JPS6113863B2 - - Google Patents
Info
- Publication number
- JPS6113863B2 JPS6113863B2 JP51119822A JP11982276A JPS6113863B2 JP S6113863 B2 JPS6113863 B2 JP S6113863B2 JP 51119822 A JP51119822 A JP 51119822A JP 11982276 A JP11982276 A JP 11982276A JP S6113863 B2 JPS6113863 B2 JP S6113863B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- formula
- divalent alkylene
- amphoteric surfactant
- 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.)
- Expired
Links
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000002947 alkylene group Chemical group 0.000 claims description 20
- 239000002280 amphoteric surfactant Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims description 6
- 229960000380 propiolactone Drugs 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- -1 hydrocarbon carboxylic acid Chemical class 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000002596 lactones Chemical class 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 11
- 238000005187 foaming Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005956 quaternization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/38—Dispersants; Agents facilitating spreading
- G03C1/385—Dispersants; Agents facilitating spreading containing fluorine
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、フルオロアルキル基含有両性界面活
性剤及びその製法に関し、更に詳しく言えば、フ
ルオロアルキル基含有の新規化合物からなる両性
界面活性剤及びその製法に関するものである。
従来、界面活性剤としてはアニオン系、カチオ
ン系、ノニオン系など種々のものが知られてお
り、パーフルオロアルキル基の如きフルオロアル
キル基を有するフツ素化界面活性剤も知られてい
る。フツ素化界面活性剤は、特異な界面活性能を
示すので、揮発性液体の蒸発抑制剤(消火剤)、
写真ゼラチン層のレベリング剤、塗料添加剤、そ
の他の各種用途に好適である。又、アニオン系フ
ツ素化界面活性剤は、フツ素樹脂製造時の乳化剤
としても広く使用されている。而して、両性界面
活性剤は、一般にPH変化の影響を受けにくい、
塩類の影響を受けにくいなどの特徴を有するもの
であるが、従来フツ素化両性界面活性剤の好適な
ものは提案されていない。
本発明者は、前記の観点からフツ素化両性界面
活性剤について種々の研究、検討を重ねた結果、
次のような知見を得るに至つた。即ち、本出願人
が別に特許出願中の方法に従つて得られるフルオ
ロアルキルカルボン酸誘導体を、モノクロル酢
酸、β−プロピオラクトン、アクリル酸などの2
倍モル以上との反応により、カルボキシル化と四
級化を同時に生起せしめると、特定の構造を持つ
ベタイン型両性界面活性剤となる新規化合物が製
造され得ることが見出された。例えば、次の化学
式によつて示される反応、
によつて得られる化合物は、両性界面活性剤とし
ての一般的特徴と共に低濃度でも表面張力を下げ
る効果が大きい、起泡性が大きく安定な泡を形成
可能であるなどの優れた界面活性効果を示すもの
である。
かくして、本発明は、前記知見に基いて完成さ
れたものであり、一般式
The present invention relates to an amphoteric surfactant containing a fluoroalkyl group and a method for producing the same, and more specifically, to an amphoteric surfactant comprising a new compound containing a fluoroalkyl group and a method for producing the same. Conventionally, various surfactants such as anionic, cationic, and nonionic surfactants have been known, and fluorinated surfactants having a fluoroalkyl group such as a perfluoroalkyl group are also known. Fluorinated surfactants exhibit unique surfactant properties, so they can be used as evaporation inhibitors (extinguishing agents) for volatile liquids,
Suitable for use as a leveling agent for photographic gelatin layers, paint additive, and other various uses. Furthermore, anionic fluorinated surfactants are also widely used as emulsifiers in the production of fluororesins. Therefore, amphoteric surfactants are generally less affected by pH changes.
Although it has characteristics such as not being easily affected by salts, no suitable fluorinated amphoteric surfactant has been proposed so far. As a result of various studies and studies on fluorinated amphoteric surfactants from the above-mentioned viewpoint, the present inventor has found that:
We came to the following findings. That is, a fluoroalkylcarboxylic acid derivative obtained according to a method for which the present applicant has separately applied for a patent is combined with two fluoroalkylcarboxylic acid derivatives such as monochloroacetic acid, β-propiolactone, and acrylic acid.
It has been found that by reacting with twice the molar amount or more to simultaneously cause carboxylation and quaternization, a new compound that becomes a betaine type amphoteric surfactant with a specific structure can be produced. For example, the reaction represented by the following chemical formula, The compound obtained by this method has the general characteristics of an amphoteric surfactant, as well as excellent surfactant effects such as being highly effective in lowering surface tension even at low concentrations, and being able to form stable foam with high foaming properties. It shows. Thus, the present invention has been completed based on the above findings, and the general formula
【式】
(但し、式中のRfは炭素数4〜18個のポリフルオ
ロアルキル基、Rは水素原子又は低級アルキル
基、Qは炭素数2〜6個の二価のアルキレン基、
Aは炭素数2〜3個の二価のアルキレン基、Bは
炭素数1〜3個の二価のアルキレン基、B′は炭素
数1〜3個の二価のアルキレン基、Mは水素原
子、NH4、又はアルカリ金属を夫々示す)で表わ
される化合物からなる新規なフルオロアルキル基
含有両性界面活性剤を提供するものである。
本発明の新規化合物において、第一に炭素数4
〜18個のポリフルオロアルキル基(Rf基)を有
することが重要である。通常Rf基は、パーフル
オロアルキル基であることが望ましく、炭素数は
6〜12個であることが望ましい。勿論、Rf基は
直鎖状でも分岐状でも良く、部分的に水素原子や
塩素原子などを含むポリフルオロアルキル基でも
良い。かゝるポリフルオロアルキル基特にパーフ
ルオロアルキル基によりフツ素化界面活性剤とし
ての諸特性が発揮され得る。第二に、−A−OH
基の存在が重要であり、かゝる水酸基によつて多
価の塩類との相溶性や良好な起泡力の如き特性が
発揮され得る。Aは炭素数2〜3個の二価のアル
キレン基であり、直鎖状でも分岐状でも良い。通
常は、人手の容易性などからAが−CH2CH2−な
るアルキレン基である実施態様が望ましい。第三
に陽イオン性の窒素原子に陰イオン性の−B′−
COO基が結合していることが重要であり、
かゝる態様によつて両性界面活性剤としての諸特
性が発揮され得る。又、陽イオン性の窒素原子に
は−B−COOM基が結合しており、前記−A−
OH基及び−B′−COO基との共存により、本発
明における両性界面活性剤としての優れた性能、
例えばカルシウムイオンなどの多価カチオンの許
容濃度が高い、有機溶剤の蒸発を抑制する効果が
大きいなどが有利に発揮され得るものである。B
及びB′は、炭素数1〜3個の二価のアルキレン基
であり、直鎖状でも分岐状でも良いが、通常は炭
素数1〜2個の直鎖状アルキレン基、即ち−CH2
−又は−CH2CH2−が好適な実施態様である。
又、BとB′は異なつたアルキレン基でも良いが、
通常は製造上の利点などからBとB′とが同じ場合
が望ましい。
而して、本発明の新規化合物において、Qは炭
素数2〜6個、好ましくは2〜4個の二価のアル
キレン基であり、分岐状又は直鎖状が採用され得
る。通常はQとして炭素数2〜4個の直鎖状のア
ルキレン基が好ましい実施態様であり、特に−
CH2CH2CH2−が選定される。又、Rは水素原子
又は炭素数1〜3個の低級アルキル基が望まし
く、特に水素原子が選定される。Mは水素原子、
NH4、又はアルカリ金属から選択され、通常はM
が水素原子である実施態様が特に好適な結果を与
え得る。尚、アルカリ金属としては、ナトリウ
ム、カリウム、リチウム、ルビジウムなどが例示
され、好ましくはナトリウム、カリウムである。
本発明の新規両性界面活性剤化合物は、種々の
合成法により製造され得るが、通常は、一般式
[Formula] (In the formula, Rf is a polyfluoroalkyl group having 4 to 18 carbon atoms, R is a hydrogen atom or a lower alkyl group, Q is a divalent alkylene group having 2 to 6 carbon atoms,
A is a divalent alkylene group having 2 to 3 carbon atoms, B is a divalent alkylene group having 1 to 3 carbon atoms, B' is a divalent alkylene group having 1 to 3 carbon atoms, and M is a hydrogen atom. , NH 4 , or an alkali metal, respectively). In the novel compound of the present invention, firstly, the number of carbon atoms is 4.
It is important to have ~18 polyfluoroalkyl groups (Rf groups). Generally, the Rf group is preferably a perfluoroalkyl group, and preferably has 6 to 12 carbon atoms. Of course, the Rf group may be linear or branched, and may also be a polyfluoroalkyl group partially containing hydrogen atoms, chlorine atoms, etc. Such polyfluoroalkyl groups, particularly perfluoroalkyl groups, can exhibit various properties as a fluorinated surfactant. Second, -A-OH
The presence of hydroxyl groups is important, and properties such as compatibility with polyvalent salts and good foaming power can be exhibited by such hydroxyl groups. A is a divalent alkylene group having 2 to 3 carbon atoms, and may be linear or branched. Normally, an embodiment in which A is an alkylene group of -CH 2 CH 2 - is desirable from the viewpoint of ease of handling. Thirdly, the anionic −B′− is attached to the cationic nitrogen atom.
It is important that the COO group is bonded,
By such embodiments, various properties as an amphoteric surfactant can be exhibited. In addition, -B-COOM group is bonded to the cationic nitrogen atom, and the -A-
Excellent performance as an amphoteric surfactant in the present invention due to coexistence with OH group and -B'-COO group,
For example, the permissible concentration of polyvalent cations such as calcium ions is high, the effect of suppressing evaporation of organic solvents is large, etc., which can be advantageously exhibited. B
and B' are divalent alkylene groups having 1 to 3 carbon atoms, which may be linear or branched, but are usually linear alkylene groups having 1 to 2 carbon atoms, i.e. -CH 2
- or -CH2CH2- is a preferred embodiment.
Also, B and B' may be different alkylene groups, but
Normally, it is desirable for B and B' to be the same from the viewpoint of manufacturing advantages. In the novel compound of the present invention, Q is a divalent alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and may be branched or linear. Generally, a preferred embodiment of Q is a linear alkylene group having 2 to 4 carbon atoms, especially -
CH 2 CH 2 CH 2 − is selected. Further, R is preferably a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms, and a hydrogen atom is particularly selected. M is a hydrogen atom,
selected from NH 4 or alkali metals, usually M
An embodiment in which is a hydrogen atom may give particularly favorable results. Note that examples of the alkali metal include sodium, potassium, lithium, and rubidium, with sodium and potassium being preferred. Although the novel amphoteric surfactant compounds of the present invention can be produced by various synthetic methods, they usually have the general formula
【式】で表わされる化合物
を、モノクロル酢酸、β−プロピオラクトン、ア
クリル酸の如きカルボキシル化剤の2倍モル以上
を用いて処理し、カルボキシル化と四級化を同時
に行なうことによつて容易に合成可能である。例
えば、次の具体的反応例などによつて合成され得
る。即ち、
などである。尚、一般式
It is easy to carry out carboxylation and quaternization simultaneously by treating the compound represented by the formula with at least twice the molar amount of a carboxylating agent such as monochloroacetic acid, β-propiolactone, or acrylic acid. can be synthesized into For example, it can be synthesized by the following specific reaction example. That is, etc. Furthermore, the general formula
【式】なる化合物は、本出願
人が別に特許出願中の方法、即ちポリフルオロア
ルキルカルボン酸類とエタノールアミン類との反
応などにより容易に入手され得る。例えば、次の
化学反応式で示される方法によつて合成され得
る。
RfCOOC3H7+NH2(CH2)3NHCH2CH2OH
→RfCONH(CH2)3NHCH2CH2OH+C3H7OH
RfCOCl+NH2(CH2)3NHCH2CH2OH+
NaOH
→RfCONH(CH2)3NHCH2CH2OH+NaCl
而して、(1)〜(3)の合成法においては、反応をジ
オキサン、テトラヒドロフラン、クロロホルム、
酢酸エチルなどの不活性溶媒中で実施するのが望
ましく、また(1)又は(3)の方法などでは、イソプロ
ピルアルコールなどの低級アルコール溶媒も使用
され得る。前記(1)と(3)の方法では、反応温度50〜
100℃、好ましくは70〜90℃で20〜30時間程度を
要するが、(2)の方法では反応温度0〜70℃、好ま
しくは20〜40℃で3〜6時間程度で実施できる。
かゝる方法によれば、目的化合物の収率をほゞ
100%にすることが可能である。又、カルボキシ
ル化剤は、The compound represented by the formula can be easily obtained by a method for which a patent application has been separately filed by the applicant, ie, reaction of polyfluoroalkylcarboxylic acids with ethanolamines. For example, it can be synthesized by the method shown by the following chemical reaction formula. RfCOOC 3 H 7 +NH 2 (CH 2 ) 3 NHCH 2 CH 2 OH →RfCONH (CH 2 ) 3 NHCH 2 CH 2 OH+C 3 H 7 OH RfCOCl+NH 2 (CH 2 ) 3 NHCH 2 CH 2 OH+
NaOH →RfCONH(CH 2 ) 3 NHCH 2 CH 2 OH+NaCl Therefore, in the synthesis methods (1) to (3), the reaction is carried out using dioxane, tetrahydrofuran, chloroform,
It is preferable to carry out the reaction in an inert solvent such as ethyl acetate, and lower alcohol solvents such as isopropyl alcohol may also be used in methods (1) or (3). In the methods (1) and (3) above, the reaction temperature is 50~
It takes about 20 to 30 hours at 100°C, preferably 70 to 90°C, but method (2) can be carried out at a reaction temperature of 0 to 70°C, preferably 20 to 40°C, for about 3 to 6 hours.
According to such a method, the yield of the target compound can be approximately reduced.
It is possible to make it 100%. In addition, the carboxylating agent is
【式】の1モル当
り2モル以上を使用するのが望ましいが、1〜2
モル程度の使用量でも目的物の収率は低下するが
採用可能である。カルボキシル化剤の使用量が少
ない場合には、四級化の生起割合が減少し、一般
式It is preferable to use 2 mol or more per 1 mol of [Formula], but 1 to 2
Even if the amount used is on the order of molar, the yield of the target product will decrease, but it can be used. If the amount of carboxylating agent used is small, the rate of quaternization will decrease and the general formula
【式】で表わされる化合物が
副生する。尚、かゝる副生物
A compound represented by the formula is produced as a by-product. Furthermore, such by-products
【式】も両性界面活性剤として
有用である。本発明のベタイン型の目的化合物を
有利に得るためには、[Formula] is also useful as an amphoteric surfactant. In order to advantageously obtain the betaine type target compound of the present invention,
【式】
の1モルに対して、カルボキシル化剤を1.5モル
以上、好ましくは2モル以上の割合で使用するの
が適当である。
本発明において、カルボキシル化剤としては、
It is appropriate to use the carboxylating agent in a proportion of 1.5 mol or more, preferably 2 mol or more, per 1 mol of the formula. In the present invention, the carboxylating agent includes:
【式】の活性水素原子(−
QNH−の水素原子)を−B−COOMに置き換
え、更に−B′−COO基を導入し得るものであ
れば、特に限定されることなく、種々例示可能で
ある。好適なカルボキシル化剤としては、第一に
X−R1−COOM(但し、R1はB又はB′に同じで
あり、Xは塩素原子又は臭素原子)なるハロゲン
置換炭化水素カルボン酸類であり、例えばモノク
ロル酢酸、β−クロルプロピオン酸などがあげら
れる。第二にVarious examples are possible without particular limitation as long as the active hydrogen atom (the hydrogen atom of -QNH-) in [Formula] can be replaced with -B-COOM and a -B'-COO group can be further introduced. be. Suitable carboxylating agents include, firstly, halogen-substituted hydrocarbon carboxylic acids such as X-R 1 -COOM (where R 1 is the same as B or B' and X is a chlorine atom or a bromine atom); Examples include monochloroacetic acid and β-chloropropionic acid. Secondly
【式】(但し、R2はB又は
B′に同じ)なるラクトン類であり、例えばβ−プ
ロピオラクトンがあげられる。第三に、R3−
COOM(但し、R3は炭素−炭素二重結合を有す
るアルケニル基であり、R3はB又はB′と同様の
炭素数を有する)なる不飽和炭化水素カルボン酸
類であり、例えばアクリル酸、ビニル酢酸、メタ
クリル酸などがあげられる。本発明においては、
モノクロル酢酸、β−プロピオラクトン、アクリ
ル酸などが、カルボキシル化剤として特に好まし
く採用され得るものである。
通常は、カルボキシル化剤として、−B−
COOMが−B−COOH(即ち、Mが水素原子)
となるものを採用し、一般式[Formula] (wherein R 2 is the same as B or B'), such as β-propiolactone. Third, R 3 −
COOM (where R 3 is an alkenyl group having a carbon-carbon double bond, and R 3 has the same number of carbon atoms as B or B') is an unsaturated hydrocarbon carboxylic acid such as acrylic acid, vinyl Examples include acetic acid and methacrylic acid. In the present invention,
Monochloroacetic acid, β-propiolactone, acrylic acid, and the like can be particularly preferably employed as the carboxylating agent. Usually, -B-
COOM is -B-COOH (i.e. M is a hydrogen atom)
By adopting the general formula
【式】なる化合物を得る
が、必要に応じて生成物をアンモニア、カ性アル
カリなどにより中和処理することにより、−B−
COOHを−B−COONH4や−B−COOMe(但
し、Meはナトリウム、カリウムなど)に変える
こともできる。
かくして得られるベタイン型化合物は、前記の
通り、一般式[Formula] is obtained, but if necessary, by neutralizing the product with ammonia, caustic alkali, etc., -B-
COOH can also be changed to -B-COONH 4 or -B-COOMe (where Me is sodium, potassium, etc.). The betaine type compound thus obtained has the general formula:
【式】
で表わされるが、典型的な具体例として次の如き
ものをあげることができる。
即ち、
などが例示され得る。かゝるベタイン型構造は、
赤外吸収スペクトル、元素分析、等電点の測定の
如き手段で確認されている。
本発明の新規両性界面活性剤は、後述の実施例
にも示されるように、種々の優れた特性を有して
いる。即ち、両性タイプ及びフツ素化タイプとし
ての一般的特性、例えば耐硬水性、耐PH変化な
どに加えて、次の表面張力を低下する力が大き
い。また、臨界ミセル濃度が小さいので、前記の
如き効果は低濃度でも発揮される。更に、起泡性
が大きく且つ安定な泡を形成可能である。
従つて、発発明の両性界面活性剤は、前記特性
を利用した各種用途に広範囲に採用され得る。例
えば、ガソリン等の可燃性液体の消火剤、ワツク
ス類のレベリング剤、写真乳剤の湿潤剤、繊維加
工時の湿潤剤などとして優れた効果を発揮する。
次に、本発明の実施例について更に具体的に説
明するが、かゝる説明によつて本発明が何ら限定
されないことは勿論である。尚、以下の実施例に
おいて、表面張力及び起泡性の測定は、次のよう
に実施した。即ち、表面張力は所定の濃度に希釈
した界面活性剤水溶液を25℃に保ち、Wilhelmy
の吊板法を用いて測定した。また起泡性は同じく
25℃で0.1%水溶液を用いてRose&Milesの方法
で測定した。
実施例 1
撹拌機、還流冷却器および温度計を装着した
200mlのフラスコに、
C8F17CONH(CH2)3NHC2H4OH 50g、
ClCH2COOH 20g,NaOH8.5g、及びイソプロ
パノール(溶媒)50gを仕込み、激しく撹拌しな
がら70℃、20時間反応せしめた。その結果、[Formula] The following are typical examples. That is, For example, Such a betaine-type structure is
This has been confirmed by means such as infrared absorption spectroscopy, elemental analysis, and isoelectric point measurements. The novel amphoteric surfactant of the present invention has various excellent properties, as shown in the Examples below. That is, in addition to the general properties of the amphoteric type and fluorinated type, such as hard water resistance and pH change resistance, it also has a large ability to lower surface tension. Furthermore, since the critical micelle concentration is small, the above-mentioned effects can be exhibited even at low concentrations. Furthermore, it is possible to form highly foamable and stable foam. Therefore, the amphoteric surfactant of the invention can be widely employed in various applications utilizing the above characteristics. For example, it exhibits excellent effects as a fire extinguisher for flammable liquids such as gasoline, a leveling agent for waxes, a wetting agent for photographic emulsions, and a wetting agent during textile processing. Next, embodiments of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations. In addition, in the following examples, surface tension and foaming properties were measured as follows. In other words, the surface tension is determined by keeping an aqueous surfactant solution diluted to a predetermined concentration at 25°C and using Wilhelmy
Measured using the hanging plate method. The foaming properties are also the same.
It was measured by the method of Rose & Miles using a 0.1% aqueous solution at 25°C. Example 1 Equipped with stirrer, reflux condenser and thermometer
In a 200ml flask, add 50g of C 8 F 17 CONH (CH 2 ) 3 NHC 2 H 4 OH,
20 g of ClCH 2 COOH, 8.5 g of NaOH, and 50 g of isopropanol (solvent) were charged, and the mixture was reacted at 70° C. for 20 hours with vigorous stirring. the result,
【式】50gが得
られた。原料C8F17CONH(CH2)3NHC2H4OHに
対する収率は98%である。この生成物の赤外吸収
スペクトルは1580cm-1に−COOによる吸収
を、3400cm-1に−COOHによる吸収を示してい
る。また、元素分析の結果は、C31.9%,H2.3
%,H4.0%,F46.8%であり、[Formula] 50g was obtained. The yield based on the raw material C8F17CONH ( CH2 ) 3NHC2H4OH is 98 %. The infrared absorption spectrum of this product shows an absorption due to -COO at 1580 cm -1 and an absorption due to -COOH at 3400 cm -1 . In addition, the results of elemental analysis are C31.9%, H2.3
%, H4.0%, F46.8%,
【式】の計算
値、C31.76%,H2.50%,N4.12%,F47.5%、と
良く一致しており、上記構造の化合物であること
が確認された。
この生成物について、起泡性及び水の表面張力
低下能を測定した結果を下記第1表に示す。
実施例 2
実施例1と同様の反応器に、
C8F17CONH(CH2)3NHC2H4OH 50g、β−プロ
ピオラクトン13.5g、及びジオキサン(溶媒)50
gを仕込み、40℃で5時間反応せしめたところ、
が収率99%で得られた。得られる生成物について
の起泡性及び表面張力低下能を下記第1表に示
す。
実施例 3
実施例1と同様の反応器に、
C8F17CONHCH2CH2NHC2OH 50g、アクリル酸
16g、及びテトラヒドロフラン(溶媒)50gを仕
込み、75℃で30時間反応せしめたところ、This was in good agreement with the calculated values of [Formula]: C31.76%, H2.50%, N4.12%, F47.5%, and it was confirmed that the compound had the above structure. The foaming properties and ability to lower the surface tension of water for this product were measured and the results are shown in Table 1 below. Example 2 In a reactor similar to Example 1, 50 g of C8F17CONH ( CH2 ) 3NHC2H4OH , 13.5 g of β-propiolactone, and 50 g of dioxane (solvent) were added.
When the mixture was charged and reacted at 40°C for 5 hours, was obtained with a yield of 99%. The foaming properties and surface tension lowering abilities of the resulting products are shown in Table 1 below. Example 3 In a reactor similar to Example 1, 50 g of C 8 F 17 CONHCH 2 CH 2 NHC 2 OH and acrylic acid were added.
When 16 g and 50 g of tetrahydrofuran (solvent) were charged and reacted at 75°C for 30 hours,
【式】が収率
97%で得られた。生成物についての起泡性及び表
面張力低下能を下記第1表に示す。
比較例 1[Formula] was obtained in a yield of 97%. The foaming properties and surface tension lowering abilities of the products are shown in Table 1 below. Comparative example 1
【式】について、起
泡性及び水の表面張力低下能を測定した結果を、
下記第1表に示す。Regarding [Formula], the results of measuring the foaming property and surface tension lowering ability of water are as follows:
It is shown in Table 1 below.
【表】
実施例4〜6および比較例2
実施例2の方法に準じて構造の異なるベタイン
化合物を合成した。合成した化合物の構造とそれ
らの水溶液の表面張力、起泡性を第2表に示す。[Table] Examples 4 to 6 and Comparative Example 2 Betaine compounds with different structures were synthesized according to the method of Example 2. Table 2 shows the structures of the synthesized compounds and the surface tension and foaming properties of their aqueous solutions.
Claims (1)
キル基、Rは水素原子又は低級アルキル基、Qは
炭素数2〜6個の二価のアルキレン基、Aは炭素
数2〜3個の二価のアルキレン基、Bは炭素数1
〜3個の二価のアルキレン基、B′は炭素数1〜3
個の二価のアルキレン基、Mは水素原子、NH4、
又はアルカリ金属を夫々示す)で表わされる化合
物からなるフルオロアルキル基含有両性界面活性
剤。 2 Rfが炭素数4〜18個のパーフルオロアルキ
ル基である特許請求の範囲第1項記載のフルオロ
アルキル基含有両性界面活性剤。 3 Aが−CH2CH2−である特許請求の範囲第1
項又は第2項記載のフルオロアルキル基含有両性
界面活性剤。 4 −B−COOMが−(CH2)nCOOH基(但
し、nは1〜2の整数を示す)である特許請求の
範囲第1項、第2項、又は第3項記載のフルオロ
アルキル基含有両性界面活性剤。 5 【式】が【式】(但 し、mは1〜2の整数を示す)である特許請求の
範囲第1項、第2項、第3項、又は第4項記載の
フルオロアルキル基含有両性界面活性剤。 6 −B−COOMが−(CH2)nCOONH4基(但
し、nは1〜2の整数を示す)である特許請求の
範囲第1項、第2項、第3項、又は第5項記載の
フルオロアルキル基含有両性界面活性剤。 7 −B−COOMが−(CH2)nCOOMe基(但
し、nは1〜2の整数、Meはナトリウム又はカ
リウムを夫々示す)である特許請求の範囲第1
項、第2項、第3項、又は第5項記載のフルオロ
アルキル基含有両性界面活性剤。 8 (但し、lは2〜4の整数を示す)である特許請
求の範囲第1項、第2項、第3項、第4項、第5
項、第6項、又は第7項記載のフルオロアルキル
基含有両性界面活性剤。 9 一般式【式】(但し、式 中Rfは炭素数4〜18個のポリフルオロアルキル
基、Rは水素原子又は低級アルキル基、Qは炭素
数2〜6個の二価のアルキレン基、Aは炭素数2
〜3個の二価のアルキレン基を夫々示す)で表わ
される化合物をカルボキシル化剤の1.5倍モル以
上で処理して、一般式 【式】(但し、式中の Rf,R,Q,Aは前記に同じであり、Bは炭素
数1〜3個の二価のアルキレン基、B′は炭素数1
〜3個の二価のアルキレン基、Mは水素原子、
NH4、又はアルカリ金属を夫々示す)で表わされ
る化合物からなるフルオロアルキル基含有両性界
面活性剤の製法。 10 カルボキシル化剤による処理の後に、中和
処理を実施する特許請求の範囲第9項記載の製
法。 11 カルボキシル化剤の使用量を
【式】 の1モルに対して2モル以上とする特許請求の範
囲第9項又は第10項記載の製法。 12 カルボキシル化剤として一般式X−R1−
COOM(但し、R1は前記B又はB′に同じであ
り、Xは塩素原子又は臭素原子であり、Mは前記
に同じである)で表わされるハロゲン置換炭化水
素カルボン酸類を使用する特許請求の範囲第9
項、第10項、又は第11項記載の製法。 13 カルボキシル化剤としてモノクロル酢酸を
使用する特許請求の範囲第12項記載の製法。 14 反応処理温度50〜100℃で実施する特許請
求の範囲第13項記載の製法。 15 カルボキシル化剤として一般式
【式】 (但し、R2は前記B又はB′と同じである)で表わ
されるラクトン類を使用する特許請求の範囲第9
項、第10項、又は第11項記載の製法。 16 カルボキシル化剤としてβ−プロピオラク
トンを使用する特許請求の範囲第15項記載の製
法。 17 反応処理温度0〜70℃で実施する特許請求
の範囲第16項記載の製法。 18 カルボキシル化剤として一般式R3−
COOM(但し、R3は炭素−炭素二重結合を有す
るアルケニル基であり、R3は前記B又はB′と同
様の炭素数を有する)で表わされる不飽和炭化水
素カルボン酸類を使用する特許請求の範囲第9
項、第10項、又は第11項記載の製法。 19 カルボキシル化剤としてアクリル酸を使用
する特許請求の範囲第18項記載の製法。 20 反応処理温度50〜100℃で実施する特許請
求の範囲第19項記載の製法。[Claims] 1 General formula [Formula] (wherein, Rf is a polyfluoroalkyl group having 4 to 18 carbon atoms, R is a hydrogen atom or a lower alkyl group, and Q is a polyfluoroalkyl group having 2 to 6 carbon atoms. Divalent alkylene group, A is a divalent alkylene group with 2 to 3 carbon atoms, B is 1 carbon number
~3 divalent alkylene groups, B' has 1 to 3 carbon atoms
divalent alkylene groups, M is a hydrogen atom, NH 4 ,
or an alkali metal, respectively). 2. The fluoroalkyl group-containing amphoteric surfactant according to claim 1, wherein Rf is a perfluoroalkyl group having 4 to 18 carbon atoms. 3. Claim 1 in which A is -CH 2 CH 2 -
The fluoroalkyl group-containing amphoteric surfactant according to item 1 or 2. 4 -B-COOM is a -( CH2 )nCOOH group (wherein n represents an integer of 1 to 2), the fluoroalkyl group-containing compound according to claim 1, 2, or 3. Amphoteric surfactant. 5. The fluoroalkyl group-containing amphoteric compound according to claim 1, 2, 3, or 4, wherein [Formula] is [Formula] (where m represents an integer of 1 to 2) surfactant. Claim 1, 2, 3, or 5, wherein 6-B-COOM is a -( CH2 ) nCOONH4 group (where n is an integer of 1 to 2) fluoroalkyl group-containing amphoteric surfactant. 7 -B-COOM is a -( CH2 )nCOOMe group (wherein n is an integer of 1 to 2, and Me represents sodium or potassium, respectively) Claim 1
The fluoroalkyl group-containing amphoteric surfactant according to item 1, 2, 3, or 5. 8 (However, l represents an integer of 2 to 4.) Claims 1, 2, 3, 4, and 5
The fluoroalkyl group-containing amphoteric surfactant according to item 1, 6, or 7. 9 General formula [formula] (wherein Rf is a polyfluoroalkyl group having 4 to 18 carbon atoms, R is a hydrogen atom or a lower alkyl group, Q is a divalent alkylene group having 2 to 6 carbon atoms, A has 2 carbons
~3 divalent alkylene groups respectively) is treated with 1.5 times the mole or more of the carboxylating agent, and the compound represented by the general formula [formula] (wherein Rf, R, Q, and A are Same as above, B is a divalent alkylene group having 1 to 3 carbon atoms, and B' is a divalent alkylene group having 1 to 3 carbon atoms.
~3 divalent alkylene groups, M is a hydrogen atom,
A method for producing a fluoroalkyl group-containing amphoteric surfactant comprising a compound represented by NH 4 or an alkali metal, respectively. 10. The production method according to claim 9, wherein a neutralization treatment is performed after the treatment with the carboxylating agent. 11. The production method according to claim 9 or 10, wherein the amount of the carboxylating agent used is 2 mol or more per 1 mol of [Formula]. 12 General formula X-R 1 − as a carboxylating agent
A patent claim using a halogen-substituted hydrocarbon carboxylic acid represented by COOM (wherein R 1 is the same as B or B' above, X is a chlorine atom or bromine atom, and M is the same as above) Range 9th
10, or 11. 13. The production method according to claim 12, wherein monochloroacetic acid is used as the carboxylating agent. 14. The manufacturing method according to claim 13, which is carried out at a reaction treatment temperature of 50 to 100°C. 15 Claim 9 in which a lactone represented by the general formula [Formula] (wherein R 2 is the same as B or B') is used as a carboxylating agent.
10, or 11. 16. The production method according to claim 15, wherein β-propiolactone is used as the carboxylating agent. 17. The manufacturing method according to claim 16, which is carried out at a reaction treatment temperature of 0 to 70°C. 18 General formula R 3 − as a carboxylating agent
A patent claim using an unsaturated hydrocarbon carboxylic acid represented by COOM (wherein R 3 is an alkenyl group having a carbon-carbon double bond, and R 3 has the same number of carbon atoms as B or B') Range 9th
10, or 11. 19. The manufacturing method according to claim 18, wherein acrylic acid is used as the carboxylating agent. 20. The manufacturing method according to claim 19, which is carried out at a reaction treatment temperature of 50 to 100°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11982276A JPS5345683A (en) | 1976-10-07 | 1976-10-07 | Fluoroalkyl-containing amphoteric surfactant and preparation thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11982276A JPS5345683A (en) | 1976-10-07 | 1976-10-07 | Fluoroalkyl-containing amphoteric surfactant and preparation thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5345683A JPS5345683A (en) | 1978-04-24 |
JPS6113863B2 true JPS6113863B2 (en) | 1986-04-16 |
Family
ID=14771095
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11982276A Granted JPS5345683A (en) | 1976-10-07 | 1976-10-07 | Fluoroalkyl-containing amphoteric surfactant and preparation thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5345683A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63125871U (en) * | 1987-02-10 | 1988-08-17 | ||
JPS63138576U (en) * | 1987-03-03 | 1988-09-12 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4917705A (en) * | 1972-06-07 | 1974-02-16 | ||
JPS50106506A (en) * | 1973-08-01 | 1975-08-22 | ||
JPS58201752A (en) * | 1982-05-19 | 1983-11-24 | Dainippon Ink & Chem Inc | Fluorine-containing tricarboxylic acid-type amphoteric compound and its preparation |
JPS59191760A (en) * | 1983-04-13 | 1984-10-30 | Hitachi Chem Co Ltd | Film-forming polymer solution |
JP2542844B2 (en) * | 1987-04-08 | 1996-10-09 | コニカ株式会社 | Silver halide photographic light-sensitive material with improved film properties |
JPH0786667B2 (en) * | 1988-04-15 | 1995-09-20 | 富士写真フイルム株式会社 | Silver halide photographic light-sensitive material |
CN113372237B (en) * | 2021-05-06 | 2022-10-04 | 宁波南大光电材料有限公司 | Fluorine-containing surfactant for immersion photoresist and preparation method thereof |
-
1976
- 1976-10-07 JP JP11982276A patent/JPS5345683A/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63125871U (en) * | 1987-02-10 | 1988-08-17 | ||
JPS63138576U (en) * | 1987-03-03 | 1988-09-12 |
Also Published As
Publication number | Publication date |
---|---|
JPS5345683A (en) | 1978-04-24 |
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