layers by cooling, and each is recovered. ハイドロフルオロカーボン又はハイドロフルオロエーテルの沸点が30〜150℃である請求項5又は6に記載の洗浄方法。   The cleaning method according to claim 5 or 6, wherein the boiling point of the hydrofluorocarbon or hydrofluoroether is 30 to 150 ° C.
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