JP4526334B2 - Azeotropic composition - Google Patents
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- JP4526334B2 JP4526334B2 JP2004259295A JP2004259295A JP4526334B2 JP 4526334 B2 JP4526334 B2 JP 4526334B2 JP 2004259295 A JP2004259295 A JP 2004259295A JP 2004259295 A JP2004259295 A JP 2004259295A JP 4526334 B2 JP4526334 B2 JP 4526334B2
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Description
本発明は、高度にフッ素化されたハイドロフルオロエ−テルをベ−スとする共沸乃至それに近い挙動を示す新規な組成物に関するものである。更に詳しくは、加工や錆止めとして金属部品に使用されているグリ−スや加工油等の脱脂及び半導体製造時のフラックス除去のために好適に使用される洗浄剤のほか、発泡剤、作動媒体、分散剤、電気絶縁剤等の用途を代替することが可能な新規な共沸様組成物に関する。 The present invention relates to a novel composition exhibiting azeotropic or close behavior based on a highly fluorinated hydrofluoroether. More specifically, in addition to cleaning agents suitably used for degreasing grease and processing oil used for metal parts as processing and rust prevention and flux removal during semiconductor manufacturing, foaming agents, working media, The present invention relates to a novel azeotrope-like composition capable of replacing applications such as a dispersant and an electrical insulating agent.
クロロフルオロカ−ボンは毒性が少なく難燃性で、化学的、熱的に安定なものが多いため、溶剤、発泡剤、冷媒等に広く使用され、フラックスや加工油等の洗浄には、クロロフルオロカ−ボン系溶剤である１,１,２−トリクロロ−１,２,２−トリフルオロエタン（ＣＦＣ−１１３,沸点約４８度）、或いは塩素系溶剤である１,１,１−トリクロロエタン等が使用されて来た。 Chlorofluorocarbons are low in toxicity and flame retardant, and many are chemically and thermally stable. Therefore, they are widely used in solvents, foaming agents, refrigerants, etc. 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113, boiling point of about 48 degrees), which is a fluorocarbon solvent, or 1,1,1-trichloroethane, which is a chlorinated solvent Has been used.
しかし、オゾン層保護の観点からウイ−ン条約（１９８５年）やモントリオ−ル議定書(１９８７年)に基づき、わが国でもＣＦＣ−１１（トリクロロフルオロメタン）、ＣＦＣ−１２（ジクロロジフルオロメタン）、ＣＦＣ−１１３、ＣＦＣ−１１４（１,２−ジクロロテトラフルオロエタン）、ＣＦＣ−１１５（クロロペンタフルオロエタン）などのクロロフルオロカ−ボンについては、１９９５年までに生産が事実上停止された。また、塩素系溶剤については、衛生や環境面の影響が懸念されている。 However, from the viewpoint of the protection of the ozone layer, CFC-11 (trichlorofluoromethane), CFC-12 (dichlorodifluoromethane), CFC- Production of chlorofluorocarbons such as 113, CFC-114 (1,2-dichlorotetrafluoroethane), and CFC-115 (chloropentafluoroethane) was virtually stopped by 1995. In addition, regarding chlorinated solvents, there are concerns about the impact on hygiene and the environment.
それに代る低沸点溶剤として、パーフルオロブチルメチルエーテルが知られているが、パーフルオロブチルメチルエーテルは、油やフラックス等の汚れに対して洗浄性能が低く、使用できる分野が限られている。 Perfluorobutyl methyl ether is known as an alternative low-boiling solvent, but perfluorobutyl methyl ether has a low cleaning performance against dirt such as oil and flux, and the fields where it can be used are limited.
そのため、パーフルオロブチルメチルエーテルの洗浄性能を改善する試みが行われてきた。例えば、特開２０００−１４３５６８号公報にはパーフルオロブチルメチルエーテル、含臭素炭化水素及び低級アルコールよりなる共沸様組成物が提案されている。さらに、特表平１０−５１０５７９号公報には、ペルフルオロブチルメチルエーテルと、ケトン、アルコール、環状アルカン、塩素化アルカン、一部フッ素化アルコール、ＨＣＦＣなどの有機溶剤との組成物が提案されている。 Therefore, attempts have been made to improve the cleaning performance of perfluorobutyl methyl ether. For example, JP 2000-143568 A proposes an azeotrope-like composition comprising perfluorobutyl methyl ether, a bromine-containing hydrocarbon and a lower alcohol. Further, JP-A-10-510579 proposes a composition of perfluorobutyl methyl ether and an organic solvent such as ketone, alcohol, cyclic alkane, chlorinated alkane, partially fluorinated alcohol, or HCFC. .
本発明者らは、従来公知の組成物とは異なり、洗浄使用工程において蒸留操作があっても組成変化が少なく組成物の特性を維持することができ、且つ回収や再利用に好都合な共沸乃至それに近い挙動(共沸様)を示す、オゾン層を破壊する恐れが無く、塩素を含まない新規な組成物を鋭意研究した結果、本発明に到達した。
本発明は、オゾン層を破壊する恐れが無く、塩素を含まないハイドロフルオロエ−テルをベ−スとして、加工や錆止めとして金属部品に使用されているグリ−スや加工油等の脱脂及び半導体製造時のフラックス除去のために好適に使用される洗浄剤ほか、発泡剤、作動媒体、分散剤、電気絶縁剤等の用途を代替することが可能な共沸乃至それに近い挙動(共沸様)を示す新規な組成物を提供する。 The present invention is based on a hydrofluoroether containing no chlorine, which has no fear of destroying the ozone layer, and is used for degreasing and semiconductors such as grease and processing oil used for metal parts as processing and rust prevention. Azeotropic or similar behavior (azeotrope-like) that can replace applications such as detergents, foaming agents, working media, dispersants, electrical insulation, etc., as well as cleaning agents that are used favorably for flux removal during manufacturing A novel composition is provided.
本発明は、ノナフルオロブチルメチルエ−テルとテトラフルオロプロパノールからなる共沸様組成物を提供する。 The present invention provides an azeotrope-like composition comprising nonafluorobutylmethyl ether and tetrafluoropropanol.
前記テトラフルオロプロパノールが、２，２，３，３−テトラフルオロプロパノールである前記した共沸様組成物は本発明の好ましい態様である。 The aforementioned azeotrope-like composition in which the tetrafluoropropanol is 2,2,3,3-tetrafluoropropanol is a preferred embodiment of the present invention.
８０〜９９．５重量％のノナフルオロブチルメチルエ−テル、および２０〜０．５重量％の２，２，３，３−テトラフルオロプロパノ−ルからなる共沸様組成物は本発明の好ましい態様である。 An azeotrope-like composition comprising 80-99.5% by weight of nonafluorobutylmethyl ether and 20-0.5% by weight of 2,2,3,3-tetrafluoropropanol is used in the present invention. This is a preferred embodiment.
９７．３重量％のノナフルオロブチルメチルエ−テルおよび２．７重量％の２，２，３，３−テトラフルオロプロパノ−ルからなる共沸様組成物は本発明の好ましい態様である。 An azeotrope-like composition consisting of 97.3% by weight nonafluorobutylmethyl ether and 2.7% by weight 2,2,3,3-tetrafluoropropanol is a preferred embodiment of the present invention.
本発明によれば、オゾン層を破壊する恐れが無く、塩素を含まないノナフルオロブチルメチルエ−テルとテトラフルオロプロパノールからなる共沸乃至それに近い挙動を示す新規な組成物が提供される。
本発明によれば、本発明は共沸乃至それに近い挙動を示す組成であるため、使用工程において蒸留操作があっても成分の組成変化が少なく、該組成物の特性を維持することができ、組成物の回収や再利用に好都合な組成物が提供される。
本発明によれば、炭化水素系油等の溶解性がノナフルオロブチルメチルエ−テル単独の場合よりも向上した組成物が提供される。
ADVANTAGE OF THE INVENTION According to this invention, the novel composition which does not have a possibility of destroying an ozone layer, and shows the azeotropy thru | or the behavior close to it consisting of nonafluoro butyl methyl ether and tetrafluoro propanol which do not contain chlorine is provided.
According to the present invention, since the present invention is a composition exhibiting azeotropic or similar behavior, there is little change in composition of components even if there is a distillation operation in the use process, and the characteristics of the composition can be maintained. A composition is provided that is convenient for recovery and reuse of the composition.
According to the present invention, there is provided a composition in which the solubility of a hydrocarbon oil or the like is improved as compared with the case of nonafluorobutylmethyl ether alone.
本発明は、ノナフルオロブチルメチルエ−テルとテトラフルオロプロパノールからなる共沸様組成物を提供する。
本発明で使用されるノナフルオロブチルメチルエ−テルは、以下にＨＦＥ−４４９ｓということがある。
The present invention provides an azeotrope-like composition comprising nonafluorobutylmethyl ether and tetrafluoropropanol.
The nonafluorobutylmethyl ether used in the present invention may be referred to as HFE-449s below.
本発明は、特表平１０−５１０５７９号公報には、ペルフルオロブチルメチルエーテルとトリフルオロエタノールまたはペンタフルオロプロパノールとの組成物を記載するが、本発明らが同公報には記載されていない特定の組成物であって、すぐれた共沸様組成物を見出したことに基づき、新規なすぐれた共沸様組成物を提供するものである。 The present invention describes a composition of perfluorobutyl methyl ether and trifluoroethanol or pentafluoropropanol in JP-A-10-510579, but the present invention does not describe a specific composition that is not described in the publication. Based on the discovery of an excellent azeotrope-like composition, a novel and superior azeotrope-like composition is provided.
本発明のテトラフルオロプロパノールとしては、２，２，３，３−テトラフルオロプロパノ−ル（以下、ＴＦＰということがある）が特に好ましい。 As the tetrafluoropropanol of the present invention, 2,2,3,3-tetrafluoropropanol (hereinafter sometimes referred to as TFP) is particularly preferable.
本発明の共沸様組成物は、ノナフルオロブチルメチルエ−テル（ＨＦＥ−４４９ｓ）、および２，２，３，３−テトラフルオロプロパノ−ル（ＴＦＰ）からなる共沸様組成物である。 The azeotrope-like composition of the present invention is an azeotrope-like composition comprising nonafluorobutylmethyl ether (HFE-449s) and 2,2,3,3-tetrafluoropropanol (TFP). .
本発明の共沸様組成物の好ましい組成としては、８０〜９９．５重量％のノナフルオロブチルメチルエ−テル、および２０〜０．５重量％の２，２，３，３−テトラフルオロプロパノ−ルからなる共沸様組成物を挙げることができる。 Preferred compositions of the azeotrope-like composition of the present invention include 80-99.5 wt% nonafluorobutylmethyl ether and 20-0.5 wt% 2,2,3,3-tetrafluoropropalyst. Mention may be made of an azeotrope-like composition comprising norm.
本発明の共沸様組成物において、特に好ましい組成として、９７．３重量％のノナフルオロブチルメチルエ−テル、および２．７重量％の２，２，３，３−テトラフルオロプロパノ−ルからなる共沸様組成物を挙げることができる。
このような組成を有する共沸様組成物は、後記した実施例１に具体的に示すとおり、沸点が低下し気相と液相の組成がほぼ同一となる共沸様組成物を示となる。
In the azeotrope-like composition of the present invention, particularly preferred compositions are 97.3% by weight of nonafluorobutylmethyl ether and 2.7% by weight of 2,2,3,3-tetrafluoropropanol. An azeotrope-like composition consisting of
The azeotrope-like composition having such a composition is an azeotrope-like composition in which the boiling point is lowered and the composition of the gas phase and the liquid phase is almost the same, as specifically shown in Example 1 described later. .
本発明において、共沸様組成物とは、共沸乃至それに近い挙動（共沸様）を示す組成物をいう。本発明の共沸様組成物においては、使用工程において蒸留操作があっても成分の組成変化が少なく共沸様組成物の特性を維持することができるため、組成物の回収や再利用に好都合である。
また、炭化水素系油等の溶解性をノナフルオロブチルメチルエ−テル単独の場合よりも向上させることができる。
In the present invention, the azeotrope-like composition refers to a composition that exhibits azeotropy or behavior close to it (azeotrope-like). In the azeotrope-like composition of the present invention, even if there is a distillation operation in the use process, the composition change of the components is small and the characteristics of the azeotrope-like composition can be maintained, so it is convenient for recovery and reuse of the composition It is.
In addition, the solubility of hydrocarbon oil and the like can be improved as compared with the case of nonafluorobutylmethyl ether alone.
本発明の共沸様組成物は、必要に応じて安定化剤を含んでいてもよい。安定化剤としては、ニトロアルカン類、エポキシド類、フラン類、ベンゾトリアゾール類、フェノール類、アミン類、ホスフェイト類から選ばれる少なくとも１種を含むことができる。安定化剤としては、従来クロロフルオロカーボン類に用いられてきたものから、適宜選択して用いることができる。これらの安定化剤の配合量は、共沸様組成物に対して０．０１〜５重量％、好ましくは０．０５〜０．５重量％であることが望ましい。 The azeotrope-like composition of this invention may contain the stabilizer as needed. The stabilizer can include at least one selected from nitroalkanes, epoxides, furans, benzotriazoles, phenols, amines, and phosphates. As the stabilizer, those conventionally used for chlorofluorocarbons can be appropriately selected and used. The amount of these stabilizers to be blended is 0.01 to 5% by weight, preferably 0.05 to 0.5% by weight, based on the azeotrope-like composition.
さらに、本発明の共沸様組成物は、本発明の特徴を損なわない範囲で、必要に応じて、アルコール類、ケトン類、エーテル類、エステル類、炭化水素類、アミン類、グリコールエーテル類、シロキサン類などの他の成分を含むことができる。 Furthermore, the azeotrope-like composition of the present invention is an alcohol, a ketone, an ether, an ester, a hydrocarbon, an amine, a glycol ether, if necessary, as long as the characteristics of the present invention are not impaired. Other components such as siloxanes can be included.
本発明の共沸様組成物は、洗浄剤、発泡剤、作動媒体、分散剤、電気絶縁剤等の用途に用いることができる。
洗浄剤用途としては、属部品、プラスチック部品、ゴム製品、ガラス製品、及びこれらを組み合わせた精密機械部品、電子部品の、微粒子や油脂などの汚染物除去用洗浄剤として、或いはドライクリーニング用洗浄剤として用いることができる。洗浄剤として用いる場合、常温洗浄法での拭い落とし、浸漬、はけ洗い、フラッシュ、スプレー、超音波洗浄、或いは、加熱洗浄法での沸騰状態での浸漬、蒸気すすぎ、蒸気洗浄等が適用でき、これらを適宜組み合わせることにより更に効果的に洗浄することができる。
The azeotrope-like composition of this invention can be used for uses, such as a cleaning agent, a foaming agent, a working medium, a dispersing agent, an electrical insulation agent.
As a cleaning agent, it is used as a cleaning agent for removing contaminants such as fine particles and oils and fats in genus parts, plastic parts, rubber products, glass products, and precision machine parts and electronic parts that combine these parts, or as a cleaning agent for dry cleaning. Can be used as When used as a cleaning agent, wiping, immersion, brushing, flushing, spraying, ultrasonic cleaning, or immersion in boiling state, steam rinsing, steam cleaning, etc. can be applied. Further, these can be washed more effectively by appropriately combining them.
分散剤用途としては、潤滑剤、撥水撥油剤、防錆剤、及び金属部品や、プラスチック部品、ガラス部品等に塗料等を均一に塗布するための媒体として、効果的に用いることができる。 As a dispersant, it can be effectively used as a medium for uniformly applying a coating material to a lubricant, a water / oil repellent, a rust preventive, a metal part, a plastic part, a glass part or the like.
次に実施例及び比較例を示して、本発明をより具体的に説明するが、本発明はこれらの例によって何ら制限されるものではない。 EXAMPLES Next, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited at all by these examples.
（実施例１）
ＨＦＥ−４４９ｓ（沸点６０．４℃（測定値））約２００ｇをフラスコ（３００ｍｌ）に入れ沸騰させた。その中に任意の量のＴＦＰ（沸点約１１０℃（測定値））を添加していき、液相の温度変化を調べた。その結果、当初６０．４℃であった沸点が、６０．１℃まで低下した。このときの液相及びガス相の組成をガスクロマトグラフ（島津製作所製ＧＣ−１４Ａ）により分析したところ、ＨＦＥ−４４９ｓが９７．３重量％、ＴＦＰが２．７重量％であった。
本実施例から、９７．３重量％のＨＦＥ−４４９ｓ及び２．７重量％のＴＦＰからなる本発明の組成物は、沸点が６０．１℃に低下し気相と液相の組成がほぼ同一となり、共沸様組成物となっていることがわかる。
Example 1
About 200 g of HFE-449s (boiling point 60.4 ° C. (measured value)) was placed in a flask (300 ml) and boiled. An arbitrary amount of TFP (boiling point: about 110 ° C. (measured value)) was added thereto, and the temperature change of the liquid phase was examined. As a result, the boiling point, which was 60.4 ° C. at the beginning, decreased to 60.1 ° C. When the composition of the liquid phase and the gas phase at this time was analyzed by a gas chromatograph (GC-14A manufactured by Shimadzu Corporation), HFE-449s was 97.3% by weight and TFP was 2.7% by weight.
From this example, the composition of the present invention consisting of 97.3% by weight of HFE-449s and 2.7% by weight of TFP has a boiling point lowered to 60.1 ° C., and the composition of the gas phase and the liquid phase is almost the same. It can be seen that the composition is an azeotropic-like composition.
本発明により、高度にフッ素化された特定のノナフルオロブチルメチルエ−テルとテトラフルオロプロパノールをベ−スとする、共使用工程において蒸留操作があっても成分の組成変化が少なく、該組成物の特性を維持することができ、組成物の回収や再利用に好都合な沸乃至それに近い挙動（共沸様）を示す新規な組成物を提供することができる。
また、本発明によれば、炭化水素系油等の溶解性がノナフルオロブチルメチルエ−テル単独の場合よりも向上した新規な共沸様組成物を提供することができる。
本発明により提供される新規な共沸様組成物は、クロロフロロカーボン、或いは塩素系溶剤の代替として、加工や錆止めとして金属部品に使用されているグリ−スや加工油等の脱脂及び半導体製造時のフラックス除去のために好適に使用される洗浄剤のほか、発泡剤、作動媒体、分散剤、電気絶縁剤等の用途に好適に用いることができる。
According to the present invention, a specific nonafluorobutylmethyl ether and tetrafluoropropanol, which are highly fluorinated, are used as a base. Thus, it is possible to provide a novel composition exhibiting boiling or a behavior close to that (azeotrope-like) that is convenient for recovery and reuse of the composition.
In addition, according to the present invention, a novel azeotrope-like composition can be provided in which the solubility of hydrocarbon oils and the like is improved as compared with the case of nonafluorobutylmethyl ether alone.
The novel azeotrope-like composition provided by the present invention is used for degreasing grease and processing oil used in metal parts as processing and rust prevention as an alternative to chlorofluorocarbons or chlorinated solvents, and during semiconductor manufacturing. In addition to the cleaning agent suitably used for removing the flux, it can be suitably used for applications such as a foaming agent, a working medium, a dispersing agent, and an electrical insulating agent.
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| JPH10510579A (en) * | 1995-05-16 | 1998-10-13 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Azeotropic compositions and uses thereof |
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| AU7128191A (en) * | 1990-02-28 | 1991-08-29 | Daikin Industries, Ltd. | Azeotropic solvent composition |
| DE4227130A1 (en) * | 1992-08-17 | 1994-02-24 | Solvay Fluor & Derivate | Compositions of 1-chloro-2,2,2-trifluoroethyl difluoromethyl ether and partially fluorinated alkanols |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH10510579A (en) * | 1995-05-16 | 1998-10-13 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Azeotropic compositions and uses thereof |
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| JP2006077042A (en) | 2006-03-23 |
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