JP2021143212A - Azeotrope-like composition - Google Patents
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- 239000000203 mixture Substances 0.000 title claims abstract description 90
- CDAVUOSPHHTNBU-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,7-tetradecafluorohept-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDAVUOSPHHTNBU-UHFFFAOYSA-N 0.000 claims abstract description 34
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 28
- 239000012459 cleaning agent Substances 0.000 claims description 13
- 239000003380 propellant Substances 0.000 claims description 7
- 239000012629 purifying agent Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 2
- DMUPYMORYHFFCT-UPHRSURJSA-N (z)-1,2,3,3,3-pentafluoroprop-1-ene Chemical compound F\C=C(/F)C(F)(F)F DMUPYMORYHFFCT-UPHRSURJSA-N 0.000 claims description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 claims description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims description 2
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 abstract description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 description 29
- 238000004140 cleaning Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 229920002545 silicone oil Polymers 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- -1 perfluoro compounds Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000013020 steam cleaning Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
本発明は、パーフルオロヘプテンとヘキサメチルジシロキサンからなる共沸混合物様組成物、それを含む清浄化剤、熱媒体及びコーティング塗料に関する。 The present invention relates to an azeotropic mixture-like composition consisting of perfluoroheptene and hexamethyldisiloxane, a purifying agent containing the same, a heat medium and a coating coating material.
これまで、多くの産業分野において、クロロフルオロカーボン(CFC)、ハイドロクロロフルオロカーボン(HCFC)およびハイドロフルオロカーボン(HFC)などのフッ素系溶剤が、エアゾール噴射剤、冷媒、溶媒、清浄化剤、熱可塑性および熱硬化性発泡体用の発泡剤(発泡体膨張剤)、熱媒、ガス状誘電体、消火剤および鎮火剤、動力サイクル作動流体、重合媒体、微粒子除去流体、キャリア流体、バフ研磨剤、および置換乾燥剤をはじめとする広範囲の用途に使用されてきた。 To date, in many industrial sectors, fluorocarbon solvents such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) have been used in aerosol propellants, refrigerants, solvents, cleaning agents, thermoplastics and heat. Foaming agents for curable foams (foam swelling agents), heat media, gaseous dielectrics, fire extinguishing agents and fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing agents, and replacements. It has been used in a wide range of applications including desiccants.
しかしながら、CFCやHCFCはオゾン層破壊物質として知られており、また、HFCはオゾン層を破壊する危険はないものの、温室効果ガスとして地球温暖化に影響を及ぼすことから、より環境負荷の少ない、すなわち、オゾン破壊係数が0であり、地球温暖化係数が非常に低い代替組成物が求められている。 However, CFCs and HCFCs are known as ozone-depleting substances, and although HFCs do not have the risk of depleting the ozone layer, they have less environmental impact because they affect global warming as greenhouse gases. That is, there is a need for an alternative composition having an ozone depletion potential of 0 and a very low global warming potential.
このような代替組成物には、使用中又は回収時の蒸留中に分留されない定沸点特性および沸騰又は蒸発時に分留しない性質を有する共沸混合物が有用であることが知られている(例えば、特許文献1、特許文献2、特許文献3)。
しかしながら、特許文献1にも記載されているとおり、共沸混合物を形成するかどうかを理論的に予測することは不可能であり、種々の組み合わせについて、優れた特性を有する新規な共沸混合物の探索が続けられている。
For such alternative compositions, azeotropic mixtures having a constant boiling point property that is not fractionated during distillation during use or recovery and a property that is not fractionated during boiling or evaporation are known to be useful (eg,). , Patent Document 1,
However, as described in Patent Document 1, it is impossible to theoretically predict whether or not an azeotropic mixture will be formed, and a novel azeotropic mixture having excellent properties for various combinations will be formed. The search continues.
フッ素系溶剤の化合物の中でも、水素が全てフッ素に置換されたパーフルオロ化合物は、地球温暖化係数が大きいと思われていたため、これまで用いられることは少なかった。しかし、パーフルオロ化合物の中で、パーフルオロヘプテン(ペルフルオロヘプテン、以下PFH)はオゾン破壊係数がゼロであり、地球温暖化係数も低いことから、各種の使用の提案がなされている(特許文献4、特許文献5)。 Among the compounds of fluorine-based solvents, perfluoro compounds in which all hydrogen is replaced with fluorine are considered to have a large global warming potential, and therefore have been rarely used so far. However, among the perfluoro compounds, perfluoroheptene (perfluoroheptene, hereinafter PFH) has a zero ozone depletion potential and a low global warming potential, so various uses have been proposed (patented). Document 4, Patent Document 5).
一方、シリコーン(ポリアルキルシロキサン、以下シリコーンと記載する。)、特に、ポリメチルシロキサンのような常温で液状のシリコーンオイル(以下、シリコーンオイルと記載する。)は、潤滑剤や離型剤その他多くの工業用途に使用されているほか、シリコーンを希釈溶剤中に溶解して、電子部品や医療器具の表面にコーティングし、製品の摺動性や撥水撥油性能を向上させる目的でも使用されている。
しかし、潤滑剤や離型剤としてシリコーンオイルを用いた際には、装置のメンテナンスや成形品の表面に残留した離型剤(シリコーンオイル)を除去するための洗浄・清浄化の必要が生じる。
On the other hand, silicone (polyalkylsiloxane, hereinafter referred to as silicone), in particular, silicone oil that is liquid at room temperature (hereinafter, referred to as silicone oil) such as polymethylsiloxane, is a lubricant, a mold release agent, and many others. In addition to being used in industrial applications, it is also used for the purpose of dissolving silicone in a diluting solvent and coating it on the surface of electronic parts and medical equipment to improve the slidability and water and oil repellency of products. There is.
However, when silicone oil is used as a lubricant or a mold release agent, it is necessary to maintain the device and to clean and clean the mold release agent (silicone oil) remaining on the surface of the molded product.
シリコーンオイル等のシリコーンを洗浄除去に使用する清浄化剤としては、HCFC類、塩素系溶剤、ジメチルシロキサン、臭素系溶剤等が使用されうるが、HCFCはオゾン層を破壊するため、使用が禁止されている。塩素系溶剤および臭素系溶剤は毒性の点で問題があり、ジメチルシロキサンは引火点が低く引火の危険性が強い。一方で、引火点がなく、毒性が低く、さらにオゾン破壊係数がゼロで地球温暖化係数が低いPFHは、シリコーンの溶解性が乏しいため、洗浄に使用することができない。
このため、シリコーンオイル等のシリコーンの洗浄除去に適したシリコーンの溶解性能を有し、かつ安全な溶剤が求められている。更に、シリコーンをコーティングする溶剤に
は、均一な薄膜を形成するために、低い表面張力や高い揮発性も求められる。
HCFCs, chlorine-based solvents, dimethylsiloxane, bromine-based solvents, etc. can be used as the cleaning agent that uses silicone such as silicone oil for cleaning and removal, but the use of HCFCs is prohibited because it destroys the ozone layer. ing. Chlorine-based solvents and bromine-based solvents have problems in terms of toxicity, and dimethylsiloxane has a low flash point and a high risk of ignition. On the other hand, PFH, which has no flash point, low toxicity, zero ozone depletion potential, and low global warming potential, cannot be used for cleaning because of its poor solubility of silicone.
Therefore, there is a demand for a safe solvent having a silicone dissolving performance suitable for cleaning and removing silicone such as silicone oil. Further, the solvent for coating silicone is required to have low surface tension and high volatility in order to form a uniform thin film.
本発明は、オゾン破壊や地球温暖化への影響が少なく、清浄化剤や熱媒体及び塗料等に適した、フッ素系溶剤の共沸混合物様組成物を提供することを目的とする。 An object of the present invention is to provide an azeotropic mixture-like composition of a fluorine-based solvent, which has little influence on ozone destruction and global warming and is suitable for a purifying agent, a heat medium, a paint, and the like.
本発明者らは、パーフルオロヘプテンとヘキサメチルジシロキサンを特定の比率で配合した組成物が共沸混合物様の性質を示し、熱媒体として使用できること、またシリコーンオイル等のシリコーンに対する溶解性が高く、清浄化剤、及び溶剤(キャリア流体)や、それを用いたコーティング塗料としての使用に適していることを見出して、本発明を完成するに至った。 The present inventors have shown that a composition containing perfluoroheptene and hexamethyldisiloxane in a specific ratio exhibits azeotropic mixture-like properties and can be used as a heat medium, and has solubility in silicone such as silicone oil. The present invention has been completed by finding that it is expensive and suitable for use as a cleaning agent, a solvent (carrier fluid), and a coating coating material using the same.
すなわち、本発明は、以下のとおりのものである。
1. 70.0〜97.0質量%のパーフルオロヘプテンと、3.0〜30.0質量%のヘキサメチルジシロキサンからなる、共沸混合物様組成物。
2. 75.0〜95.0質量%のパーフルオロヘプテンと、5.0〜25.0質量%のヘキサメチルジシロキサンからなる、1に記載の共沸混合物様組成物。
3. 75.0〜90.0質量%のパーフルオロヘプテンと、
10.0〜25.0質量%のヘキサメチルジシロキサンからなる、
1又は2に記載の共沸混合物様組成物。
4.1〜3のいずれかに記載の共沸混合物様組成物を含む清浄化剤。
5. 更に噴射剤を含む、4に記載の清浄化剤。
6. 噴射剤が空気、窒素、二酸化炭素、2,3,3,3−テトラフルオロプロペン、trans-1,3,3,3−テトラフルオロプロペン、1,2,3,3,3−ペンタフルオロプロペン、ジフルオロメタン、トリフルオロメタン、ジフルオロエタン、トリフルオロエタン、テトラフルオロエタン、ペンタフルオロエタン、炭化水素又はジメチルエーテル並びにそれらの混合物のいずれかである5に記載の清浄化剤。
7. シリコーン除去用の、4〜6のいずれかに記載の清浄化剤。
8. 蒸気脱脂用の、4〜6のいずれかに記載の清浄化剤。
9. 1〜3のいずれかに記載の共沸混合物様組成物を含む熱媒体。
10. 1〜3のいずれかに記載の共沸混合物様組成物を含む溶剤。
11. シリコーン用である10に記載の溶剤。
12.10又は11に記載の溶剤及びシリコーンを含むコーティング塗料。
That is, the present invention is as follows.
1. 1. An azeotropic mixture-like composition comprising 70.0 to 97.0% by mass of perfluoroheptene and 3.0 to 30.0% by mass of hexamethyldisiloxane.
2. The azeotropic mixture-like composition according to 1, which comprises 75.0 to 95.0% by mass of perfluoroheptene and 5.0 to 25.0% by mass of hexamethyldisiloxane.
3. 3. With 75.0-90.0% by mass of perfluoroheptene,
Consisting of 10.0-25.0% by mass of hexamethyldisiloxane,
The azeotropic mixture-like composition according to 1 or 2.
A purifying agent containing the azeotropic mixture-like composition according to any one of 4.1 to 3.
5. 4. The cleaning agent according to 4, further comprising a propellant.
6. The propellants are air, nitrogen, carbon dioxide, 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, 5. The purifying agent according to 5, which is any one of difluoromethane, trifluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, hydrocarbon or dimethyl ether and a mixture thereof.
7. The cleaning agent according to any one of 4 to 6 for removing silicone.
8. The cleaning agent according to any one of 4 to 6 for steam degreasing.
9. A heat medium containing the azeotropic mixture-like composition according to any one of 1 to 3.
10. A solvent containing the azeotropic mixture-like composition according to any one of 1 to 3.
11. 10. The solvent according to 10 for silicone.
12. A coating coating material containing the solvent and silicone according to 11.10 or 11.
本発明によれば、オゾン破壊係数が0であり、地球温暖化係数の非常に低い、共沸混合物様組成物を提供することができる。
本発明の組成物は、共沸混合物様の性質を示し、シリコーンの溶解度が高いため、清浄化剤、熱媒体、溶剤及びコーティング塗料として有用である。本発明の組成物はまた、引火性でなく毒性も低いため、これらの用途に安全に使用できるという利点も有する。
According to the present invention, it is possible to provide an azeotropic mixture-like composition having an ozone depletion potential of 0 and a very low global warming potential.
The composition of the present invention exhibits azeotropic mixture-like properties and has a high solubility of silicone, so that it is useful as a cleaning agent, a heat medium, a solvent and a coating coating material. The compositions of the present invention also have the advantage of being safe to use in these applications because they are not flammable and have low toxicity.
以下、本発明について、詳細に説明する。
本発明の共沸混合物様組成物は、パーフルオロヘプテン(PFH)およびヘキサメチルジシロキサン(以下HMDS)から本質的になる。
Hereinafter, the present invention will be described in detail.
The azeotropic mixture-like composition of the present invention consists essentially of perfluoroheptene (PFH) and hexamethyldisiloxane (HMDS).
本発明において、PFHは、その構造異性体・立体異性体に特に制限はなく、単一の異性体でも、それらの異性体の混合物であってもよいが、直鎖タイプのPFHを用いることがHMDSとの共沸組成におけるHMDS組成比がより大きくできる可能性があるため好ましい。なかでも、シス若しくはトランス−パーフルオロ−3−ヘプテン又はその混合物が好ましく、特にトランス−パーフルオロ−3−ヘプテン又はそれを含む混合物、例えば、トランス−パーフルオロ−3−ヘプテンの割合が50質量%以上であることが好ましく、60質量%以上であればより好ましく、70質量%以上であれば更に好ましく、80質量%以上である異性体の混合物は、特に好ましい。 In the present invention, the structural isomer and stereoisomer of the PFH are not particularly limited, and may be a single isomer or a mixture of those isomers, but a linear type PFH may be used. It is preferable because the HMDS composition ratio in the azeotropic composition with HMDS may be larger. Of these, cis or trans-perfluoro-3-heptene or a mixture thereof is preferable, and in particular, the proportion of trans-perfluoro-3-heptene or a mixture containing it, for example, trans-perfluoro-3-heptene is 50% by mass. The above is preferable, 60% by mass or more is more preferable, 70% by mass or more is further preferable, and a mixture of isomers of 80% by mass or more is particularly preferable.
当該技術分野で認められているように、共沸組成物は、2つ以上の異なる成分の混合物であり、それは、所与の圧力下で液体形態にあるとき、実質的に一定温度で沸騰し、その温度は、個々の成分の沸騰温度より高いか又は低く、かつ、それは沸騰中の全体液体組成と本質的に同一である蒸気組成を提供する(例えば、M.F.Doherty and M.F.Malone、Conceptual Design of Distillation Systems、McGraw−Hill(NewYork)、2001年、185〜186、351〜359頁を参照)。 As recognized in the art, an azeotropic composition is a mixture of two or more different components, which, when in liquid form under a given pressure, boils at a substantially constant temperature. , Its temperature is above or below the boiling temperature of the individual components, and it provides a vapor composition that is essentially identical to the overall liquid composition during boiling (eg, MF Doherty and MF). . Malone, Conceptual Design of Distillation Systems, McGraw-Hill (NewYork), 2001, 185-186, pp. 351-359).
この時、液の組成を共沸混合液の組成に近い範囲で、種々変化させて定圧の気液平衡関係を測定してみると、共沸混合物の沸点が極大又は極小となることが知られている。 At this time, when the vapor-liquid equilibrium relationship of constant pressure is measured by changing the composition of the liquid in a range close to the composition of the azeotropic mixture, it is known that the boiling point of the azeotropic mixture becomes maximum or minimum. ing.
従って、共沸組成物の本質的な特徴は、所与の圧力で、液体組成物の沸点が固定されていること、かつ、沸騰中の組成物の上方の蒸気の組成が、本質的に沸騰中の全体液体組成物の組成である(すなわち、液体組成物の成分の分留が起こらない)ことである。共沸組成物が異なる圧力で沸騰にかけられるとき、共沸組成物の各成分の沸点および質量百分率の両方が変わる場合があることもまた当該技術分野で認められている。従って、共沸組成物は、成分間に存在する特有の関係の観点から又は成分の組成範囲の観点から、或いは指定圧力での固定沸点によって特徴付けられる組成物の各成分の正確な質量百分率の観点から、定義されてもよい。 Therefore, the essential characteristics of the azeotropic composition are that, at a given pressure, the boiling point of the liquid composition is fixed, and the composition of the vapor above the composition in boiling is essentially boiling. It is the composition of the whole liquid composition inside (ie, fractional distillation of the components of the liquid composition does not occur). It is also acknowledged in the art that when the azeotropic composition is boiled at different pressures, both the boiling point and the mass percentage of each component of the azeotropic composition may change. Thus, the azeotropic composition is the exact mass percentage of each component of the composition characterized in terms of the unique relationships that exist between the components, in terms of the composition range of the components, or by the fixed boiling point at a specified pressure. From a point of view, it may be defined.
本発明の目的のためには、本発明の共沸混合物様組成物は、共沸組成物のように挙動する(すなわち、定沸点特性又は沸騰若しくは蒸発時に分留しない傾向を有する)組成物を意味する。それ故に、沸騰中や蒸発中に、気液組成は、それらが仮に変化する場合でも、最小限の程度または無視できる程度しか変化しない。これは、沸騰中や蒸発中に、気液組成がかなりの程度変化する非共沸混合物様組成物とは対照的である。 For the purposes of the present invention, the azeotropic mixture-like compositions of the present invention behave like azeotropic compositions (ie, have constant boiling characteristics or tend not to fractionate during boiling or evaporation). means. Therefore, during boiling and evaporation, the gas-liquid composition changes to a minimal or negligible degree, even if they change. This is in contrast to non-azeotropic mixture-like compositions, where the gas-liquid composition changes to a large extent during boiling and evaporation.
また、本発明の共沸混合物様組成物は、実質的に温度差なしの液相線および気相線を示す。すなわち、所与の圧力下での液相温度と気相温度との差は小さな値であろう。本発明では、(最低共沸点を基準として)2℃以下の液相温度との差の組成物は共沸混合物様であると考える。 In addition, the azeotropic mixture-like composition of the present invention exhibits a liquid phase line and a gas phase line with substantially no temperature difference. That is, the difference between the liquid phase temperature and the gas phase temperature under a given pressure will be small. In the present invention, the composition having a difference from the liquid phase temperature of 2 ° C. or lower (based on the minimum azeotropic boiling point) is considered to be azeotropic mixture-like.
さらに、あるシステムの相対揮発度が1.0に近づくときに、そのシステムが共沸組成
物又は共沸混合物様組成物を形成すると定義されることはこの分野で周知のことである。相対揮発度は、成分1の揮発度対成分2の揮発度の比である。蒸気中のある成分のモル分率対液体中のそれの比がその成分の揮発度である。
Moreover, it is well known in the art that when the relative volatility of a system approaches 1.0, the system is defined to form an azeotropic composition or an azeotropic mixture-like composition. The relative volatility is the ratio of the volatility of component 1 to the volatility of
本発明の共沸混合物様組成物は、必要に応じて安定化剤として、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、アミン類又はホスフェイト類を1種又はそれ以上含んでもよく、その配合量は、共沸混合物様組成物に対して0.01〜5質量%、好ましくは0.05〜0.5質量%である。 The azeotropic mixture-like composition of the present invention may contain one or more nitroalkanes, epoxides, furans, benzotriazoles, phenols, amines or phosphates as stabilizers, if necessary. The blending amount thereof is often 0.01 to 5% by mass, preferably 0.05 to 0.5% by mass, based on the azeotropic mixture-like composition.
本発明の共沸混合物様組成物はまた、本発明の特徴を損なわない範囲で、必要に応じて、(フッ素含有アルコール以外の)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んでもよい。 The co-boiling mixture-like composition of the present invention also contains alcohols (other than fluorine-containing alcohols), ketones, ethers, esters, hydrocarbons, as required, as long as the characteristics of the present invention are not impaired. It may contain other components such as amines, glycol ethers and siloxanes.
本発明の共沸混合物様組成物は、地球温暖化係数(GWP)が約100以下、好ましくは50以下、より好ましくは10以下である。ここで、本発明におけるGWPは、世界気象機関の報告書である「Scientific Assessment of Ozone Depletion, 2002」に定義されるものである。 The azeotropic mixture-like composition of the present invention has a global warming potential (GWP) of about 100 or less, preferably 50 or less, and more preferably 10 or less. Here, the GWP in the present invention is defined in the report of the World Meteorological Organization, "Scientific Assessment of Ozone Depletion, 2002".
本発明のPFHおよびHMDSを含む共沸混合物様組成物は、大気圧下での沸点が、68〜70℃の範囲にあることが好ましく、その配合量は、PFH:HMDS=70〜97質量%:3.0〜30質量%であり、好ましくは、HMDS:5〜25質量%であり、より好ましくは10〜25質量%であり、10質量%を超えて25質量%以下、中でも11質量%以上20質量%以下の範囲は特に好ましい。
本発明の共沸混合物様組成物においては、HMDS組成比が大きい範囲を選択することが、シリコーン溶解性が大きくなるため好ましく、また、PFHよりHMDSの方が一般的に安価であるため、経済的な面からも好ましい。
The azeotropic mixture-like composition containing PFH and HMDS of the present invention preferably has a boiling point in the range of 68 to 70 ° C. under atmospheric pressure, and the blending amount thereof is PFH: HMDS = 70 to 97% by mass. : 3.0 to 30% by mass, preferably HMDS: 5 to 25% by mass, more preferably 10 to 25% by mass, more than 10% by mass and 25% by mass or less, especially 11% by mass. The range of 20% by mass or less is particularly preferable.
In the azeotropic mixture-like composition of the present invention, it is preferable to select a range in which the HMDS composition ratio is large because the silicone solubility is high, and HMDS is generally cheaper than PFH, which is economical. It is also preferable from the aspect of the above.
本発明の共沸混合物様組成物は、従来からハロゲン化炭化水素が使用されてきたエアゾール噴射剤、冷媒、溶媒、清浄化剤、微粒子除去流体、熱可塑性および熱硬化性発泡体用の発泡剤(発泡体膨張剤)、熱媒、ガス状誘電体、消火剤および鎮火剤、動力サイクル作動流体、重合媒体、キャリア流体、バフ研磨剤、および置換乾燥剤等の広範囲の用途に使用することができる。 The co-boiling mixture-like composition of the present invention comprises an aerosol propellant, a refrigerant, a solvent, a cleaning agent, a fine particle removing fluid, and a foaming agent for thermoplastic and thermosetting foams in which halogenated hydrocarbons have been conventionally used. Can be used in a wide range of applications such as (foam swelling agents), heat media, gaseous dielectrics, fire extinguishing agents and fire extinguishing agents, power cycle working fluids, polymerization media, carrier fluids, buffing abrasives, and replacement desiccants. can.
特に、本発明の共沸混合物様組成物は、GWPが低く、不燃性であり、シリコーンに対する溶解性が高いため、シリコーンオイル等のシリコーン除去のための洗浄剤やシリコーン用の溶剤に適している。 In particular, the azeotropic mixture-like composition of the present invention has a low GWP, is nonflammable, and has high solubility in silicone, and is therefore suitable as a cleaning agent for removing silicone such as silicone oil and a solvent for silicone. ..
本発明の共沸混合物様組成物を含む洗浄剤を使用する洗浄方法としては、噴射剤(クレーム参照)との組成物を用いて、洗浄対象物に噴射(スプレー)する方法(噴射洗浄)や、浸漬洗浄、超音波洗浄、蒸気洗浄、シャワー洗浄など各種の方法を用いることができ、それらを組み合わせて用いることもできる。 As a cleaning method using a cleaning agent containing the co-boiling mixture-like composition of the present invention, a method of spraying (spraying) a composition with a propellant (see claims) or a method of spraying on an object to be cleaned (spray cleaning) or , Immersion cleaning, ultrasonic cleaning, steam cleaning, shower cleaning and the like can be used, and they can also be used in combination.
一般に、工業用途、特に精密洗浄や基板など高いレベルのクリーン度が求められる用途では、蒸気脱脂(Vapor degreasing。蒸気洗浄、及び浸漬洗浄・超音波洗浄・蒸気リンス洗浄との組み合わせによる洗浄プロセス)が、よく用いられる。 In general, for industrial applications, especially applications that require a high level of cleanliness such as precision cleaning and substrates, steam degreasing (Vapor degreasing, a cleaning process that combines immersion cleaning, ultrasonic cleaning, and steam rinsing cleaning) is used. , Often used.
〔実施例1〕
PFHおよびHMDSよりなる混合物の沸点、粘度、表面張力、密度、引火点の測定及
び算出を、それぞれ以下の方法で行った。
[Example 1]
The boiling point, viscosity, surface tension, density, and flash point of the mixture consisting of PFH and HMDS were measured and calculated by the following methods, respectively.
使用したPFHの異性体分布は、以下の割合であった。
シス−パーフルオロヘプテン−2: 4.6質量%
シス−パーフルオロヘプテン−3: 2.3質量%
トランス−パーフルオロヘプテン−2: 4.5質量%
トランス−パーフルオロヘプテン−3: 88.6質量%
The isomer distribution of PFH used was as follows.
Sis-perfluorohepten-2: 4.6% by mass
Sis-perfluorohepten-3: 2.3% by mass
Trans-perfluorohepten-2: 4.5% by weight
Trans-perfluorohepten-3: 88.6% by mass
また、HMDSとしては、KF−96−0.65CS(信越シリコーン製)を使用した。 Further, as HMDS, KF-96-0.65CS (manufactured by Shin-Etsu Silicone) was used.
[沸点(平衡還流沸点)]
冷却水温度を5℃とし、またホットプレートとフラスコの間に何もしかずに直に加熱した以外は、JIS K 2233に準じて沸点(平衡還流沸点)を測定した。
[Boiling point (equilibrium reflux boiling point)]
The boiling point (equilibrium reflux boiling point) was measured according to JIS K 2233, except that the cooling water temperature was set to 5 ° C. and the hot plate and the flask were heated directly with nothing.
[粘度、表面張力、密度]
混合物の粘度、表面張力、密度を以下の計算式により算出した。
[Viscosity, surface tension, density]
The viscosity, surface tension and density of the mixture were calculated by the following formulas.
・表面張力:Macleod−Sugdenの相関式
σ1/4=[P](ρL−ρV)/MW
σ;表面張力
P:パラコール係数
ρL:液比重
ρv:蒸気比重,
MW:分子量
なお、PFHの表面張力値は13.8mN/m(NIST REFPROP Ver.10より。25℃設定)、HMDSの表面張力値は15.9mN/m(信越化学工業株式会社カタログより引用)とした。
-Surface tension: Macleod-Sugden correlation equation σ1 / 4 = [P] (ρL-ρV) / MW
σ; Surface tension P: Paracol coefficient ρL: Liquid specific density ρv: Vapor specific gravity,
MW: Molecular weight The surface tension value of PFH is 13.8 mN / m (from NIST REFPROP Ver.10, set at 25 ° C.), and the surface tension value of HMDS is 15.9 mN / m (quoted from Shin-Etsu Chemical Co., Ltd. catalog). And said.
・粘度:McAllisterの方法
lnηm=Σxif(ηi)
η:粘度
x:モル分率
f(η):粘度の対数
なお、PFHの粘度は0.77mPa・s(NIST REFPROP Ver.10より。25℃設定)、HMDSの粘度は0.494mPa・s(信越化学工業株式会社カタログより引用)とした。
-Viscosity: McAllister's method lnηm = Σxif (ηi)
η: Viscosity x: Mole fraction f (η): Logarithm of viscosity The viscosity of PFH is 0.77 mPa · s (from NIST REFPROP Ver.10, set at 25 ° C.), and the viscosity of HMDS is 0.494 mPa · s (from NIST REFPROP Ver.10). (Quoted from the Shinetsu Chemical Industry Co., Ltd. catalog).
・密度:アマガーの法則
Vm=ΣxjVj
V:密度
x:モル分率
なお、PFHの密度値は1.63g/ml(NIST REFPROP Ver.10より。25℃設定)、HMDSの比重は0.76g/ml(信越化学工業株式会社カタログより引用)とした。
・ Density: Amager's Law Vm = ΣxjVj
V: Density x: Mole fraction The density value of PFH is 1.63 g / ml (from NIST REFPROP Ver.10, set at 25 ° C.), and the specific gravity of HMDS is 0.76 g / ml (from Shin-Etsu Chemical Co., Ltd. catalog). Citation).
[引火点]
引火点の測定は、JIS K 2265−1980に準じたタグ密閉式およびクリーブランド開放式引火点試験により測定した。
[Flash point]
The flash point was measured by a tag closed type and a Cleveland open type flash point test according to JIS K 2265 to 1980.
[シリコーン洗浄試験方法]
*テストピース; 60×6×1mmアルミニウム板(AL1100)
*手順
アルミテストピース5枚をシリコーンオイルKF−96−100CS(信越シリコーン製)に浸漬付着させ、付着オイル量を測定した。
その後、オイルが付着したテストピースを沸騰している試験液に1分間浸漬することによって洗浄し、洗浄後のアルミテストピースの重量によりオイル付着量を測定して、除去率を算出した。
[Silicone cleaning test method]
* Test piece; 60 x 6 x 1 mm aluminum plate (AL1100)
* Procedure Five aluminum test pieces were immersed in silicone oil KF-96-100CS (manufactured by Shin-Etsu Silicone) and adhered, and the amount of adhered oil was measured.
Then, the test piece to which oil was attached was washed by immersing it in a boiling test solution for 1 minute, and the amount of oil attached was measured by the weight of the aluminum test piece after washing to calculate the removal rate.
[測定結果]
PFHおよびHMDSよりなる混合物の沸点(平衡還流沸点)の変化を、図1に示す。
[Measurement result]
The change in boiling point (equilibrium reflux boiling point) of the mixture consisting of PFH and HMDS is shown in FIG.
PFHおよびHMDSよりなる混合物は、共沸混合物様組成物を形成するので、熱媒体としての使用に適している。通常熱媒体は密閉系で使用されるが、場合によっては開放されるケースもある。その際、非共沸混合物では組成変化が生じるが、共沸混合物では組成変化が生じないので、組成は一定のままでありその能力変化は生じず、使用機器への影響がない。 The mixture consisting of PFH and HMDS forms an azeotropic mixture-like composition and is therefore suitable for use as a heat medium. Usually, the heat medium is used in a closed system, but in some cases, it is opened. At that time, the composition of the non-azeotropic mixture changes, but the composition of the azeotropic mixture does not change. Therefore, the composition remains constant and its capacity does not change, and there is no effect on the equipment used.
PFHおよびHMDSが85:15(質量%比)である混合物の沸点、粘度、表面張力、密度、引火点を測定及び算出した結果を、表1に示す。
PFHおよびHMDSよりなる混合物は、地球温暖化係数(GWP)が極めて低く、引火点も無いため、環境負荷が少なく、安全に使用できる。 The mixture consisting of PFH and HMDS has an extremely low global warming potential (GWP) and no flash point, so that it has a low environmental load and can be used safely.
PFHおよびHMDSが85:15(質量%比)である混合物及びPFH単体を試験液として用いて行ったシリコーン洗浄試験の結果を表2に示す。
PFHおよびHMDSよりなる混合物は、シリコーンに対する親和性・溶解性が大きく、PFH単体よりも非常に高い除去率を示している。また、シリコーンに対する親和性・溶解性が高いことから、シリコーン用の溶剤として、またシリコーンを含むコーティング塗料としても適している。 The mixture consisting of PFH and HMDS has a high affinity and solubility in silicone, and exhibits a much higher removal rate than PFH alone. In addition, since it has high affinity and solubility for silicone, it is suitable as a solvent for silicone and as a coating paint containing silicone.
Claims (12)
3.0〜30.0質量%のヘキサメチルジシロキサンからなる、
共沸混合物様組成物。 With 70.0 to 97.0% by mass of perfluoroheptene,
Consisting of 3.0 to 30.0% by mass of hexamethyldisiloxane
Azeotrope-like composition.
5.0〜25.0質量%のヘキサメチルジシロキサンからなる、
請求項1に記載の共沸混合物様組成物。 With 75.0-95.0% by mass of perfluoroheptene,
Consisting of 5.0-25.0% by weight hexamethyldisiloxane,
The azeotropic mixture-like composition according to claim 1.
10.0〜25.0質量%のヘキサメチルジシロキサンからなる、
請求項1又は2に記載の共沸混合物様組成物。 With 75.0-90.0% by mass of perfluoroheptene,
Consisting of 10.0-25.0% by mass of hexamethyldisiloxane,
The azeotropic mixture-like composition according to claim 1 or 2.
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