JPS62266169A - Preparation of monomolecular film - Google Patents
Preparation of monomolecular filmInfo
- Publication number
- JPS62266169A JPS62266169A JP61108847A JP10884786A JPS62266169A JP S62266169 A JPS62266169 A JP S62266169A JP 61108847 A JP61108847 A JP 61108847A JP 10884786 A JP10884786 A JP 10884786A JP S62266169 A JPS62266169 A JP S62266169A
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydrophilic
- monomolecular film
- compound
- substrate
- 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
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 125000006239 protecting group Chemical group 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 32
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 27
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 12
- 239000002356 single layer Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 235000021314 Palmitic acid Nutrition 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010511 deprotection reaction Methods 0.000 description 3
- -1 dimethylisopropylsilyl group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- KFPPFDUBWHHKCH-UHFFFAOYSA-N 16-[dimethyl(propan-2-yl)silyl]oxyhexadecan-1-ol Chemical compound CC(C)[Si](C)(C)OCCCCCCCCCCCCCCCCO KFPPFDUBWHHKCH-UHFFFAOYSA-N 0.000 description 1
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- YCXVDEMHEKQQCI-UHFFFAOYSA-N chloro-dimethyl-propan-2-ylsilane Chemical compound CC(C)[Si](C)(C)Cl YCXVDEMHEKQQCI-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000005043 dihydropyranyl group Chemical group O1C(CCC=C1)* 0.000 description 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- GJBXIPOYHVMPQJ-UHFFFAOYSA-N hexadecane-1,16-diol Chemical compound OCCCCCCCCCCCCCCCCO GJBXIPOYHVMPQJ-UHFFFAOYSA-N 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
- B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
- Manufacturing Optical Record Carriers (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は有機単分子膜、特に親水性基材に吸着可能で
あり、かつ吸着後に気体側表面（纂材と反対側〉に親水
性基、もしくは反応性親水性基を有することを特徴とす
る有機単分子膜の製造方法に関するものである。Detailed Description of the Invention [Industrial Application Field] This invention is capable of adsorbing onto an organic monomolecular film, especially a hydrophilic substrate, and after adsorption, a hydrophilic group is formed on the gas side surface (the side opposite to the fiber). Alternatively, the present invention relates to a method for producing an organic monomolecular film characterized by having a reactive hydrophilic group.
［従来の技術］
有機化合物の単分子膜、累積膜には数多くの用途がある
。エレクトロニクスの分野では、例えば、膜厚を正確に
制御した半導体装置用絶縁膜、磁気ディスク装置等の保
護潤滑膜、光電変換膜、光学的情報記録膜、光学的情報
記憶膜などへの応用が検討されている。これらの目的の
ために、単分子膜、累積膜を作製する方法として、水面
上で両親媒性物質を高度に分子配向させて単分子層とし
、その単分子層を基材上に写し取る方法、いわゆるラン
グミュア−ブロジェット法が多く用いられている。[Prior Art] Monomolecular films and cumulative films of organic compounds have many uses. In the field of electronics, for example, applications are being considered for insulating films for semiconductor devices with precisely controlled film thickness, protective lubricant films for magnetic disk drives, photoelectric conversion films, optical information recording films, optical information storage films, etc. has been done. For these purposes, methods for producing monomolecular films and cumulative films include a method in which amphiphilic substances are highly oriented on the water surface to form a monomolecular layer, and the monomolecular layer is transferred onto a substrate; The so-called Langmuir-Blodgett method is often used.
［発明が解決しようとする問題点］
しかしながら、この方法で作製される単分子膜、累積膜
を構成する月利分子は、一般に長鎖アルキル基の一方の
末端のみに親水基を右ＭるｂのＣある。かかる構成分子
から成る単分子膜、累積膜を作製する場合は、熱力学的
な安定１ノ１の問題がら、膜の支台、覆−イｒわＩ５基
祠と逆側である気体側に疎水性部分を露出さゼた膜構成
にしでおく必要がある。ｂし気体側に親水基部分を露出
さＥ！でおいても、放置しであくだＣｊで構成分子の反
転が起こり、表面は疎水＝ｌ’ｌに変わってしまうこと
が知られている。[Problems to be Solved by the Invention] However, the molecules constituting the monomolecular film or cumulative film produced by this method generally have a hydrophilic group at only one end of the long chain alkyl group. There is a C. When producing a monomolecular film or a cumulative film composed of such constituent molecules, due to thermodynamic stability issues, it is necessary to It is necessary to maintain a membrane structure in which the hydrophobic portion is exposed. b and expose the hydrophilic group part on the gas side E! It is known that even if Cj is left untreated, the constituent molecules will be inverted and the surface will become hydrophobic = l'l.
したがって従来は親水・［（Ｉ阜を気体側（、Ｔ露出し
た形の単分子膜を形成りることは非常に困難であり、従
って単分子膜あるいはその累積膜を作製後にぞの十に親
水・１］１物質を吸着させたり膜に物質を反応させて新
しい機能を付与り−るに（３１、この田難さが人ぎイ【
問題とイ宋−）Ｔいた。Therefore, in the past, it was very difficult to form a monomolecular film with the surface exposed to the gas side.・1] Adding new functions by adsorbing a substance or reacting the substance to a membrane (31, this difficulty is a challenge for humans [
Problem and Lee Song -) T was there.
しかし、親水・１ノ１基には一般に反応性に富むものか
多く、もしかかる肱が作成Ｃ′きれば、中分子膜、ある
いＣ５ｔその累積膜の表面に反応１ノ１を付与できるこ
とになる。親水４ノｊ基のこのよう４１反応性あるいは
親水性そのものを利用しＣ１例えば、半導体装置用絶縁
層、磁気ｆ゛イスク装置の保護潤滑層、光重変換機能を
持つ層、光学的情報記録層、）Ｉｌ′１学的情報記憶［
閃などを単分子膜ＩＴ、 Ｍ設【−」ることか−Ｃ″さ
るように１．ｆるｔ）けである、。However, many hydrophilic 1-1 groups are generally highly reactive, and if such a group can be created, it is possible to impart reactive 1-1 to the surface of a middle molecular film or a cumulative film of C5t. Become. Utilizing this 41 reactivity or hydrophilicity itself of the hydrophilic 4-j group, C1 can be used, for example, insulating layers for semiconductor devices, protective lubricant layers for magnetic disk devices, layers with a light weight conversion function, and optical information recording layers. ,) Il′1logical information storage [
The monomolecular film IT, such as a flash, is set as 1.ft).
本発明の目的（Ｊｌ、以ト述ｌ＼Ｉご問題点を解決（す
るために、新規へ単分子膜の製）前方法を提供づること
にあるか、具体的には、親水′［）１支台に吸ン１１１
■能Ｃ゛あり、かつ吸着後に気体側、’ｊ’ ／、ｒ
１７） ’Ｉ’ｉ阜祠ど基材側に親水・１ノ１阜を有づ
る有機単分子膜の製）六プノ法を１、＋惧づ−ることに
ある。The purpose of the present invention is to provide a new method for producing a monolayer film to solve the problems mentioned above, specifically, to solve the problems mentioned above. Suction 111 on one stand
■With function C, and after adsorption, on the gas side, 'j' /, r
17) The purpose of this method is to develop an organic monomolecular film having a hydrophilic layer on the base material side.
［問題点を解決するための手段］
本発明ＩＪ、一般式：
％式％）
（式中、Ｘ（Ｊ良親水″１〕１基、Ｉ−＜ １１：炭素
原子数かＦ’、 １１十、望ましくＩに１４１こ（十の
炭化水素すを示−１）で示される１伸また（５ｔ２種Ｊ
χ１−のａ（幾化合物の一プｊの親水・１／１基を疎水
１１保護基（、二☆換し・−ｃｉＬ 一般式：
Ｘ′−Ｒ′（）
（式中、Ｘ’１．を親水性基、Ｒ′ｌＪ、炭素原１′数
か８１ス十、望ましくは１４以十の炭化水素基を示す）
Ｃ′示される１種またｌ」、２種以上の首は化合物とと
もにラングミュアーブ［１ジ■ツ１〜法を用いて同時に
親水性基板上に配向制御して吸着ざ１！る事を特徴とす
る単分子膜の製造方法である。[Means for solving the problems] IJ of the present invention, general formula: % formula %) (wherein, , preferably I is 141 (indicating 10 hydrocarbons - 1) or (5t 2 species J
a of χ1-(1/1 hydrophilic group of compound j is replaced with hydrophobic 11 protecting group (, di☆-ciL) General formula: X'-R'() (in the formula, X'1. is a hydrophilic group, R'lJ is a hydrocarbon group having 1' or 81 carbon atoms, preferably 14 or more)
One or more of the compounds shown in C' are simultaneously aligned and adsorbed onto a hydrophilic substrate using Langmuirb's method. This is a method for producing a monomolecular film, which is characterized by:
本発明の要旨とするところは、回−の親水性基を両末端
（こ右Ｊ−る有機化合物および片末端に親水・ｉ〕１基
を右Ｊる有機化合物を原石としで、ラングミュアーブ［
１ジＴツト法を用いて親水性基Ｈ上に基材側と気体側の
両方に親水・１）１阜を持つ単分子膜を製造するに際し
、原１！：１物質の一部として、同一の親水性基を両末
端に有する化合物の一方の親水・１ノ１基のみを疎水・
１１１保護基によって保護（）ておいたものを表面に必
要とされる親水″［）１阜の早に応じて用いることによ
り、気体側に親水↑ノｌ棋が必要量だ（Ｊ存在した単分
子膜の製造方法を提供することである。The gist of the present invention is to use an organic compound having two hydrophilic groups at both ends (an organic compound with two hydrophilic groups and one hydrophilic group at one end) as raw stone, [
When producing a monomolecular film having hydrophilic groups H on both the substrate side and the gas side using the 1-zit method, the base 1! :As part of one substance, only one hydrophilic group of a compound having the same hydrophilic group at both ends is hydrophobic.
By using the 111 protected group () according to the amount of hydrophilicity required on the surface, the amount of hydrophilicity↑Nol on the gas side is the required amount (J An object of the present invention is to provide a method for manufacturing a molecular membrane.
本発明における単分子膜の親水性基である、前記一般式
（Ｉ）および（１’Ｉ）のＸおよびＸ′とし一１雪）〜
で（よじド目キシル基、カルホキシル
］−基、チオカルボキシル阜、ジーチ４カル小ーＶシル
基、スルレノイノ阜、スルホ基、カルバ［−イル基、゛
１イカルバモーイル阜、アミノ基、買（奥ツノミノ阜等
があげられ、単分子膜形成物質はこれらの親水・１〕１
基のうちの１種を両末端に有するｆ１機化合物Ｊづよび
前記有機化合物の親水↑ノ１基と同一また（Ｊ ｉｔ１
５“＋９． ／−にる親水性基を片末端（こ右する右Ｉ
幾化合物（゛ある、。X and X' of the general formulas (I) and (1'I), which are the hydrophilic groups of the monomolecular film in the present invention, are Examples include carboxyl group, dithi-4-carboxylic group, sulurenoin group, sulfo group, carba[-yl group, 1-carbamoyl group, amino group, and monolayer group, and monolayer-forming substances include these. Hydrophilic・1〕1
The f1 machine compound J having one of the groups at both ends and the hydrophilic ↑1 group of the organic compound or (J it1
5"+9. Add the hydrophilic group at /- to one end (this right I
There are several compounds.
また前記−・般式（Ｉ）および（Ｔｌ）におε−Ｊる［
【および１マ′ とし２てはそれぞれ］−価および一価
の鎖式飽和炭化水素基、鎖式不飽和炭化水素基またはこ
れらの炭化水素基の一部に１個また１」１２個以トのフ
ｌーニレン拮を含む炭化水素基があげられる。In addition, the general formula (I) and (Tl) have ε-J[
[and 1 and 2 respectively]-valent and monovalent chain-type saturated hydrocarbon groups, chain-type unsaturated hydrocarbon groups, or a part of these hydrocarbon groups has 1 or 12 or more Examples include hydrocarbon groups containing fluorylene.
Ｒおよびｔｔ’ｔａ同一でも相異なっていてーしよい．
。R and tt'ta may be the same or different.
.
一般式（Ｉ＞の化合物および一般式（Ｉ）の化合物の使
用割合は、単分子膜表面に妃Ｉンとする親水性基の早に
よって適宜選択することができるが、通常は一般式（Ｉ
＞の化合物を３モル％以上−、好まＩ，’ ＜ １：１
０モル％以上存在さぜる。また、各化合物はてれそれ１
種のみを用いてもよいし、もし）必要があれば２種以上
を混合して用いてもよい。The proportions of the compound of general formula (I>) and the compound of general formula (I) can be appropriately selected depending on the number of hydrophilic groups to be attached to the surface of the monolayer.
>3 mol% or more of the compound, preferably I,'< 1:1
It is present in an amount of 0 mol% or more. In addition, each compound has 1
Seeds alone may be used, or if necessary, two or more types may be used in combination.
本発明の方法によれば、両末端に親水性基を有する化合
物については両末端の親水性基のうちの一方を疎水性保
護基で保護することによってラングミュアーブロジエツ
１〜法を用いて単分子膜を形成することができる。すな
わち一方の親水性基を疎水性基に変換してあ（プば通常
用いられている両親媒１）１物貿と全く同等に扱うこと
ができる。そのために用いることのできる疎水゛１ノ１
保護基としては、トリメデルシリル基、ジメチルイソプ
ロピルシリル基、ジメヂルターシャリーブヂルシリル基
のような１〜リアルキルシリル基、ジヒドロピラニル基
等を含むエーテル系保護基、同じくエステル系保護基、
トリフロロ酢酸アミド等のようなアミド系保ｍｌなと一
般に有機合成化学の分野で用いられるもののうち適切な
ものを用いればよい。これらの疎水性保護基の選択にあ
たっては、一般式（Ｉ＞の化合物の一方の親水性基のみ
が選択的に保護されること、および親水性基材に単分子
膜を作製した後に、表面の疎水性保護基が脱保護されヤ
ずいことなどを考慮して選択される。また疎水性保護基
の導入方法としては直接一方の親水性基を疎水＝Ｉ’ｌ
保護基に変換する方法であっても、あるいは両方の親水
性基を疎水性保護基に変換した後、一方の保護基のみを
脱保護する方法であってもよい。According to the method of the present invention, for compounds having hydrophilic groups at both ends, one of the hydrophilic groups at both ends is protected with a hydrophobic protecting group, and Langmuir-Brosiert's method 1~ is used. A monolayer can be formed. That is, by converting one hydrophilic group to a hydrophobic group (if the amphiphile 1 is commonly used), it can be treated exactly the same as a single product. Hydrophobic ``1 no 1'' that can be used for that purpose
Examples of the protecting group include 1-alkylsilyl groups such as trimedelsilyl group, dimethylisopropylsilyl group, and dimethyltert-butylsilyl group, ether-based protecting groups including dihydropyranyl group, and ester-based protecting groups.
Appropriate amide-based polymers such as trifluoroacetic acid amide and the like generally used in the field of organic synthetic chemistry may be used. When selecting these hydrophobic protecting groups, it is important to remember that only one hydrophilic group of the compound of general formula (I>) is selectively protected, and that after forming a monomolecular film on a hydrophilic substrate, the surface The hydrophobic protecting group is selected taking into consideration that it will be difficult to deprotect.Also, as a method for introducing the hydrophobic protecting group, one hydrophilic group is directly attached to the hydrophobic = I'l
It may be a method of converting into a protecting group, or a method of converting both hydrophilic groups into a hydrophobic protecting group and then deprotecting only one of the protecting groups.
一方、片末端のみに親水性基を有する化合物は、その親
水性基を保護する必要はなく、通常はそのまま用いられ
るが、両末端に親水性基を有する化合物についての適切
な脱保護条件で同時に脱保護されるならば、疎水性保護
基によって保護されていても差し支えない。On the other hand, compounds with a hydrophilic group at only one end do not need to protect the hydrophilic group and are usually used as is, but compounds with hydrophilic groups at both ends can be deprotected simultaneously under appropriate deprotection conditions. If it is deprotected, it may be protected by a hydrophobic protecting group.
このようにして水面上で片方の親水性基のみが保護され
た化合物おにび片末端に親水性基をイ１する化合物を同
時にラングミュアーブ目ジェット法によって親水性１ｔ
、Ｊ上に写し取る。水面上ではその保護基がはずれない
ように、水中の各種イオン濃度、水の温度、水面上での
展開時間などの諸条イ！１を適切に選択する必要がある
。水中には、水面の単分子膜のＪ福を生成するような金
属イオンが含まれていてもよい。In this way, a compound with only one hydrophilic group protected on the water surface and a compound with a hydrophilic group at one end are simultaneously added to the hydrophilic compound using the Langmuirbian jet method.
, copy it on J. In order to prevent the protective group from being removed on the water surface, there are various rules such as the concentration of various ions in the water, the temperature of the water, and the development time on the water surface. 1 must be selected appropriately. The water may contain metal ions that generate a monomolecular film on the water surface.
得られる単分子膜は表面が疎水性保護基で保護されてい
るので適当に調製した試薬溶液の中に浸すか、適当な試
薬蒸気に曝すなどの方法によって遊離の親水性基とする
ことができる。Since the surface of the resulting monomolecular film is protected with a hydrophobic protecting group, it can be made into free hydrophilic groups by immersing it in an appropriately prepared reagent solution or by exposing it to an appropriate reagent vapor. .
［作 用］
両末端に同一の親水性基を有する一般式（Ｉ）の化合物
、および片末端に親水性基を有する一般式（ＩＩ）の化
合物の混合物を原料とし、保護基とその保護条件あるい
は脱保護条件を適切に選択することにより、ラングミュ
ア−ブロジェット法によって、親水性基材上に、表面に
望ましい親水性基を望ましい量たり持たせた単分子膜を
作製することができる。本発明の方法によると一般式（
Ｉ）の化合物の片末端の親水性基を疎水性保護基により
疎水化しておくため、一般式（Ｉ＞の化合物を片末端の
みに親水性基を有する物質として扱うことができ、水面
」二で単分子膜として容易に配向させることができる。[Function] Using a mixture of a compound of general formula (I) having the same hydrophilic group at both ends and a compound of general formula (II) having a hydrophilic group at one end as a raw material, protecting groups and their protection conditions are used as raw materials. Alternatively, by appropriately selecting deprotection conditions, a monomolecular film having a desired amount of desired hydrophilic groups on the surface can be produced on a hydrophilic substrate by the Langmuir-Blodgett method. According to the method of the present invention, the general formula (
Since the hydrophilic group at one end of the compound of I) is made hydrophobic with a hydrophobic protecting group, the compound of general formula (I>) can be treated as a substance having a hydrophilic group only at one end, and the water surface "2" can be easily oriented as a monolayer.
なお、親水性基材に写し取った後の一般式（Ｉ＞の疎水
性保護基の脱保護は、表面に目的通りの親水性基を設（
プるための手段である。In addition, deprotection of the hydrophobic protecting group of the general formula (I> after transferring it to a hydrophilic substrate is carried out by setting the desired hydrophilic group on the surface (
It is a means to
［実施例］ 次に本発明を実施例によって説明する。[Example] Next, the present invention will be explained by examples.
実施例１
１．１６−シヒドロキシヘキ１ナデカン（４ｍｎｏりの
テｌ〜ラヒドロフラン（２０７り溶液に等量のジメチル
イソプロピルシリルクロリドと等量の１〜リエヂルアミ
ンを加え、３０分間５０’Ｃで加熱した。Ｏ′Ｃに冷却
後、ヘキサンを３０ｍｆ！加え、Ｏ′Ｃの水で水洗（３
Ｘ３０ｍ＆）シた。硫酸マグネシウムで乾燥後、減圧で
溶媒を除去し、シリカゲルカラムで精製して、１６−（
ジメチルイソプロピルシリロキシ）ヘキサデカノールを
得た。この物質２５μｍｏｒ！と、ヘキサデカン酸２５
μｍｏｆ！を１０ｍｌ１のクロロホルムに）容解して、
蒸留水上に展開し、表面圧を２５ｄｙｎ／Ｃｍ２に保ち
つつ、石英基板上に写し取った。写し取ったままの基板
表面の表面エネルギーを液滴の接触角から針筒すると、
１８ｅｒＯ／Ｃｍ”であり、非常に疎水性が大きかった
。Example 1 To a solution of 1.16-cyhydroxyhexylnadecane (4 mmol of terahydrofuran (207) was added an equal amount of dimethylisopropylsilyl chloride and an equivalent amount of 1-liezylamine, and heated at 50'C for 30 minutes. After cooling to O'C, add 30mf! of hexane and wash with water at O'C (30 mf!).
X30m &) Shita. After drying with magnesium sulfate, the solvent was removed under reduced pressure and purified with a silica gel column to obtain 16-(
Dimethylisopropylsilyloxy)hexadecanol was obtained. This substance is 25 μmol! and hexadecanoic acid 25
μmof! in 10 ml of chloroform),
It was developed on distilled water and transferred onto a quartz substrate while maintaining the surface pressure at 25 dyn/Cm2. If we calculate the surface energy of the surface of the substrate as it was copied from the contact angle of the droplet, we get
18erO/Cm'', and was extremely hydrophobic.
続いてこの基板を酢酸−水（３： １ ）溶液に浸して
からよく水洗することにより基板上に１．１６−シヒド
ロキシヘキサデカンとへキ昏ナデ′カン酸の等早漏合物
よりなる単分子膜を得た。基板表面の表面エネルギーは
４８６ｒＯ／Ｃｍ”と大きく、高い親水・１４を示した
。この単分子膜の高い親水性は、室温で１週間放置して
おいても全く変化しイｙかった。Subsequently, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to form a single molecule consisting of an isopropylene compound of 1,16-hydroxyhexadecane and hexadecanoic acid on the substrate. A membrane was obtained. The surface energy of the substrate surface was as large as 486 rO/Cm'', indicating high hydrophilicity.The high hydrophilicity of this monomolecular film did not change at all even after being left at room temperature for one week.
次に、この１，１６−ジヒトロキシヘキサデカンとヘキ
サデカン酸の等％’（Ｎ合物が単分子膜として配向、吸
着した石英基板上で、この単分子膜表面の親水性基（こ
こでは水酸基）の反応性を利用した実験を行なった。Next, on a quartz substrate on which the 1,16-dihydroxyhexadecane and hexadecanoic acid were oriented and adsorbed in equal proportions (N compound) as a monolayer, hydrophilic groups (here, hydroxyl groups) on the surface of the monolayer were deposited. ) experiments were conducted using the reactivity of
分子量約３０００の重合体
０＝Ｃ＝Ｎ−ＣＦ２（Ｃ２Ｆ４０）ｐ−（ＣＦ２０）ｑ
−ＣＦ２−Ｎ＝Ｃ＝０（ｒｌ：Ｑ＝１：１、各構造単位
は不規ｆａ１１である）をフレオンに溶解し、０．０８
重量％の溶液を作製した。この溶液を水酸基が表面に設
けられている前記石英基板−にに２５００回／分の回転
速度で回転塗イｌ、 １００ ’Ｃで焼成した後、フレ
オンで洗浄した。Polymer 0=C=N-CF2(C2F40)p-(CF20)q with a molecular weight of about 3000
-CF2-N=C=0 (rl:Q=1:1, each structural unit is irregular fa11) was dissolved in Freon, and 0.08
A wt% solution was prepared. This solution was coated on the quartz substrate having hydroxyl groups on its surface at a rotational speed of 2500 times/min, baked at 100'C, and washed with Freon.
得られた基板の表面エネルキーを重合体と接触させる前
と比較したところ、接触前の４８から１５ｅｒ’（１／
Ｃｍ２に大幅に減少していることかわかった。When the surface energy key of the obtained substrate was compared with that before contacting with the polymer, it was found that the surface energy key of the obtained substrate changed from 48 before contact to 15er' (1/
It was found that the amount decreased significantly to Cm2.
もし水酸基とイワシアナ−１〜基が反応１）ていな【ノ
れば、フレオンによる洗浄で手合体は甲分子膜トからは
ずれてしまうはずである。従って本発明の方法で製）告
した甲分子膜上の親水性基の反！；＋”；＋性がｈ効に
いかされ、単分子膜表面の水酸基は手合体の末端のイソ
シアナ−１へ基と長窓していることがわかる。If there is no reaction between the hydroxyl group and the sardine-1 ~ group, the hand-coupled body should be removed from the A-molecule membrane by washing with Freon. Therefore, the hydrophilic groups on the molecular membrane A prepared by the method of the present invention are It can be seen that the + property is utilized for the h effect, and the hydroxyl group on the monomolecular film surface forms a long window with the isocyanate-1 group at the end of the hand bond.
実施例２
実施例１で調整した１６−（ジメヂル、イソ１１１ピＪ
レシリロキシ）へキサデカノール２０μｍＯｆ！と、ヘ
キｑ−ｊ＝カン酸３０ｆＩｍＯｆ！を１０ｍ１のクロ目
ホルムに溶解して、蒸留水上に展開し、表面圧を２５
（Ｉ Ｖ １１ ／ ｃ…２に保ちつつ、石英基板上に
写し取った。′ダし取ったままの基板表面の表面エネル
ギーを液滴の接触角からｈＩ算するど、１８ｅｒｇ／ｃ
’ｍ２であり、非常に疎水性が人ぎかった。Example 2 16-(dimedyl, iso111piJ) prepared in Example 1
Resilyloxy) Hexadecanol 20μmOf! And, hexq-j=kanoic acid 30fImOf! was dissolved in 10 ml of black form, spread on distilled water, and the surface pressure was adjusted to 25
(It was transferred onto a quartz substrate while maintaining an IV of 11/c...2. The surface energy of the surface of the substrate as it was transferred was calculated from the contact angle of the droplet, hI was 18erg/c.
'm2, and was very hydrophobic.
続いてこの基板を酢酸−水（３： １ ）溶液に浸して
からよく水洗することにより基板上に１．１６−シヒド
ロキシヘキサデカンとヘキサデカン酸の−，１，２−
２：３）捏合物よりなる単分子膜を得た。基板表面の表
面１−ネルギーは４８ｅｒｇ／ｃｍ２と大きく、高い親
水性を示した。この単分子膜の高い親水性は、室温で１
週間放置しておいても全く変化しなかった。Subsequently, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to form a mixture of -,1,2-2:3) of 1,16-hydroxyhexadecane and hexadecanoic acid on the substrate. A monomolecular film was obtained. The surface 1-energy of the substrate surface was as large as 48 erg/cm2, indicating high hydrophilicity. The high hydrophilicity of this monolayer is 1 at room temperature.
Even after leaving it for a week, there was no change at all.
実施例３
実施例１で゛調整した１［−（ジメチルイソプロ１１１
９９日キシ〉ベキ１ナデカノール５μｍｏｆ！と、ヘキ
サデカン酸４５μｌｌｌ０ｆ！を１０ｍ１のり■ロホル
ムに溶解して、蒸留水上に展開し、表面圧を２５ｄｙｎ
／Ｃｍ２に保ちつつ、石英基板上に写し取った。写し取
ったままの基板表面の表面エネルギーを液滴の接触角か
らｉ■Ｉると、２０ｅｒｏ／ｃｍ２テアＩ’）、非常ニ
疎水性が大きかった。Example 3 1[-(dimethylisopro111) prepared in Example 1
99 days Kishi > 1 Nadecanol 5μmof! And hexadecanoic acid 45μlll0f! Dissolve it in 10 ml of glue and spread it on distilled water, and set the surface pressure to 25 dyn.
/Cm2 and was copied onto a quartz substrate. If the surface energy of the surface of the substrate as copied was calculated from the contact angle of the droplet, it was found to be 20 ero/cm 2 tar I'), indicating extremely high hydrophobicity.
続いてこの基板を酢酸−水（３： １ ）溶液に浸して
からよく水洗することにより基板上に１．１６−シヒド
ロキシヘキサデカンとヘキサデカン酸との１：９混合物
よりなる単分子膜を得た。基板表面の表面エネルギーは
４９ｅｒｇ／ｃｍ”と大きく、高い親水性を示した。こ
の単分子膜の高い親水性は、室温で１週間放置しておい
ても全く変化しなかった。Subsequently, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to obtain a monomolecular film made of a 1:9 mixture of 1,16-hydroxyhexadecane and hexadecanoic acid on the substrate. . The surface energy of the substrate surface was as large as 49 erg/cm'', indicating high hydrophilicity. The high hydrophilicity of this monomolecular film did not change at all even after being left at room temperature for one week.
実施例４
実施例１で調整した１６−（ジメチルイソプ］］ピルシ
リロキシ〉へキサデカノール４５ｆ１ｍｏｆ！ど、ベキ
１ｊデ′カン酸５μｍｏｐをｉｏｍｆ！のクロロホルム
に）８解して、蒸留水上に展開し、表面圧を２５（ハｌ
ｎ／ｃｍ２′に保ちつつ、石英基板上に写し取った。写
し取ったままの基板表面の表向エネルギーを液滴の接触
角から計算すると、１７ｅｒｇ／ｃ＋＋＋２であり、非
常に疎水性が大きかった。Example 4 16-(dimethylisop]]pyrsilyloxy>hexadecanol 45f1mof!do,1j'decanoic acid (5 μmop) prepared in Example 1 was dissolved in chloroform (iomf!), spread on distilled water, and the surface Increase the pressure to 25 (Har)
It was copied onto a quartz substrate while maintaining the density at n/cm2'. The surface energy of the surface of the substrate as imaged was calculated from the contact angle of the droplet, and was 17erg/c++2, indicating extremely high hydrophobicity.
続いてこの基板を酢酸−水（３： １ ）溶液に浸して
からよく水洗することにより基板上に１．１６−ジヒド
１］キシヘキザデカンとベキ１ｆデカン酸の９：１混合
物よりなる単分子膜を１ｑだ。基板表面の表面エネルギ
ーは４９ｅｒｇ／ｃ…２と大きく、高い親水性を示した
。この単分子膜の高い親水性は、室温で１週間放置して
おいても全く変化しなかった。Next, this substrate was immersed in an acetic acid-water (3:1) solution and thoroughly washed with water to form a monomolecular film made of a 9:1 mixture of 1,16-dihydro1]xyhexadecane and 1f-decanoic acid on the substrate. It's 1q. The surface energy of the substrate surface was as large as 49erg/c...2, indicating high hydrophilicity. The high hydrophilicity of this monomolecular film did not change at all even after being left at room temperature for one week.
［発明の効果］
以−Ｆ説明したように本発明の方法によって’ｒ％られ
る単分子膜は親水性基をその表面に有しているので、親
水性基の反応性あるい１は親水性そのものこ、＼
を利用して種々の応用が期待される。[Effects of the Invention] As explained below, the monomolecular film prepared by the method of the present invention has hydrophilic groups on its surface. As such, various applications are expected using \.
−１５−拝゛・-15- Dear
Claims (1)
水素基を示す） で示される１種または２種以上の有機化合物の一方の親
水性基を疎水性保護基に変換して後、一般式： Ｘ′−Ｒ′ （式中、Ｘ′は親水性基、Ｒ′は炭素原子数が８以上の
炭化水素基を示す） で示される１種または２種以上の有機化合物とともにラ
ングミュア−ブロジエツト法を用いて同時に親水性基板
上に配向制御して吸着させる事を特徴とする単分子膜の
製造方法。(1) One of one or more organic compounds represented by the general formula: X-R-X (wherein, X is a hydrophilic group and R is a hydrocarbon group having 8 or more carbon atoms) After converting the hydrophilic group into a hydrophobic protecting group, the general formula: A method for producing a monomolecular film, which comprises simultaneously adsorbing one or more organic compounds shown on a hydrophilic substrate using the Langmuir-Blodget method while controlling orientation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61108847A JPS62266169A (en) | 1986-05-12 | 1986-05-12 | Preparation of monomolecular film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61108847A JPS62266169A (en) | 1986-05-12 | 1986-05-12 | Preparation of monomolecular film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62266169A true JPS62266169A (en) | 1987-11-18 |
Family
ID=14495092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61108847A Pending JPS62266169A (en) | 1986-05-12 | 1986-05-12 | Preparation of monomolecular film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62266169A (en) |
-
1986
- 1986-05-12 JP JP61108847A patent/JPS62266169A/en active Pending
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