JPH04284837A - Preparation of polymer membrane - Google Patents
Preparation of polymer membraneInfo
- Publication number
- JPH04284837A JPH04284837A JP7380591A JP7380591A JPH04284837A JP H04284837 A JPH04284837 A JP H04284837A JP 7380591 A JP7380591 A JP 7380591A JP 7380591 A JP7380591 A JP 7380591A JP H04284837 A JPH04284837 A JP H04284837A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polymer solution
- concentration
- film
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005597 polymer membrane Polymers 0.000 title abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 76
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 239000004094 surface-active agent Substances 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000002861 polymer material Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 67
- 239000010409 thin film Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000693 micelle Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 229920006254 polymer film Polymers 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 230000007480 spreading Effects 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract 1
- -1 polydimethylsiloxane Polymers 0.000 description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000003945 anionic surfactant Substances 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000005192 alkyl ethylene group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000005332 diethylamines Chemical class 0.000 description 2
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005609 naphthenate group Chemical group 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- GDWZLADUGAKASM-UHFFFAOYSA-N 2-chloroethynylbenzene Chemical group ClC#CC1=CC=CC=C1 GDWZLADUGAKASM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は膜厚の非常に薄い高分子
薄膜を製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a very thin polymer film.
【０００２】0002
【従来技術】近年、種々の分野において膜を用いた技術
の進歩はめざましく、気体や液体の選択的な分離性、絶
縁性、導電性、偏光性、耐熱性などの各種の機能性を備
えた高分子膜が開発されている。この内、とくに膜によ
る分離技術においては、選別される気体や液体の選択透
過性が高いことと共に、被処理体の透過量を多くして処
理能力を高めるために、できるだけ膜厚が薄いことが望
まれ、従来から薄膜を製造する種々の方法が検討されて
きた。[Prior Art] In recent years, there has been remarkable progress in technology using membranes in various fields. Polymer membranes have been developed. Among these, in separation technology using membranes in particular, in addition to having high selective permeability for the gases and liquids to be separated, it is important that the membrane thickness be as thin as possible in order to increase the amount of permeation through the object to be processed and increase processing capacity. Various methods for producing thin films have been considered in the past.
【０００３】高分子薄膜を形成する方法としては、膜形
成性高分子材料と揮発性溶媒とからなる高分子溶液を支
持液体表面に展開させて、揮発性溶媒を蒸発させること
により高分子膜を形成する方法が、Ｌａｎｇｕｍｕｉｒ
−Ｂｌｏｄｇｅｔｔの単分子膜製造法に準じた方法とし
て広く知られている。この方法は高分子薄膜を簡便に製
造できる非常に有利な方法であるが、高分子の種類によ
っては展開がうまく進まず、膜が形成できなかったり、
所望の厚みの薄膜が得られなかったりするという問題が
あった。[0003] As a method for forming a polymer thin film, a polymer solution consisting of a film-forming polymer material and a volatile solvent is spread on the surface of a supporting liquid, and the volatile solvent is evaporated to form a polymer film. The method of forming is Langmuir
- It is widely known as a method similar to Blodgett's monolayer manufacturing method. This method is a very advantageous method for easily producing thin polymer films, but depending on the type of polymer, the development may not proceed well and the film may not be formed.
There was a problem that a thin film with a desired thickness could not be obtained.
【０００４】これを解決するため、上記高分子溶液に界
面活性剤などの添加剤を添加して、高分子溶液の表面張
力を低下させ、展開性を向上させる方法が特開昭５７−
７１６０５号に提案されている。この方法は高分子溶液
を展開させる展開圧Ｓが、支持液体の表面張力ａ、高分
子溶液の表面張力ｂ、支持液体と高分子溶液の界面張力
ｃとの間に次式の関係にあることから説明される。[0004] In order to solve this problem, a method has been proposed in Japanese Patent Laid-Open No. 1983-1997 in which additives such as surfactants are added to the polymer solution to lower the surface tension of the polymer solution and improve its spreadability.
No. 71605. This method requires that the developing pressure S for developing the polymer solution has the following relationship among the surface tension a of the supporting liquid, the surface tension b of the polymer solution, and the interfacial tension c between the supporting liquid and the polymer solution. It is explained from.
【０００５】Ｓ＝ａ−（ｂ＋ｃ）[0005]S=a-(b+c)
【０００６】すなわち、高分子溶液に界面活性剤を加え
ると、高分子溶液の表面張力ｂと支持液体と高分子溶液
の界面張力ｃとが低下するため、展開圧Ｓが大きくなっ
て展開性が向上し、高分子薄膜が形成できるのである。In other words, when a surfactant is added to a polymer solution, the surface tension b of the polymer solution and the interfacial tension c between the supporting liquid and the polymer solution decrease, so the spreading pressure S increases and the spreadability decreases. This makes it possible to form thin polymer films.
【０００７】しかしながら、この手段を用いても高分子
の種類によっては十分に薄い膜が形成できない場合があ
り、更に改良が望まれていた。However, even if this method is used, it may not be possible to form a sufficiently thin film depending on the type of polymer, and further improvements have been desired.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記従来技術
の欠点を解消すべくなされたものであり、高分子薄膜の
形成において、支持液体表面を展開する高分子溶液の展
開性を高め、どの様な膜形成性高分子からも薄膜を安定
に製造できる方法を提供することを課題とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art, and it is an object of the present invention to improve the spreadability of a polymer solution spreading on the surface of a supporting liquid in the formation of a thin polymer film. The present invention aims to provide a method that can stably produce thin films from various film-forming polymers.
【０００９】[0009]
【課題を解決する手段】上記課題を解決するため、本発
明は、「膜形成性高分子材料と揮発性溶媒とからなる高
分子溶液を支持液体表面に展開させて高分子薄膜を製造
する方法において、該支持液体と該高分子溶液とにお互
いに異なる界面活性剤を添加することを特徴とする高分
子薄膜の製造方法」を要旨とした。[Means for Solving the Problems] In order to solve the above problems, the present invention provides a method for producing a thin polymer film by spreading a polymer solution consisting of a film-forming polymer material and a volatile solvent on the surface of a supporting liquid. , the gist was ``a method for producing a thin polymer film, characterized in that different surfactants are added to the support liquid and the polymer solution''.
【００１０】また、請求項２に記載の発明は、「請求項
１に記載の発明において、支持液体に添加する界面活性
剤の濃度が、界面活性剤の臨界ミセル濃度の百分の一か
ら百万分の一の濃度であることを特徴とする高分子薄膜
の製造方法」を要旨とした。[0010] The invention according to claim 2 also provides the following advantages: ``In the invention according to claim 1, the concentration of the surfactant added to the support liquid ranges from 1/100 to 100% of the critical micelle concentration of the surfactant. The abstract was ``a method for manufacturing thin polymer films characterized by a one-tenth concentration.''
【００１１】また、請求項３に記載の発明は、「請求項
１または２に記載の発明において、膜形成性高分子材料
と揮発性溶媒とからなる高分子溶液に添加する界面活性
剤の濃度が、界面活性剤の臨界ミセル濃度の千分の一か
ら千倍の濃度であることを特徴とする高分子薄膜の製造
方法」を要旨とした。[0011] Furthermore, the invention according to claim 3 provides that, in the invention according to claim 1 or 2, the concentration of a surfactant added to a polymer solution consisting of a film-forming polymer material and a volatile solvent is ``A method for producing a thin polymer film characterized in that the concentration of the surfactant is between 1/1000 and 1,000 times the critical micelle concentration of the surfactant.''
【００１２】また、請求項４に記載の発明は、「請求項
１〜３のいずれかに記載の発明において、支持液体が水
または水溶液であることを特徴とする高分子薄膜の製造
方法」を要旨とした。[0012] The invention according to claim 4 also provides a method for producing a thin polymer film according to any one of claims 1 to 3, characterized in that the supporting liquid is water or an aqueous solution. This is the summary.
【００１３】本発明に使用する膜形成性高分子材料とし
ては、例えば、ポリジメチルシロキサン、ポリエチルメ
チルアセチレン、ポリプロピルアセチレン、ポリトリメ
チルシリルプロピン、ポリｔ−ブチルアセチレン、ポリ
１，２−ビス（トリメチルシリル）アセチレン、ポリフ
ェニルアセチレン、ポリ１−クロロ２−フェニルアセチ
レン等や、これらの誘導体またはこれらを用いた共重合
体などがあるが、これらに限定されず、高分子溶液にし
た場合に支持液体表面に展開して薄膜を形成することが
できれば、どのような高分子でも使用できる。Film-forming polymeric materials used in the present invention include, for example, polydimethylsiloxane, polyethylmethylacetylene, polypropylacetylene, polytrimethylsilylpropyne, polyt-butylacetylene, poly1,2-bis( Examples include, but are not limited to, trimethylsilyl) acetylene, polyphenylacetylene, poly-1-chloro-2-phenylacetylene, derivatives thereof, and copolymers using these, and when made into a polymer solution, the supporting liquid Any polymer can be used as long as it can be spread on the surface to form a thin film.
【００１４】また、揮発性溶媒としては膜形成性高分子
材料を溶解することができて、かつ支持液体に不溶であ
るか、若しくは支持液体への溶解が僅かである有機溶媒
が適しており、例えば、ヘプタン、ヘキサンなどの脂肪
族炭化水素、ベンゼン、トルエン、キシレンなどの芳香
族炭化水素、シクロヘキサンなどの脂環式炭化水素、シ
クロヘキサノールなどの脂環式アルコールなどが好適に
使用できる。[0014] Suitable volatile solvents are organic solvents that can dissolve the film-forming polymeric material and are insoluble in the supporting liquid or only slightly soluble in the supporting liquid. For example, aliphatic hydrocarbons such as heptane and hexane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane, and alicyclic alcohols such as cyclohexanol can be suitably used.
【００１５】上記の膜形成性高分子材料を揮発性溶媒に
溶解することにより高分子溶液が作製される。この高分
子溶液の表面張力を低下させて展開性を高めるために、
本発明において高分子溶液には界面活性剤が添加される
。高分子溶液に添加される界面活性剤は、揮発性溶媒に
溶解して高分子溶液の表面張力を低下させることができ
るものであればよく、アニオン界面活性剤、カチオン界
面活性剤、非イオン界面活性剤、両性界面活性剤、シリ
コーン系界面活性剤、フッ素系界面活性剤などが用いら
れる。A polymer solution is prepared by dissolving the above film-forming polymer material in a volatile solvent. In order to lower the surface tension of this polymer solution and increase its spreadability,
In the present invention, a surfactant is added to the polymer solution. The surfactant added to the polymer solution may be any surfactant as long as it can dissolve in a volatile solvent and lower the surface tension of the polymer solution, such as anionic surfactants, cationic surfactants, and nonionic surfactants. Active agents, amphoteric surfactants, silicone surfactants, fluorine surfactants, etc. are used.
【００１６】アニオン界面活性剤としては、脂肪酸塩、
ナフテン酸塩などのカルボン酸型アニオン界面活性剤や
、硫酸アルキル塩、硫酸アルキルポリオキシエチレン塩
などの硫酸エステル型アニオン界面活性剤や、α−オレ
フィンスルホン酸塩、アルキルベンゼンスルホン酸塩な
どのスルホン酸型アニオン界面活性剤や、リン酸アルキ
ル塩、リン酸アルキルポリオキシエチレン塩などのリン
酸エステル型アニオン界面活性剤がある。また、カチオ
ン界面活性剤としては、第一級アミン塩などのアルキル
アミン塩や、アシルアミノエチルジエチルアミン塩など
のアシルアミン塩、アルキルトリメチルアンモニウム塩
、アルキルジメチルベンジルアンモニウム塩などの第四
級アンモニウム塩、イミダゾリン、イミダゾリウム塩、
アミン誘導体などがある。非イオン界面活性剤としては
、アルキルポリオキシエチレンエーテル、脂肪酸ポリオ
キシエチレンエステル、脂肪酸ポリオキシエチレンソル
ビタンエステルなどがあり、シリコーン系界面活性剤と
しては、スルホン酸変性シリコーン、アンモニウム塩変
性シリコーン、ポリエーテル変性シリコーンなどがある
。[0016] As the anionic surfactant, fatty acid salts,
Carboxylic acid type anionic surfactants such as naphthenates, sulfate ester type anionic surfactants such as alkyl sulfate salts and alkyl sulfate polyoxyethylene salts, and sulfonic acids such as α-olefin sulfonates and alkylbenzene sulfonates. There are phosphate type anionic surfactants and phosphate ester type anionic surfactants such as alkyl phosphate salts and alkyl polyoxyethylene phosphate salts. In addition, as cationic surfactants, alkyl amine salts such as primary amine salts, acyl amine salts such as acylaminoethyl diethylamine salts, quaternary ammonium salts such as alkyltrimethylammonium salts, alkyldimethylbenzyl ammonium salts, imidazoline , imidazolium salt,
These include amine derivatives. Nonionic surfactants include alkyl polyoxyethylene ethers, fatty acid polyoxyethylene esters, fatty acid polyoxyethylene sorbitan esters, etc. Silicone surfactants include sulfonic acid-modified silicones, ammonium salt-modified silicones, and polyethers. There are modified silicones, etc.
【００１７】高分子溶液に添加した界面活性剤の濃度は
、臨界ミセル濃度付近であることが望ましく、臨界ミセ
ル濃度の千分の一から千倍の濃度範囲、とくには百分の
一から百倍の濃度範囲にあるのがよい。The concentration of the surfactant added to the polymer solution is preferably around the critical micelle concentration, and is preferably in the range of 1/1000 to 1,000 times the critical micelle concentration, particularly 1/100 to 100 times the critical micelle concentration. It is best to keep the concentration within the range.
【００１８】一方、本発明に使用する支持液体は、高分
子溶液を液面で支持し、展開できるものであれば、どの
ような液体であってもよいが、例示した膜形成性高分子
材料や揮発性溶媒からなる高分子溶液を用いる場合、支
持液体には水または水溶液を使用するのが望ましい。On the other hand, the support liquid used in the present invention may be any liquid as long as it can support and spread the polymer solution on the liquid surface. When using a polymer solution consisting of a volatile solvent or a volatile solvent, it is desirable to use water or an aqueous solution as the supporting liquid.
【００１９】支持液体に添加される界面活性剤には、支
持液体に溶解して支持液体の表面張力を低下させること
ができるアニオン界面活性剤、カチオン界面活性剤、非
イオン界面活性剤、両性界面活性剤、シリコーン系界面
活性剤、フッ素系界面活性剤などが用いられる。アニオ
ン界面活性剤としては、脂肪酸塩、ナフテン酸塩などの
カルボン酸型アニオン界面活性剤や、硫酸アルキル塩、
硫酸アルキルポリオキシエチレン塩などの硫酸エステル
型アニオン界面活性剤や、α−オレフィンスルホン酸塩
、アルキルベンゼンスルホン酸塩などのスルホン酸型ア
ニオン界面活性剤や、リン酸アルキル塩、リン酸アルキ
ルポリオキシエチレン塩などのリン酸エステル型アニオ
ン界面活性剤がある。また、カチオン界面活性剤として
は、第一級アミン塩などのアルキルアミン塩や、アシル
アミノエチルジエチルアミン塩などのアシルアミン塩、
アルキルトリメチルアンモニウム塩、アルキルジメチル
ベンジルアンモニウム塩などの第四級アンモニウム塩、
イミダゾリン、イミダゾリウム塩、アミン誘導体などが
ある。非イオン界面活性剤としては、アルキルポリオキ
シエチレンエーテル、脂肪酸ポリオキシエチレンエステ
ル、脂肪酸ポリオキシエチレンソルビタンエステルなど
があり、シリコーン系界面活性剤としては、スルホン酸
変性シリコーン、アンモニウム塩変性シリコーン、ポリ
エーテル変性シリコーンなどがある。Surfactants added to the support liquid include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants that can be dissolved in the support liquid to lower the surface tension of the support liquid. Active agents, silicone surfactants, fluorine surfactants, etc. are used. Examples of anionic surfactants include carboxylic acid type anionic surfactants such as fatty acid salts and naphthenates, alkyl sulfate salts,
Sulfate ester type anionic surfactants such as alkyl sulfate polyoxyethylene salts, sulfonic acid type anionic surfactants such as α-olefin sulfonates and alkylbenzene sulfonates, alkyl phosphate salts, and alkyl polyoxyethylene phosphates. There are phosphate ester type anionic surfactants such as salts. In addition, as cationic surfactants, alkylamine salts such as primary amine salts, acylamine salts such as acylaminoethyl diethylamine salt,
Quaternary ammonium salts such as alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts,
Examples include imidazolines, imidazolium salts, and amine derivatives. Nonionic surfactants include alkyl polyoxyethylene ethers, fatty acid polyoxyethylene esters, fatty acid polyoxyethylene sorbitan esters, etc. Silicone surfactants include sulfonic acid-modified silicones, ammonium salt-modified silicones, and polyethers. There are modified silicones, etc.
【００２０】本発明においては支持液体に添加される界
面活性剤は、高分子溶液に添加される界面活性剤とは異
なる界面活性剤が使用される。これは、本来、支持液体
表面に高分子溶液を展開させる展開圧Ｓ＝ａ−（ｂ＋ｃ
）を考えた場合、支持液体に界面活性剤を加えると、支
持液体と高分子溶液との間に働く界面張力ｃと共に支持
液体の表面張力ａまで低下してしまうため、展開圧Ｓは
変らないか、むしろ小さくなるので高分子薄膜の展開性
は悪くなると考えられていたのであるが、支持液体と高
分子溶液の各々に互いに異なる界面活性剤を用いると、
驚くべきことに支持液体と高分子溶液との間に働く界面
張力ｃは、予想されるよりも著しく低下して展開圧Ｓは
大きくなることがわかったからである。この理由は明ら
かではないが、支持液体と高分子溶液の界面において各
々の溶液に含まれる界面活性剤が相互作用を起こして、
界面活性剤を混合して用いた場合のように、各々の界面
活性剤が持つ界面張力を低下させる能力以上に界面張力
を低下させることができるのだと推定される。In the present invention, the surfactant added to the support liquid is different from the surfactant added to the polymer solution. This is originally the development pressure S = a - (b + c
), when a surfactant is added to the supporting liquid, the interfacial tension c acting between the supporting liquid and the polymer solution decreases to the surface tension of the supporting liquid a, so the developing pressure S remains unchanged. It was thought that the spreadability of the polymer thin film would deteriorate because the polymer thin film would become smaller, but if different surfactants were used in the support liquid and the polymer solution,
Surprisingly, it was found that the interfacial tension c acting between the support liquid and the polymer solution was significantly lower than expected, and the developing pressure S was increased. The reason for this is not clear, but the surfactants contained in each solution interact at the interface between the support liquid and the polymer solution.
It is presumed that the interfacial tension can be lowered more than the ability of each surfactant to lower the interfacial tension, such as when a mixture of surfactants is used.
【００２１】なお、支持液体と高分子溶液との間に働く
界面張力ｃの低下の度合いは、高分子溶液に添加される
界面活性剤と、支持液体に添加される界面活性剤の組合
せによって影響を受けるため、使用する膜形成性高分子
材料、揮発性溶媒、支持液体などの種類に応じて、界面
張力ｃの低下の度合いの大きい界面活性剤の組合せを選
択することが望ましい。[0021] The degree of reduction in the interfacial tension c acting between the support liquid and the polymer solution is influenced by the combination of the surfactant added to the polymer solution and the surfactant added to the support liquid. Therefore, it is desirable to select a combination of surfactants that will reduce the interfacial tension c to a large degree, depending on the type of film-forming polymer material, volatile solvent, supporting liquid, etc. used.
【００２２】また、支持液体に添加された界面活性剤の
濃度は、臨界ミセル濃度の百分の一から百万分の一、特
には千分の一から十万分の一の濃度範囲にある事が望ま
しい。これは、上記範囲の低濃度であれば、支持液体の
表面張力ａをほとんど低下させずにすむのに対して、支
持液体と高分子溶液との間に働く界面張力ｃは高分子溶
液中の界面活性剤との相互作用により十分低下させるこ
とができるので、展開圧Ｓをより大きくすることができ
るからである。The concentration of the surfactant added to the support liquid is in the range of 1/100 to 1/1 million, particularly 1/1,000 to 1/100,000 of the critical micelle concentration. things are desirable. This is because if the concentration is low in the above range, the surface tension a of the support liquid will hardly decrease, whereas the interfacial tension c acting between the support liquid and the polymer solution This is because the developing pressure S can be made larger because it can be sufficiently lowered by interaction with the surfactant.
【００２３】[0023]
【作用】本発明の方法によれば、膜形成性高分子材料を
揮発性溶媒に溶解した高分子溶液に界面活性剤を添加す
ることによって、高分子溶液の表面張力ｂを低下させ、
更に支持液体に高分子溶液に加えた界面活性剤とは異な
る界面活性剤を加えることによって、支持液体の表面張
力ａに比して、支持液体と高分子溶液との間に働く界面
張力ｃを双方の界面活性剤の相互作用によって著しく低
下させ、支持液体表面に高分子溶液を展開させる展開圧
Ｓを大きくすることができる。従って、上記高分子溶液
を上記支持液体表面に供給すれば、高分子溶液は速やか
に拡散し、これに伴って揮発性溶媒が蒸発して非常に薄
い高分子薄膜を得ることができる。[Operation] According to the method of the present invention, by adding a surfactant to a polymer solution in which a film-forming polymer material is dissolved in a volatile solvent, the surface tension b of the polymer solution is lowered;
Furthermore, by adding a surfactant different from the surfactant added to the polymer solution to the support liquid, the interfacial tension c acting between the support liquid and the polymer solution can be reduced compared to the surface tension a of the support liquid. The interaction between both surfactants makes it possible to significantly reduce the pressure S and increase the pressure S for spreading the polymer solution on the surface of the supporting liquid. Therefore, if the polymer solution is supplied to the surface of the support liquid, the polymer solution will quickly diffuse, and the volatile solvent will evaporate along with this, making it possible to obtain a very thin polymer film.
【００２４】なお、この際、支持液体に添加された界面
活性剤の濃度を、臨界ミセル濃度の百分の一から百万分
の一の濃度範囲にすれば、支持液体の表面張力ａの低下
を押えながら、支持液体と高分子溶液との間に働く界面
張力ｃを低下させることができ、結果として展開圧Ｓを
より大きくできるので、より高分子薄膜の展開性は向上
する。[0024] At this time, if the concentration of the surfactant added to the support liquid is in the range of 1/100 to 1/1 million of the critical micelle concentration, the surface tension a of the support liquid can be reduced. It is possible to reduce the interfacial tension c acting between the support liquid and the polymer solution while suppressing this, and as a result, the spreading pressure S can be increased, so that the spreading properties of the polymer thin film are further improved.
【００２５】[0025]
【実施例】実施例１〜３
重量平均分子量２３１万のポリトリメチルシリルプロピ
ンをヘキサンに溶解して濃度２．３重量％の高分子溶液
に調整し、この溶液にジアルキルスルホ琥珀酸エステル
ナトリウム塩（第一工業製薬株式会社製、ネオコールＳ
Ｗ）を臨界ミセル濃度（ＣＭＣ）となるように添加した
。一方、支持液体として水を用意し、ラウリルトリメチ
ルアンモニウムクロライドを臨界ミセル濃度（ＣＭＣ）
の千分の１（実施例１）、１万分の１（実施例２）、１
０万分の１（実施例３）の濃度となるように添加し、ス
テンレス製水槽（３２５ｍｍ×３７０ｍｍ×５０ｍｍ）
に満たした。上記高分子溶液約０．１５ＣＣをピペット
により水面上ぎりぎりから垂直に落としたところ、スム
ーズに展開が進み、膜厚が約２００オングストロームの
均一な超薄膜が得られた。[Examples] Examples 1 to 3 Polytrimethylsilylpropyne having a weight average molecular weight of 2.31 million was dissolved in hexane to prepare a polymer solution with a concentration of 2.3% by weight, and dialkyl sulfosuccinate sodium salt ( Neocol S manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
W) was added to reach the critical micelle concentration (CMC). On the other hand, water was prepared as a supporting liquid, and lauryltrimethylammonium chloride was added to the critical micelle concentration (CMC).
1/1000th (Example 1), 1/10,000th (Example 2), 1
It was added to a concentration of 1/00,000 (Example 3) and placed in a stainless steel water tank (325 mm x 370 mm x 50 mm).
filled with. When about 0.15 cc of the above polymer solution was dropped vertically from just above the water surface using a pipette, it spread smoothly and a uniform ultra-thin film with a thickness of about 200 angstroms was obtained.
【００２６】なお、薄膜が展開して形成される状態を目
視により観察し、以下の評価基準により評価して表１に
示した。
評価基準
◎：ほぼ水槽一杯に、均一な厚みで、薄膜が形成された
。
○：水槽一杯には広がらないが、水面の面積の２／３を
越える十分な面積にほぼ均一な厚みで、薄膜が形成され
た。
△：水面の面積の２／３以下で、厚みにムラがあったり
、シワがある薄膜が形成された。
×：高分子溶液はほとんど広がらず、薄膜は形成されな
かった。The state in which the thin film was developed and formed was visually observed and evaluated according to the following evaluation criteria, which is shown in Table 1. Evaluation Criteria ◎: A thin film was formed with a uniform thickness almost filling the entire water tank. ○: Although it did not spread to fill the water tank, a thin film was formed with a substantially uniform thickness over a sufficient area exceeding 2/3 of the water surface area. Δ: A thin film with uneven thickness or wrinkles was formed on 2/3 or less of the area of the water surface. ×: The polymer solution hardly spread, and no thin film was formed.
【００２７】[0027]
【表１】[Table 1]
【００２８】比較例１
重量平均分子量２３１万のポリトリメチルシリルプロピ
ンをヘキサンに溶解して濃度２．３重量％の高分子溶液
に調整し、一方、支持液体として水を用意し、ステンレ
ス製水槽（３２５ｍｍ×３７０ｍｍ×５０ｍｍ）に満た
した。上記高分子溶液約０．１５ＣＣをピペットにより
水面上ぎりぎりから垂直に落としたところ、展開が進ま
ず、薄膜を得ることができなかった。Comparative Example 1 Polytrimethylsilylpropyne having a weight average molecular weight of 2.31 million was dissolved in hexane to prepare a polymer solution with a concentration of 2.3% by weight. On the other hand, water was prepared as a supporting liquid, and a stainless steel water tank ( 325mm x 370mm x 50mm). When about 0.15 cc of the above polymer solution was dropped vertically from just above the water surface using a pipette, development did not proceed and a thin film could not be obtained.
【００２９】比較例２
重量平均分子量２３１万のポリトリメチルシリルプロピ
ンをヘキサンに溶解して濃度２．３重量％の高分子溶液
に調整し、この溶液にジアルキルスルホ琥珀酸エステル
ナトリウム塩（第一工業製薬株式会社製、ネオコールＳ
Ｗ）を臨界ミセル濃度（ＣＭＣ）となるように添加した
。一方、支持液体として水を用意し、ステンレス製水槽
（３２５ｍｍ×３７０ｍｍ×５０ｍｍ）に満たした。上
記高分子溶液約０．１５ＣＣをピペットにより水面上ぎ
りぎりから垂直に落としたところ、ある程度展開したが
、十分な面積を持つ薄膜は得られなかった。薄膜が展開
して形成される状態を目視により観察し、その評価を表
２に示した。Comparative Example 2 Polytrimethylsilylpropyne having a weight average molecular weight of 2.31 million was dissolved in hexane to prepare a polymer solution with a concentration of 2.3% by weight, and dialkyl sulfosuccinate sodium salt (Daiichi Kogyo Co., Ltd.) was added to this solution. Manufactured by Pharmaceutical Co., Ltd., Neocol S
W) was added to reach the critical micelle concentration (CMC). On the other hand, water was prepared as a supporting liquid and filled in a stainless steel water tank (325 mm x 370 mm x 50 mm). When about 0.15 cc of the above polymer solution was dropped vertically from just above the water surface using a pipette, it spread to some extent, but a thin film with a sufficient area could not be obtained. The state in which the thin film was developed and formed was visually observed, and the evaluations are shown in Table 2.
【００３０】比較例３
重量平均分子量２３１万のポリトリメチルシリルプロピ
ンをヘキサンに溶解して濃度２．３重量％の高分子溶液
を調整した。一方、支持液体として水を用意し、ラウリ
ルトリメチルアンモニウムクロライドを臨界ミセル濃度
（ＣＭＣ）の１万分の１の濃度となるように添加し、ス
テンレス製水槽（３２５ｍｍ×３７０ｍｍ×５０ｍｍ）
に満たした。上記、高分子溶液約０．１５ＣＣをピペッ
トにより水面上ぎりぎりから垂直に落としたところ、ほ
とんど展開せず、薄膜は得られなかった。Comparative Example 3 Polytrimethylsilylpropyne having a weight average molecular weight of 2.31 million was dissolved in hexane to prepare a polymer solution having a concentration of 2.3% by weight. On the other hand, prepare water as a supporting liquid, add lauryltrimethylammonium chloride to a concentration of 1/10,000 of the critical micelle concentration (CMC), and prepare water in a stainless steel water tank (325 mm x 370 mm x 50 mm).
filled with. When about 0.15 cc of the above polymer solution was dropped vertically from just above the water surface using a pipette, it hardly spread and no thin film was obtained.
【００３１】[0031]
【表２】[Table 2]
【００３２】実施例４〜６
重量平均分子量２３１万のポリトリメチルシリルプロピ
ンをヘキサンに溶解して濃度２．３重量％の高分子溶液
に調整し、この溶液にアルキルエチレンオキサイド（第
一工業製薬株式会社製、ノイゲンＥＴ−１３５）を臨界
ミセル濃度（ＣＭＣ）となるように添加した。一方、支
持液体として水を用意し、ラウリルトリメチルアンモニ
ウムクロライドを臨界ミセル濃度（ＣＭＣ）の千分の１
（実施例４）、１万分の１（実施例５）、１０万分の１
（実施例６）の濃度となるように添加し、ステンレス製
水槽（３２５ｍｍ×３７０ｍｍ×５０ｍｍ）に満たした
。上記、高分子溶液０．１５ＣＣをピペットにより水面
上ぎりぎりから垂直に落としたところ、スムーズに展開
が進み、十分な面積を持つ膜厚が約１５０オングストロ
ームの均一な超薄膜が得られた。薄膜が展開して形成さ
れる状態を目視により観察し、その評価を表３に示した
。Examples 4 to 6 Polytrimethylsilylpropyne having a weight average molecular weight of 2.31 million was dissolved in hexane to prepare a polymer solution having a concentration of 2.3% by weight, and alkyl ethylene oxide (Daiichi Kogyo Seiyaku Co., Ltd.) was added to this solution. Neugen ET-135 (manufactured by Nippon Express Co., Ltd.) was added to the solution at a critical micelle concentration (CMC). On the other hand, prepare water as a supporting liquid and add lauryltrimethylammonium chloride to 1/1000 of the critical micelle concentration (CMC).
(Example 4), 1/10,000 (Example 5), 1/100,000
(Example 6) and filled a stainless steel water tank (325 mm x 370 mm x 50 mm). When 0.15 cc of the above polymer solution was dropped vertically from just above the water surface using a pipette, the development progressed smoothly and a uniform ultra-thin film with a sufficient area and a film thickness of approximately 150 angstroms was obtained. The state in which the thin film was developed and formed was visually observed, and the evaluation is shown in Table 3.
【００３３】実施例７〜９
重量平均分子量２３１万のポリトリメチルシリルプロピ
ンをヘキサンに溶解して濃度２．３重量％の高分子溶液
に調整し、この溶液にアルキルエチレンオキサイド（第
一工業製薬株式会社製、ノイゲンＥＴ−１３５）を臨界
ミセル濃度（ＣＭＣ）となるように添加した。一方、支
持液体として水を用意し、ドデシルベンゼンスルホン酸
ナトリウムを臨界ミセル濃度（ＣＭＣ）の千分の１（実
施例７）、１万分の１（実施例８）、１０万分の１（実
施例９）の濃度となるように添加し、ステンレス製水槽
（３２５ｍｍ×３７０ｍｍ×５０ｍｍ）に満たした。上
記、高分子溶液０．１５ＣＣをピペットにより水面上ぎ
りぎりから垂直に落としたところ、スムーズに展開が進
み、十分な面積を持つ膜厚が約１５０オングストローム
の均一な超薄膜が得られた。
薄膜が展開して形成される状態を目視により観察し、そ
の評価を表３に示した。Examples 7 to 9 Polytrimethylsilylpropyne having a weight average molecular weight of 2.31 million was dissolved in hexane to prepare a polymer solution having a concentration of 2.3% by weight, and alkyl ethylene oxide (Daiichi Kogyo Seiyaku Co., Ltd.) was added to this solution. Neugen ET-135 (manufactured by Nippon Express Co., Ltd.) was added to the solution at a critical micelle concentration (CMC). On the other hand, water was prepared as a supporting liquid, and sodium dodecylbenzenesulfonate was added to 1/1000th (Example 7), 1/10,000th (Example 8), and 1/100,000th (Example 7) of the critical micelle concentration (CMC). 9), and filled a stainless steel water tank (325 mm x 370 mm x 50 mm). When 0.15 cc of the above polymer solution was dropped vertically from just above the water surface using a pipette, the development progressed smoothly and a uniform ultra-thin film with a sufficient area and a film thickness of approximately 150 angstroms was obtained. The state in which the thin film was developed and formed was visually observed, and the evaluation is shown in Table 3.
【００３４】実施例１０〜１２
重量平均分子量２３１万のポリトリメチルシリルプロピ
ンをヘキサンに溶解して濃度２．３重量％の高分子溶液
に調整し、この溶液にポリエーテル変性シリコーン（信
越化学株式会社製 ＫＦ−６１８）を臨界ミセル濃度
（ＣＭＣ）となるように添加した。一方、支持液体とし
て水を用意し、ポリスチリルフェニルエーテルを臨界ミ
セル濃度（ＣＭＣ）の千分の１（実施例１０）、１万分
の１（実施例１１）、１０万分の１（実施例１２）の濃
度となるように添加し、ステンレス製水槽（３２５ｍｍ
×３７０ｍｍ×５０ｍｍ）に満たした。上記、高分子溶
液０．１５ＣＣをピペットにより水面上ぎりぎりから垂
直に落としたところ、スムーズに展開が進み、十分な面
積を持つ膜厚が約１５０オングストロームの均一な超薄
膜が得られた。薄膜が展開して形成される状態を目視に
より観察し、その評価を表３に示した。Examples 10 to 12 Polytrimethylsilylpropyne having a weight average molecular weight of 2,310,000 was dissolved in hexane to prepare a polymer solution with a concentration of 2.3% by weight, and polyether-modified silicone (Shin-Etsu Chemical Co., Ltd.) was added to this solution. KF-618) was added to reach the critical micelle concentration (CMC). On the other hand, water was prepared as a supporting liquid, and polystyrylphenyl ether was added to the critical micelle concentration (CMC) of 1/1000th (Example 10), 1/10,000th (Example 11), and 1/100,000th (Example 12). ) in a stainless steel water tank (325 mm).
x 370 mm x 50 mm). When 0.15 cc of the above polymer solution was dropped vertically from just above the water surface using a pipette, the development progressed smoothly and a uniform ultra-thin film with a sufficient area and a film thickness of approximately 150 angstroms was obtained. The state in which the thin film was developed and formed was visually observed, and the evaluation is shown in Table 3.
【００３５】[0035]
【表３】[Table 3]
【００３６】[0036]
【発明の効果】本発明の方法では、膜形成性高分子材料
を揮発性溶媒に溶解した高分子溶液と、支持液体の双方
に互いに異なる界面活性剤を添加しているので、高分子
溶液の表面張力ｂを低下させると共に、双方の界面活性
剤の相互作用によって支持液体と高分子溶液との間に働
く界面張力ｃを著しく低下させることができ、結果とし
て、支持液体表面に高分子溶液を展開させる展開圧Ｓを
大きくすることを可能にしている。このため、本発明の
方法によれば、通常であれば、展開性が悪くて支持液体
の表面に広がらず、薄膜を形成できないような膜形成性
高分子を用いても、十分な面積を持つ均一な膜厚の薄膜
を簡便に製造することができる。Effects of the Invention In the method of the present invention, different surfactants are added to both the polymer solution in which a film-forming polymer material is dissolved in a volatile solvent and the supporting liquid. In addition to reducing the surface tension b, it is possible to significantly reduce the interfacial tension c that acts between the support liquid and the polymer solution due to the interaction of both surfactants, and as a result, the polymer solution can be deposited on the surface of the support liquid. This makes it possible to increase the deployment pressure S for deployment. Therefore, according to the method of the present invention, even if a film-forming polymer that normally has poor spreadability and does not spread over the surface of the supporting liquid and cannot form a thin film, it can have a sufficient surface area. A thin film with uniform thickness can be easily produced.
【００３７】とくに、支持液体に添加される界面活性剤
の濃度を、臨界ミセル濃度の百分の一から百万分の一の
濃度範囲にすれば、支持液体の表面張力ａの低下を押え
ながら、支持液体と高分子溶液との間に働く界面張力ｃ
を低下させることができ、結果として展開圧Ｓをより大
きくできるので、より薄い高分子薄膜を安定に製造する
ことができる。In particular, if the concentration of the surfactant added to the support liquid is in the range of 1/100 to 1/1 million of the critical micelle concentration, the surface tension a of the support liquid can be suppressed. , the interfacial tension c acting between the supporting liquid and the polymer solution
can be lowered, and as a result, the spreading pressure S can be increased, so that a thinner polymer thin film can be stably produced.
Claims (4)
らなる高分子溶液を支持液体表面に展開させて高分子薄
膜を製造する方法において、該支持液体と該高分子溶液
とにお互いに異なる界面活性剤を添加することを特徴と
する高分子薄膜の製造方法。Claim 1. A method for producing a thin polymer film by spreading a polymer solution consisting of a film-forming polymer material and a volatile solvent on the surface of a supporting liquid, in which the supporting liquid and the polymer solution are mixed with each other. A method for producing a polymer thin film characterized by adding different surfactants.
が、界面活性剤の臨界ミセル濃度の百分の一から百万分
の一の濃度である請求項１に記載の高分子薄膜の製造方
法。2. The production of a polymer thin film according to claim 1, wherein the concentration of the surfactant added to the support liquid is from 1/100 to 1/1 million of the critical micelle concentration of the surfactant. Method.
らなる高分子溶液に添加する界面活性剤の濃度が、界面
活性剤の臨界ミセル濃度の千分の一から千倍の濃度であ
る請求項１または２に記載の高分子薄膜の製造方法。[Claim 3] The concentration of the surfactant added to the polymer solution consisting of a film-forming polymer material and a volatile solvent is from 1/1000 to 1,000 times the critical micelle concentration of the surfactant. A method for producing a polymer thin film according to claim 1 or 2.
項１〜３のいずれかに記載の高分子薄膜の製造方法。4. The method for producing a thin polymer film according to claim 1, wherein the supporting liquid is water or an aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7380591A JPH04284837A (en) | 1991-03-13 | 1991-03-13 | Preparation of polymer membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7380591A JPH04284837A (en) | 1991-03-13 | 1991-03-13 | Preparation of polymer membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04284837A true JPH04284837A (en) | 1992-10-09 |
Family
ID=13528753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7380591A Pending JPH04284837A (en) | 1991-03-13 | 1991-03-13 | Preparation of polymer membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04284837A (en) |
-
1991
- 1991-03-13 JP JP7380591A patent/JPH04284837A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kovalchuk et al. | Fluoro-vs hydrocarbon surfactants: why do they differ in wetting performance? | |
| Hu et al. | Surfactant-enhanced cellulose nanocrystal Pickering emulsions | |
| US10138366B2 (en) | Water-in-oil polyacrylamide-based microemulsions and related methods | |
| US10092885B2 (en) | Emulsions and methods of making emulsions | |
| De Folter et al. | Oil-in-water Pickering emulsions stabilized by colloidal particles from the water-insoluble protein zein | |
| US11046853B2 (en) | Systems and methods for creating durable lubricious surfaces via interfacial modification | |
| DE2319853C2 (en) | Process for the coacervation of an aqueous dispersion containing solid particles | |
| JP2006321764A (en) | Fluorine-containing organosilicon compound and fluorine-containing surfactant | |
| WO1995017453A1 (en) | Elastomeric film, method for preparing same, and uses thereof | |
| US20130231429A1 (en) | Emulsion Compositions Comprising Polyacrylamide Copolymer and Ethylene Oxide - Propylene Oxide Copolymer | |
| US20220032338A1 (en) | Fabrication of Crosslinked and Reactive Nanoporous Polymer Coatings Using Spray-Based Methods | |
| TWI307272B (en) | A disposable wipe for treating a selected surface and a method of polishing a piece of furniture | |
| JPH04284837A (en) | Preparation of polymer membrane | |
| AU2014414847B2 (en) | Unit dose fabric softener | |
| CA1331338C (en) | Aqueous film-forming compositions for controlling the release of active agents and process of making same | |
| Park et al. | Highly stable, electrostatically attractive silicone nanoemulsions produced by interfacial assembly of amphiphilic triblock copolymers | |
| Grigoreva et al. | Aggregation behaviour of poly (fluoro (meth) acrylate)-block-poly (acrylic acid) copolymers at the air/water interface | |
| CA2796080C (en) | Aqueous based process to fabricate nanostructured block copolymer films | |
| TW201209224A (en) | Etchant composition and method for forming metal wiring | |
| Wang et al. | Fabrication of polymersomes with controllable morphologies through dewetting W/O/W double emulsion droplets | |
| JP3460344B2 (en) | Emulsion, method for producing the same, and polymer particles | |
| DE3518875A1 (en) | Coating composition, process for the coating of plastic articles, and plastic articles which have a polymer coating | |
| Ahmed et al. | Forces between mica and end-grafted statistical copolymers of sulfobetaine and oligoethylene glycol in aqueous electrolyte solutions | |
| Suga et al. | Phase separation of mixed LB films containing spin probe molecules | |
| JPS6268841A (en) | Polyvinyl alcohol composition having excellent anticissing property |