JPS6355524B2 - - Google Patents
Info
- Publication number
- JPS6355524B2 JPS6355524B2 JP27845385A JP27845385A JPS6355524B2 JP S6355524 B2 JPS6355524 B2 JP S6355524B2 JP 27845385 A JP27845385 A JP 27845385A JP 27845385 A JP27845385 A JP 27845385A JP S6355524 B2 JPS6355524 B2 JP S6355524B2
- Authority
- JP
- Japan
- Prior art keywords
- quaternary ammonium
- group
- cmc
- salt
- carboxymethyl
- 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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 42
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 42
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 19
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000005359 phenoxyalkyl group Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 18
- -1 CMC quaternary ammonium salts Chemical class 0.000 description 16
- 239000008186 active pharmaceutical agent Substances 0.000 description 11
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 229960003872 benzethonium Drugs 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- SIYLLGKDQZGJHK-UHFFFAOYSA-N dimethyl-(phenylmethyl)-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]ammonium Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 SIYLLGKDQZGJHK-UHFFFAOYSA-N 0.000 description 3
- 229940102728 methylbenzethonium Drugs 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MTCUAOILFDZKCO-UHFFFAOYSA-N Decamethonium Chemical compound C[N+](C)(C)CCCCCCCCCC[N+](C)(C)C MTCUAOILFDZKCO-UHFFFAOYSA-N 0.000 description 2
- VZJFGSRCJCXDSG-UHFFFAOYSA-N Hexamethonium Chemical compound C[N+](C)(C)CCCCCC[N+](C)(C)C VZJFGSRCJCXDSG-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229950000405 decamethonium Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229950002932 hexamethonium Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RZTDURBNLDNTQU-UHFFFAOYSA-N (3,4-dichlorophenyl)methyl-dodecyl-dimethylazanium Chemical class CCCCCCCCCCCC[N+](C)(C)CC1=CC=C(Cl)C(Cl)=C1 RZTDURBNLDNTQU-UHFFFAOYSA-N 0.000 description 1
- SIHFYNZIBKOFFK-UHFFFAOYSA-N 1-tetradecylpyridin-1-ium Chemical class CCCCCCCCCCCCCC[N+]1=CC=CC=C1 SIHFYNZIBKOFFK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000007884 disintegrant Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- DXIVDWCVGRNPIW-UHFFFAOYSA-N dodecyl-hexadecyl-dimethylazanium Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC DXIVDWCVGRNPIW-UHFFFAOYSA-N 0.000 description 1
- YXUPZGKORWTXID-UHFFFAOYSA-N domiphen Chemical compound CCCCCCCCCCCC[N+](C)(C)CCOC1=CC=CC=C1 YXUPZGKORWTXID-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JJPVWQWOOQYHCB-UHFFFAOYSA-N triethyl(phenyl)azanium Chemical compound CC[N+](CC)(CC)C1=CC=CC=C1 JJPVWQWOOQYHCB-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- KMVDECFGXJKYHV-UHFFFAOYSA-L trimethyl-[10-(trimethylazaniumyl)decyl]azanium;dichloride Chemical compound [Cl-].[Cl-].C[N+](C)(C)CCCCCCCCCC[N+](C)(C)C KMVDECFGXJKYHV-UHFFFAOYSA-L 0.000 description 1
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
(イ) 産業上の技術分野
この発明は新規なカルボキシメチルセルロース
の第四アンモニウム塩に関し、詳しくは無水グル
コース単位当りのカルボキシメチル基による置換
度（以下DSと呼称する）が1.5〜3.0のカルボキシ
メチルセルロース（以下CMCと呼称する）の第
四アンモニウム塩及びその製造法に関する。
(ロ) 従来の技術
カルボキシメチルセルロースは、セルロース
に、アルカリの存在下モノクロル酢酸を作用させ
て製造されるセルロースエーテルであり、水溶性
高分子電解質として増粘剤、分散剤、保護コロイ
ド剤、接着剤などとして広く使用されている。
従来のCMCは、DSが0.5〜1.7のものが一般的
であり、特にDSが1.5以下のナトリウム塩が広く
市販されている。また第四アンモニウム塩やカル
シウム塩も一部に市販されており、カルシウム塩
は水に不溶で主として崩壊剤として使用されてい
る。
これまで、CMCの第四アンモニウム塩として
は、ジメチルラウリルセチルアンモニウム塩（西
独特許第1103336号公報）、トリメチルオクタデシ
ルアンモニウム塩（米国特許第2881074号公報）、
ドデシルジメチル（３，４−ジクロロベンジル）
アンモニウム塩（Deut.Apotheker−Ztg.、106
（35）、1206−８（1966）〕、テトラデシルピリジニ
ウム塩及びセチルトリメチルアンモニウム塩
〔Pharm.Ind.、37、(2)、100、（1975）〕などが知
られている。
これらのCMCの第四アンモニウム塩は、CMC
の可溶性高分子物質としての特性を利用するとと
もに、第四アンモニウム基の有する特性を利用す
る用途に用いられるものである。しかしこれらの
CMC第四アンモニウム塩は、CMCのDSがいず
れも1.5未満のものであり、第四アンモニウム基
はCMCのカルボキシメチル基と１：１の分子比
率で反応するものであるから、導入できる第四ア
ンモニウム基はグルコース単位当り1.5分子未満
であり、これ以上の量の第四アンモニウム基の特
性を利用することができない。さらに第四アンモ
ニウム基の分子量が小さいとき（アルキル基が低
級の場合など）は水溶性（有機溶媒には不溶）で
あるが、第四アンモニウム基の分子量が大きくな
ると（アルキル基が高級の場合など）非水溶性で
あり、さらにアルコールやアセトンのような極性
溶媒やトルエンのような非極性溶媒にも充分に溶
解しない。したがつて溶媒溶液として用いる用途
には使用しにくい。
(ハ) 発明が解決しようとする問題点
この発明の目的は上記の状況においてなされた
ものであつて、導入する第四アンモニウム基を増
やすことにより、その特性をより一層利用でき
て、しかも第四アンモニウム基の種類を選択する
ことによつて水や有機溶媒に溶解しうるCMCの
第四アンモニウム塩を得ることにある。
(ニ) 問題点を解決するための手段と作用
この発明は、下記式：
〔式中、Ｒは水素原子又はカルボキシメチル基の
第四アンモニウム塩であり、ｎは10〜1000であ
る。但し無水グルコース単位当りカルボキシメチ
ル基の置換度は1.5〜3.0であり、カルボキシメチ
ル基の第四アンモニウム塩は、副式：
で表わされ、R1〜R4のうち三つがそれぞれC1-30
の直鎖もしくは分枝状の飽和もしくは不飽和の脂
肪族炭化水素基またはアラルキル基であり、一つ
がトリアルキルアンモニウムアルキル基、フエノ
キシアルキル基、モノもしくはジアルキルフエノ
キシアルキレンオキシアルキレン基、またはアリ
ール基である）
で表されるカルボキシメチルセルロースの第四ア
ンモニウム塩を提供するものである。
この発明のCMCの第四アンモニウム塩で上記
副式中の四アンモニウム基：
(a) Industrial technical field The present invention relates to a novel quaternary ammonium salt of carboxymethylcellulose, and more specifically, carboxymethylcellulose (hereinafter referred to as DS) having a degree of substitution by carboxymethyl groups per anhydroglucose unit (hereinafter referred to as DS) of 1.5 to 3.0. The present invention relates to a quaternary ammonium salt of CMC (hereinafter referred to as CMC) and a method for producing the same. (b) Prior art Carboxymethylcellulose is a cellulose ether produced by treating cellulose with monochloroacetic acid in the presence of an alkali, and is used as a water-soluble polymer electrolyte as a thickener, dispersant, protective colloid, and adhesive. It is widely used as such. Conventional CMC generally has a DS of 0.5 to 1.7, and especially sodium salts with a DS of 1.5 or less are widely commercially available. Some quaternary ammonium salts and calcium salts are also commercially available, and calcium salts are insoluble in water and are mainly used as disintegrants. So far, quaternary ammonium salts of CMC include dimethyl laurylcetylammonium salt (West German Patent No. 1103336), trimethyloctadecyl ammonium salt (US Patent No. 2881074),
Dodecyldimethyl (3,4-dichlorobenzyl)
Ammonium salts (Deut.Apotheker−Ztg., 106
(35), 1206-8 (1966)], tetradecylpyridinium salt and cetyltrimethylammonium salt [Pharm.Ind., 37, (2), 100, (1975)], and the like. These quaternary ammonium salts of CMC are
It is used for applications that take advantage of the properties of the quaternary ammonium group as a soluble polymer substance and the properties of the quaternary ammonium group. But these
CMC quaternary ammonium salts are those in which the DS of CMC is less than 1.5, and the quaternary ammonium group reacts with the carboxymethyl group of CMC at a molecular ratio of 1:1, so the quaternary ammonium salt that can be introduced is There are less than 1.5 molecules of groups per glucose unit, and the properties of quaternary ammonium groups cannot be exploited in larger amounts. Furthermore, when the molecular weight of the quaternary ammonium group is small (such as when the alkyl group is lower), it is water-soluble (insoluble in organic solvents); however, when the molecular weight of the quaternary ammonium group becomes large (such as when the alkyl group is higher), ) It is insoluble in water, and it is also poorly soluble in polar solvents such as alcohol and acetone, and non-polar solvents such as toluene. Therefore, it is difficult to use it as a solvent solution. (c) Problems to be solved by the invention The purpose of this invention was achieved in the above-mentioned situation, and by increasing the number of quaternary ammonium groups introduced, the characteristics of quaternary ammonium groups can be further utilized. The objective is to obtain a quaternary ammonium salt of CMC that is soluble in water and organic solvents by selecting the type of ammonium group. (d) Means and effects for solving the problems This invention is based on the following formula: [In the formula, R is a hydrogen atom or a quaternary ammonium salt of a carboxymethyl group, and n is 10 to 1000. However, the degree of substitution of carboxymethyl group per anhydroglucose unit is 1.5 to 3.0, and the quaternary ammonium salt of carboxymethyl group has the sub-formula: Three of R 1 to R 4 are C 1-30, respectively.
a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group or aralkyl group, one of which is a trialkylammonium alkyl group, a phenoxyalkyl group, a mono- or dialkylphenoxyalkyleneoxyalkylene group, or The present invention provides a quaternary ammonium salt of carboxymethyl cellulose represented by: In the quaternary ammonium salt of CMC of this invention, the tetraammonium group in the above subformula:
【式】の分子量の比較的小さいものとし
ては、ヘキサメトニウム、デカメトニウム、フエ
ニルトリメチルアンモニウム、フエニルトリエチ
ルアンモニウムなどが挙げられる。
第四アンモニウム基の分子量が大きなものとし
てはベンゼトニウム、メチルベンゼトニウム、ラ
ウリルフエノキシエチルジメチルアンモニウムな
どが挙げられる。
この発明のCMCの第四アンモニウム塩で第四
アンモニウム基の分子量が大きいものは一般に非
水溶性であるが、第四アンモニウム基によつて
種々の有機溶媒に可溶なものが得られる。たとえ
ばCMCのDS2.4のベンゼトニウムあるいはメチル
ベンゼトニウムはメタノール、エタノール、イソ
プロパノールに可溶である。
一方この発明のCMCの第四アンモニウム塩で
第四アンモニウム基の分子量が比較的小さなもの
は一般に水溶性である。
上記のように、この発明によれば、第四アンモ
ニウム基を選択することによつて、水溶性及び有
機溶媒に可溶性のCMC第四アンモニウム塩が得
られ、CMCの可溶性高分子物質としての特性、
すなわち増粘性、保護コロイド性などを有すると
ともに、第四アンモニウム基の特性、例えば帯電
防止性を利用したプラスチツクの帯電防止剤、毛
髪との親和性を利用した化粧料、殺菌剤などの広
範な用途に用いることができる。しかもCMCの
DS値が従来のものより高いので、結合する第四
アンモニウム基の量が増大する。したがつて従来
のCMC第四アンモニウム塩よりも第四アンモニ
ウム基の特性を強く保有させることができる。
この発明の化合物は無水グルコース単位当りの
カルボキシメチル基による置換度が1.5〜3.0のカ
ルボキシメチルセルロース又はその塩の溶液と、
対応する第四アンモニウム化合物もしくはその溶
液とを混合して反応させ、生成したカルボキシメ
チルセルロース第四アンモニウム塩を分離精製す
ることによつて製造することができる。
上記製造に用いられるDS1.5〜3.0のCMCは、
例えば特開昭58−176202号公報に記載の多段エー
テル化法で得られるものなどを用いることができ
る。
またこのCMCの塩を出発原料として用いる場
合には、ナトリウム塩やカリウム塩のごときアル
カリ金属塩、カルシウム塩が挙げられるがナトリ
ウム塩が好ましいものである。
上記CMCと反応させる出発原料の対応する第
四アンモニウム化合物としては、その陰イオンが
塩素、臭素、弗素の各イオンのようなハロゲンイ
オン、硫酸イオン、硝酸イオン、リン酸イオンな
どの第四アンモニウム化合物である。
上記２つの原料を反応させるには、少なくとも
CMCもしくはその塩を溶液の形態としておいて、
両原料を接触させて反応させればよい。特に
CMCの塩の水溶液に、対応する第四アンモニウ
ム化合物もしくはその水溶液を添加して反応させ
るのが好ましい。
また上記反応は通常室温近傍で行われる。
また第四アンモニウム化合物は、CMC中のカ
ルボキシメチル基と当量あるいは過剰量で用いる
のが好ましいが、当量よりも少ない量で反応させ
ることもできる。
上記のようにして得られた反応混合液から、次
のようにしてCMCの第四アンモニウム塩が得ら
れる。生成したCMCの第四アンモニウム塩が水
溶性の場合には、アルコール、アセトンのような
親水性溶媒を添加して沈殿させ、これら溶媒の含
水液で洗浄して第四アンモニウム化合物及び塩を
除去した後乾燥する。生成したCMC第四アンモ
ニウム塩が非水溶性の場合は生成した沈殿を水で
よく洗浄後乾燥する。次にこの発明を実施例によ
つてこの発明を説明する。
(ホ) 実施例
実施例 １
下記のごときDS、粘度のCMCナトリウム塩の
１％水溶液200ｇに当量の下記各種第４級アンモ
ニウム化合物の水溶液を添加し、攪拌した。生成
した沈殿を別し、充分水洗した後、常温で真空
乾燥して各CMC第４級アンモニウム塩を得た。
(1) 使用したCMCナトリウム塩
DS 2.41
DP 700
１％水溶液粘度 610cps
(2) 使用した第四アンモニウム化合物
表１にCMC第四アンモニウム塩の溶解性を示
す。Examples of compounds having a relatively small molecular weight of the formula include hexamethonium, decamethonium, phenyltrimethylammonium, phenyltriethylammonium, and the like. Examples of those having a large molecular weight of quaternary ammonium groups include benzethonium, methylbenzethonium, and laurylphenoxyethyldimethylammonium. The quaternary ammonium salts of CMC of the present invention having a large molecular weight of the quaternary ammonium group are generally insoluble in water, but those that are soluble in various organic solvents can be obtained due to the quaternary ammonium group. For example, CMC's benzethonium or methylbenzethonium, which has a DS of 2.4, is soluble in methanol, ethanol, and isopropanol. On the other hand, quaternary ammonium salts of CMC of the present invention in which the molecular weight of the quaternary ammonium group is relatively small are generally water-soluble. As described above, according to the present invention, by selecting a quaternary ammonium group, a water-soluble and organic solvent-soluble CMC quaternary ammonium salt can be obtained, and the characteristics of CMC as a soluble polymer substance,
In other words, it has thickening properties, protective colloid properties, etc., and has a wide range of applications such as antistatic agents for plastics that utilize the properties of quaternary ammonium groups, such as antistatic agents for plastics, cosmetics that utilize their affinity with hair, and disinfectants. It can be used for. Moreover, CMC
Since the DS value is higher than conventional ones, the amount of quaternary ammonium groups attached is increased. Therefore, it is possible to retain the characteristics of the quaternary ammonium group more strongly than the conventional CMC quaternary ammonium salt. The compound of this invention comprises a solution of carboxymethylcellulose or a salt thereof having a degree of substitution by carboxymethyl groups per anhydroglucose unit of 1.5 to 3.0;
It can be produced by mixing and reacting a corresponding quaternary ammonium compound or a solution thereof, and separating and purifying the resulting carboxymethylcellulose quaternary ammonium salt. The CMC of DS1.5 to 3.0 used in the above manufacturing is
For example, those obtained by the multistage etherification method described in JP-A-58-176202 can be used. When using the salt of CMC as a starting material, examples include alkali metal salts such as sodium salt and potassium salt, and calcium salts, with sodium salt being preferred. The quaternary ammonium compounds corresponding to the starting materials to be reacted with the above CMC include quaternary ammonium compounds whose anions include halogen ions such as chlorine, bromine, and fluorine ions, sulfate ions, nitrate ions, and phosphate ions. It is. In order to react the above two raw materials, at least
CMC or its salt is in the form of a solution,
Both raw materials may be brought into contact and reacted. especially
It is preferable to add a corresponding quaternary ammonium compound or its aqueous solution to an aqueous solution of a CMC salt and cause the reaction to occur. Further, the above reaction is usually carried out near room temperature. Further, the quaternary ammonium compound is preferably used in an amount equivalent to or in excess of the carboxymethyl group in CMC, but it can also be reacted in an amount less than the equivalent amount. A quaternary ammonium salt of CMC is obtained from the reaction mixture obtained as described above in the following manner. When the generated quaternary ammonium salt of CMC was water-soluble, a hydrophilic solvent such as alcohol or acetone was added to precipitate it, and the quaternary ammonium compound and salt were removed by washing with a water-containing solution of these solvents. Dry afterwards. If the generated CMC quaternary ammonium salt is water-insoluble, the generated precipitate is thoroughly washed with water and then dried. Next, this invention will be explained with reference to Examples. (e) Examples Example 1 To 200 g of a 1% aqueous solution of CMC sodium salt having the following DS and viscosity, an equivalent amount of an aqueous solution of the following various quaternary ammonium compounds was added and stirred. The generated precipitate was separated, thoroughly washed with water, and then vacuum dried at room temperature to obtain each CMC quaternary ammonium salt. (1) CMC sodium salt used DS 2.41 DP 700 1% aqueous solution viscosity 610 cps (2) Quaternary ammonium compound used Table 1 shows the solubility of CMC quaternary ammonium salts.
【表】
× 不溶 △ 部分的に溶解 ○ 溶解
第１図にベンゼトニウムCMCの赤外吸収スペ
クトルを示す。（CMC NaのDS2.41）
主要な吸収帯
1610cm-1 −COO
830cm-1 １，４置換フエニル
700〜770cm-1 モノ置換フエニル
980〜1170cm-1 セルロースのＣ−Ｏ伸縮振動及
びグルコース環
第２図にメチルベンゼトニウムCMCの赤外吸
収スペクトルを示す。（CMC NaのDS2.41）
主要な吸収帯
1610cm-1 −COO
700〜770cm-1 モノ置換フエニル
980〜1170cm-1 セルロースのＣ−Ｏ伸縮振動及
びグルコース環
実施例 ２
下記のDS、粘度のCMCナトリウム塩の１％水
溶液200ｇに当量の下記の第四アンモニウム化合
物を添加し、次いでアセトンを加えて沈殿させた
後、90％アセトン水溶液で洗浄し、常温で真空乾
燥して、各CMC第四アンモニウム塩を得た。得
られた生成物はいずれも水溶性であつたが、エタ
ノールなどの低級アルコールには完溶しなかつ
た。
(1) 使用したCMCナトリウム塩
DS 2.41
DP 700
１％水溶液粘度 610cps
(2) 使用した第四アンモニウム化合物
ヘキサメトニウムクロリド
デカメトニウムクロリド
第３図にヘキサメトニウムCMCの赤外吸収ス
ペクトルを示す（CMC NaのDS2.41）
主要な吸収帯
1610cm-1 −COO
2930cm-1 −CH2−
1000〜1170cm-1 セルロースのＣ−Ｏ伸縮振動及
びグルコース環
第４図にデカメトニウムCMCの赤外吸収スペ
クトルを示す
主要な吸収帯
1600cm-1 −COO
2930cm-1 −CH2−
1000〜1170cm-1 セルロースのＣ−Ｏ伸縮振動及
びグルコース環
(ヘ) 発明の効果
この発明によれば、導入する第四アンモニウム
基を増やすことによつて、その特性をより一層利
用できて、しかも第四アンモニウム基の種類を選
択することによつて水や有機溶媒に溶解しうる
CMC第四アンモニウム塩を得ることができる。[Table] × Insoluble △ Partially dissolved ○ Dissolved Figure 1 shows the infrared absorption spectrum of benzethonium CMC. (DS2.41 of CMC Na) Main absorption band 1610 cm -1 -COO 830 cm -1 1,4-substituted phenyl 700-770 cm -1 Mono-substituted phenyl 980-1170 cm -1 C-O stretching vibration of cellulose and glucose ring 2nd The figure shows the infrared absorption spectrum of methylbenzethonium CMC. (DS2.41 of CMC Na) Main absorption band 1610 cm -1 -COO 700 to 770 cm -1 Monosubstituted phenyl 980 to 1170 cm -1 C-O stretching vibration of cellulose and glucose ring Example 2 DS below, CMC of viscosity Add an equivalent amount of the following quaternary ammonium compound to 200 g of 1% aqueous solution of sodium salt, then add acetone to precipitate, wash with 90% acetone aqueous solution, vacuum dry at room temperature, and prepare each CMC quaternary ammonium compound. Got salt. All of the obtained products were water-soluble, but not completely soluble in lower alcohols such as ethanol. (1) CMC sodium salt used DS 2.41 DP 700 1% aqueous solution viscosity 610 cps (2) Quaternary ammonium compound used Hexamethonium chloride decamethonium chloride Figure 3 shows the infrared absorption spectrum of hexamethonium CMC (DS2.41 of CMC Na) Main absorption band 1610cm -1 -COO 2930cm -1 -CH 2 - 1000~1170cm -1 C-O stretching of cellulose Vibration and glucose ring Figure 4 shows the infrared absorption spectrum of decamethonium CMC . ) Effects of the Invention According to this invention, by increasing the number of quaternary ammonium groups introduced, its characteristics can be further utilized, and by selecting the type of quaternary ammonium groups, it is possible to can be dissolved in
CMC quaternary ammonium salts can be obtained.
第１〜４図はそれぞれこの発明のCMC第四ア
ンモニウム塩の赤外線吸収スペクトル図である。
1 to 4 are infrared absorption spectra of the CMC quaternary ammonium salt of the present invention, respectively.
Claims (1)
第四アンモニウム塩であり、ｎは10〜1000であ
る。但し無水グルコース単位当りカルボキシメチ
ル基の置換度は1.5〜3.0であり、カルボキシメチ
ル基の第四アンモニウム塩は、副式： で表わされ、R1〜R4のうち三つがそれぞれC1-30
の直鎖もしくは分枝状の飽和もしくは不飽和の脂
肪族炭化水素基またはアラルキル基であり、一つ
がトリアルキルアンモニウムアルキル基、フエノ
キシアルキル基、モノもしくはジアルキルフエノ
キシアルキレンオキシアルキレン基、またはアリ
ール基である） で表されるカルボキシメチルセルロースの第四ア
ンモニウム塩。[Claims] 1. The following formula: (In the formula, R is a hydrogen atom or a quaternary ammonium salt of a carboxymethyl group, and n is 10 to 1000. However, the degree of substitution of the carboxymethyl group per anhydroglucose unit is 1.5 to 3.0, and the degree of substitution of the carboxymethyl group is 1.5 to 3.0. Quaternary ammonium salts have the subformula: Three of R 1 to R 4 are C 1-30, respectively.
a straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group or aralkyl group, one of which is a trialkylammonium alkyl group, a phenoxyalkyl group, a mono- or dialkylphenoxyalkyleneoxyalkylene group, or A quaternary ammonium salt of carboxymethyl cellulose represented by (an aryl group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27845385A JPS62138501A (en) | 1985-12-11 | 1985-12-11 | Carboxymethycellulose quaternary ammonium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27845385A JPS62138501A (en) | 1985-12-11 | 1985-12-11 | Carboxymethycellulose quaternary ammonium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62138501A JPS62138501A (en) | 1987-06-22 |
| JPS6355524B2 true JPS6355524B2 (en) | 1988-11-02 |
Family
ID=17597549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27845385A Granted JPS62138501A (en) | 1985-12-11 | 1985-12-11 | Carboxymethycellulose quaternary ammonium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62138501A (en) |
-
1985
- 1985-12-11 JP JP27845385A patent/JPS62138501A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62138501A (en) | 1987-06-22 |
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