JP2007254588A - Method for manufacturing partial acid carboxymethylcellulose - Google Patents
Method for manufacturing partial acid carboxymethylcellulose Download PDFInfo
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- JP2007254588A JP2007254588A JP2006080677A JP2006080677A JP2007254588A JP 2007254588 A JP2007254588 A JP 2007254588A JP 2006080677 A JP2006080677 A JP 2006080677A JP 2006080677 A JP2006080677 A JP 2006080677A JP 2007254588 A JP2007254588 A JP 2007254588A
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- carboxymethylcellulose
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- 239000002253 acid Substances 0.000 title claims abstract description 93
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims description 64
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims description 64
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims description 13
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims description 13
- 238000006266 etherification reaction Methods 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 238000004537 pulping Methods 0.000 claims 1
- 150000003297 rubidium Chemical class 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 abstract description 15
- 239000001913 cellulose Substances 0.000 abstract description 15
- 239000000243 solution Substances 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 3
- 238000010828 elution Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 244000299461 Theobroma cacao Species 0.000 description 2
- 235000009470 Theobroma cacao Nutrition 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 159000000006 cesium salts Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- -1 CMC salt Chemical class 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002785 Croscarmellose sodium Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- WVHBHPATSLQXGC-UHFFFAOYSA-N benzene;ethanol Chemical compound CCO.C1=CC=CC=C1 WVHBHPATSLQXGC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 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
- 159000000005 rubidium salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000007885 tablet disintegrant Substances 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
本発明は部分酸型カルボキシメチルセルロース（以下、部分酸型ＣＭＣという）の製造方法に関する。 The present invention relates to a method for producing partial acid type carboxymethyl cellulose (hereinafter referred to as partial acid type CMC).
部分酸型ＣＭＣは、カルボキシメチルセルロース塩（以下、ＣＭＣ塩という）を酸によって部分的に酸型に置換することによって得られるものである。該部分酸型ＣＭＣは、ＣＭＣ塩を不溶化させることにより、水への膨潤度を調整する事ができるため、錠剤の崩壊剤、打錠菓子、ココア飲料などの粘度調整剤として一般的に用いられている。 The partial acid type CMC is obtained by partially replacing a carboxymethyl cellulose salt (hereinafter referred to as CMC salt) with an acid. Since the partial acid type CMC can adjust the degree of swelling in water by insolubilizing the CMC salt, it is generally used as a viscosity modifier for tablet disintegrants, tablet confectionery, cocoa beverages, etc. ing.
従来、部分酸型ＣＭＣの製造方法としては、精製されたＣＭＣ塩粉末を原料として酸を溶媒中に添加し、ＣＭＣ塩を酸型ＣＭＣに置換する方法が開示されている（特許文献１および特許文献２参照）。しかしながら、このような従来の部分酸型ＣＭＣの製造方法は、ＣＭＣ塩を原料とすることにより、部分酸型ＣＭＣを得るための固有設備が必要である点、ＣＭＣ塩の粉末原料を用いるため、部分酸型ＣＭＣを精製する過程における精製溶媒への溶出、流出することによる歩留低下、ＣＭＣ塩の原料仕込み、取り出し工程でつきまとう手作業による作業環境の低下等の問題があった。 Conventionally, as a method for producing a partial acid type CMC, there has been disclosed a method in which a purified CMC salt powder is used as a raw material, an acid is added to a solvent, and the CMC salt is replaced with an acid type CMC (Patent Document 1 and Patent). Reference 2). However, such a conventional method for producing a partial acid type CMC uses a CMC salt as a raw material, and therefore requires a specific facility for obtaining a partial acid type CMC. There are problems such as elution into the purification solvent in the process of purifying the partial acid type CMC, yield reduction due to outflow, raw material preparation of CMC salt, and reduction in working environment due to manual work involved in the extraction process.
本発明は、ＣＭＣ塩の粉末原料を用いた際に生じる、部分酸型ＣＭＣの精製溶媒への溶出および流出のない部分酸型ＣＭＣの製造方法を提供することを目的とする。 An object of the present invention is to provide a method for producing a partial acid type CMC which is produced when a powder raw material of a CMC salt is used, and does not elute into or flow out from a purified solvent of the partial acid type CMC.
本発明は、（ａ）原料パルプをアルカリセルロース化し、さらにエーテル化してＣＭＣ塩水溶液を製造する工程、
（ｂ）該ＣＭＣ塩水溶液を中和し、ｐＨを８．０以下に調整する工程、
（ｃ）工程（ｂ）でｐＨを調整したＣＭＣ塩水溶液における溶媒を一部除去し、ＣＭＣ塩の固形分濃度を３０〜８０重量％に調整する工程、および
（ｄ）工程（ｃ）で固形分濃度を調整したＣＭＣ塩水溶液に、目的とする酸型エーテル化度に必要な理論モル量の１．１〜１．３倍の酸を添加し、撹拌後、６０〜１１０℃で３０〜６０分間加熱および撹拌する工程
を含む部分酸型ＣＭＣの製造方法に関する。
The present invention includes (a) a process for producing a CMC salt aqueous solution by converting a raw material pulp into an alkali cellulose and further etherifying it,
(B) neutralizing the CMC salt aqueous solution and adjusting the pH to 8.0 or less,
(C) A part of the solvent in the CMC salt aqueous solution whose pH is adjusted in step (b) is partially removed to adjust the solid content concentration of the CMC salt to 30 to 80% by weight; and (d) solid in step (c). An acid of 1.1 to 1.3 times the theoretical molar amount required for the desired degree of acid etherification is added to the CMC salt aqueous solution with the adjusted partial concentration, and after stirring, 30 to 60 at 60 to 110 ° C. The present invention relates to a method for producing partial acid CMC, which includes a step of heating and stirring for a minute.
また、本発明は、前記の製造方法によって得られる部分酸型ＣＭＣであって、全エーテル化度が０．３０〜２．５０であり、酸型のエーテル化度が全エーテル化度の１．０〜８０．０％である部分酸型ＣＭＣにも関する。 Moreover, this invention is partial acid type CMC obtained by the said manufacturing method, Comprising: The total etherification degree is 0.30-2.50, The etherification degree of an acid type is 1. It also relates to a partial acid type CMC that is 0-80.0%.
部分酸型ＣＭＣにおける残余カルボキシメチル基が、ナトリウム塩、カリウム塩、リチウム塩、ルビジウム塩およびセシウム塩からなる群より選ばれる少なくとも１種のアルカリ塩であることが好ましい。 The residual carboxymethyl group in the partial acid type CMC is preferably at least one alkali salt selected from the group consisting of sodium salts, potassium salts, lithium salts, rubidium salts and cesium salts.
本発明によれば、原料パルプから部分酸型ＣＭＣを同一設備で製造することができ、さらに、酸の添加量、加熱温度および撹拌時間を特定の条件に設定することで、目的通りに酸型エーテル化度の比率を調製することができる。 According to the present invention, the partial acid type CMC can be produced from the raw pulp with the same equipment, and further, the acid type can be obtained as intended by setting the addition amount of the acid, the heating temperature and the stirring time to specific conditions. The ratio of the degree of etherification can be adjusted.
本発明は、（ａ）原料パルプをアルカリセルロース化し、さらにエーテル化してＣＭＣ塩水溶液を製造する工程、（ｂ）該ＣＭＣ塩水溶液を中和し、ｐＨを８．０以下に調整する工程、（ｃ）工程（ｂ）でｐＨを調整したＣＭＣ塩水溶液における溶媒を一部除去し、ＣＭＣ塩の固形分濃度を３０〜８０重量％に調整する工程、および（ｄ）工程（ｃ）で固形分濃度を調整したＣＭＣ塩水溶液に、目的とする酸型エーテル化度に必要な理論モル量の１．１〜１．３倍の酸を添加し、撹拌後、６０〜１１０℃で３０〜６０分間加熱および撹拌する工程を含む部分酸型ＣＭＣの製造方法に関する。 The present invention includes: (a) a step of alkali-cellulose-making raw pulp and further etherifying to produce an aqueous CMC salt solution; (b) a step of neutralizing the aqueous CMC salt solution and adjusting the pH to 8.0 or less; c) a step of partially removing the solvent in the CMC salt aqueous solution whose pH is adjusted in step (b) to adjust the solid content concentration of the CMC salt to 30 to 80% by weight; and (d) solid content in step (c). To the adjusted CMC salt aqueous solution, 1.1 to 1.3 times the theoretical molar amount necessary for the desired degree of acid etherification is added, and after stirring, at 60 to 110 ° C. for 30 to 60 minutes. The present invention relates to a method for producing partial acid CMC, which includes a step of heating and stirring.
ここで、部分酸型ＣＭＣとは、ＣＭＣ塩を酸によって部分的に遊離酸に置換したＣＭＣ（以下、ＣＭＣ−Ｈという）を意味する。 Here, the partial acid type CMC means CMC (hereinafter referred to as CMC-H) in which a CMC salt is partially substituted with a free acid by an acid.
工程（ａ）における原料パルプは、リンターパルプ、針葉樹材を主としたＮ材パルプ、広葉樹材を主としたＬ材パルプが用いられる。原料パルプは、チップ状、綿状に粉砕するか、あるいはシート状のまま用いることができるが、アルカリセルロース化およびエーテル化するときに用いる薬剤との反応を促進させるために、原料パルプは粉砕して用いることが好ましい。 As the raw material pulp in the step (a), linter pulp, N material pulp mainly composed of softwood materials, and L material pulp mainly composed of hardwood materials are used. The raw pulp can be crushed into chips, cotton, or used in the form of a sheet, but the raw pulp is pulverized in order to accelerate the reaction with the chemicals used for alkali celluloseation and etherification. Are preferably used.
アルカリセルロース化に用いるアルカリとしては、通常アルカリ金属水酸化物が好ましく、例えば水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化ルビジウム、水酸化セシウム等の１価の金属の水酸化物があげられる。これらの中で、価格および得られるＣＭＣ塩の特性の点から水酸化ナトリウムが好ましい。 Alkali metal hydroxide is usually preferred as the alkali used for alkali celluloseification, and examples thereof include monovalent metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide. It is done. Among these, sodium hydroxide is preferable from the viewpoint of the price and the characteristics of the obtained CMC salt.
アルカリの配合量は、原料パルプ中のセルロースのグルコース単位量に対して、モル比で１．５〜６．０倍が好ましく、２．０〜４．０倍がより好ましい。アルカリの配合量が１．５倍より小さいと、アルカリセルロースを充分に生成させることができず、エーテル化が不充分となる傾向がある。一方、アルカリの配合量が４．０倍より大きいと、特に支障はないがアルカリを浪費することになり、また、得られるＣＭＣ塩の水溶液の粘度が低下する傾向がある。 The alkali compounding amount is preferably 1.5 to 6.0 times, more preferably 2.0 to 4.0 times in terms of a molar ratio with respect to the glucose unit amount of cellulose in the raw pulp. If the blending amount of the alkali is less than 1.5 times, the alkali cellulose cannot be sufficiently produced, and etherification tends to be insufficient. On the other hand, when the blending amount of the alkali is larger than 4.0 times, there is no particular problem, but the alkali is wasted, and the viscosity of the obtained CMC salt aqueous solution tends to decrease.
アルカリセルロース化を行うときの反応温度は、３０〜５０℃が好ましく、３０〜４０℃がより好ましい。アルカリセルロース化の反応温度が３０℃より低いと、アルカリセルロースを充分に生成させることができない傾向がある。一方、反応温度が５０℃より高いと、得られるＣＭＣ塩の水溶液の粘度が低下する傾向がある。また、アルカリセルロース化を行うときの反応時間は、３０〜６０分間が好ましく、４０〜５０分間がより好ましい。反応時間が３０分間より短いと、アルカリセルロースを充分に生成させることができない傾向がある。一方、反応時間が６０分間より長いと、得られるＣＭＣ塩の水溶液の粘度が低下する傾向がある。 30-50 degreeC is preferable and, as for the reaction temperature when performing alkali cellulose conversion, 30-40 degreeC is more preferable. When the reaction temperature for alkali cellulose formation is lower than 30 ° C., there is a tendency that alkali cellulose cannot be generated sufficiently. On the other hand, when reaction temperature is higher than 50 degreeC, there exists a tendency for the viscosity of the aqueous solution of the obtained CMC salt to fall. Moreover, 30-60 minutes are preferable and, as for the reaction time when performing alkali cellulose conversion, 40-50 minutes are more preferable. When the reaction time is shorter than 30 minutes, there is a tendency that alkali cellulose cannot be generated sufficiently. On the other hand, when reaction time is longer than 60 minutes, there exists a tendency for the viscosity of the aqueous solution of the CMC salt obtained to fall.
アルカリセルロース化を行うときの溶媒は、アルカリとの相溶性をもたせるため、含水有機溶媒が使用される。有機溶媒としては、エタノール、メタノール、ｎ−プロピルアルコール、イソプロピルアルコール（以下、ＩＰＡという）、ｎ−ブチルアルコール、イソブチルアルコールなどの炭素数１〜４のアルコール類、アセトン、ジエチルケトン、メチルエチルケトンなどのケトン類、ジオキサン、ジエチルエーテルなどが挙げられる。これらは単独で用いてもよく、２種以上の混合物として用いてもよい。とくに入手の手軽さ、低価格、取り扱いやすさの点で、ＩＰＡ、エタノール、メタノールが好ましい。さらに、エタノール−ベンゼン、エタノール−トルエン、ＩＰＡ−ベンゼンなどの混合溶媒も使用できる。 A water-containing organic solvent is used as the solvent for carrying out the alkali celluloseification because it has compatibility with alkali. Examples of the organic solvent include ethanol, methanol, n-propyl alcohol, isopropyl alcohol (hereinafter referred to as IPA), alcohols having 1 to 4 carbon atoms such as n-butyl alcohol and isobutyl alcohol, and ketones such as acetone, diethyl ketone and methyl ethyl ketone. , Dioxane, diethyl ether and the like. These may be used alone or as a mixture of two or more. In particular, IPA, ethanol, and methanol are preferable in terms of easy availability, low cost, and ease of handling. Furthermore, mixed solvents, such as ethanol-benzene, ethanol-toluene, and IPA-benzene, can also be used.
含水有機溶媒中の水と有機溶媒の重量比としては、反応系中のアルカリ濃度を充分に高濃度に保つことができるという観点から、水：有機溶媒が１０：９０〜４０：６０が好ましく、１５：８５〜３０：７０がより好ましい。水と有機溶媒との重量比が１０：９０を外れて水の量が少なくなると、水によるセルロース分子へのアタックが減少し、結晶化領域の破壊が少なくなるため、水溶液としたときに透明性が高いＣＭＣ塩を得ることが困難になる。一方、水と有機溶媒との重量比が４０：６０をはずれて水の量が多くなると、水とカルボキシメチルエーテル化剤とのあいだでの副反応が進み、カルボキシメチルエーテル化剤の有効利用率が低下する。 The weight ratio of water to the organic solvent in the water-containing organic solvent is preferably 10:90 to 40:60 of water: organic solvent from the viewpoint that the alkali concentration in the reaction system can be kept sufficiently high. 15: 85-30: 70 is more preferable. When the weight ratio of water and the organic solvent is outside 10:90 and the amount of water is reduced, the attack on the cellulose molecules by water is reduced and the crystallization region is less destroyed. It is difficult to obtain a high CMC salt. On the other hand, when the weight ratio of water and the organic solvent exceeds 40:60 and the amount of water increases, the side reaction between water and the carboxymethyl etherifying agent proceeds, and the effective utilization rate of the carboxymethyl etherifying agent is increased. Decreases.
含水有機溶媒の配合量は、原料パルプに対して、重量比で２．５〜１０倍が好ましく、３〜８倍がより好ましい。含水有機溶媒の配合量が２．５倍より小さいと、含水有機溶媒と原料パルプ中のセルロースとが充分に撹拌混合されなくなるため、撹拌時の反応機に対する負荷が大きくなり、また均一反応に支障をきたす傾向がある。一方、含水有機溶媒の配合量が１０倍より大きいと、原料経費が高くなる傾向がある。 The blending amount of the water-containing organic solvent is preferably 2.5 to 10 times, more preferably 3 to 8 times by weight with respect to the raw material pulp. If the amount of the water-containing organic solvent is less than 2.5 times, the water-containing organic solvent and cellulose in the raw pulp will not be sufficiently stirred and mixed, increasing the load on the reactor during stirring and hindering uniform reaction. There is a tendency to cause. On the other hand, if the amount of the water-containing organic solvent is larger than 10 times, the raw material cost tends to be high.
次に、得られたアルカリセルロースにエーテル化剤を反応させてエーテル化する。エーテル化は、通常アルカリ過剰下で進行させる。エーテル化剤としては、例えばモノクロル酢酸、モノクロル酢酸ナトリウム、モノクロル酢酸メチル、モノクロル酢酸エチル等が使用される。エーテル化剤の配合量は、目的とするＣＭＣ塩のエーテル化度によって決定されるため、特に制限はないが、通常原料パルプ中のグルコース単位量に対して、モル比で０．５〜６倍が好ましく、２〜４倍がより好ましい。エーテル化剤の配合量が、０．５倍より小さいと、ＣＭＣ塩のエーテル化度が低く、目的とするエーテル化度が得にくい傾向がある。一方、エーテル化剤の配合量が６倍より大きいと、特に支障はないが、高価なエーテル化剤を無駄に使用する傾向がある。 Next, the obtained alkali cellulose is reacted with an etherifying agent to be etherified. Etherification is usually allowed to proceed in the presence of excess alkali. As the etherifying agent, for example, monochloroacetic acid, sodium monochloroacetate, methyl monochloroacetate, ethyl monochloroacetate or the like is used. The blending amount of the etherifying agent is determined by the degree of etherification of the target CMC salt, and is not particularly limited, but is usually 0.5 to 6 times in molar ratio to the glucose unit amount in the raw pulp. Is preferable, and 2 to 4 times is more preferable. If the blending amount of the etherifying agent is less than 0.5 times, the degree of etherification of the CMC salt is low, and the desired degree of etherification tends to be difficult to obtain. On the other hand, if the blending amount of the etherifying agent is more than 6 times, there is no particular problem, but there is a tendency to use an expensive etherifying agent wastefully.
エーテル化を行うときの反応温度は、７５〜１００℃が好ましく、８０〜９０℃がより好ましい。反応温度が７５℃より低いと、エーテル化が不充分になる傾向がある。一方、反応温度が１００℃より高いと反応溶媒の沸点をこえる場合があり、溶媒が揮発する傾向がある。また、反応時間は、５０〜１２０分間が好ましく、５０〜９０分間がより好ましい。反応時間が５０分間より短いとエーテル化が不充分になる傾向がある。一方、反応時間が９０分間より長いと、特に支障はないが時間の浪費となり、得られるＣＭＣ塩の粘度が低下する傾向がある。 75-100 degreeC is preferable and, as for the reaction temperature when performing etherification, 80-90 degreeC is more preferable. When the reaction temperature is lower than 75 ° C., etherification tends to be insufficient. On the other hand, when the reaction temperature is higher than 100 ° C., the boiling point of the reaction solvent may be exceeded and the solvent tends to volatilize. The reaction time is preferably 50 to 120 minutes, more preferably 50 to 90 minutes. When the reaction time is shorter than 50 minutes, etherification tends to be insufficient. On the other hand, when the reaction time is longer than 90 minutes, there is no particular problem, but time is wasted and the viscosity of the obtained CMC salt tends to decrease.
工程（ｂ）においてＣＭＣ塩水溶液のｐＨを調整する。工程（ａ）によって得られたＣＭＣ塩水溶液において、アルカリセルロース化に用いたアルカリが過剰量であるとアルカリ性となるため、有機酸を添加することにより、過剰のアルカリを中和させる。有機酸としては、例えば酢酸、クエン酸、リンゴ酸、スルファミン酸、プロピオン酸、ギ酸等が挙げられる。これらの中で、液状品である点、および中和調整のしやすさから酢酸が好ましい。また、エーテル化に用いたエーテル化剤が酸であって、酸が過剰量であると、ＣＭＣ塩水溶液が酸性となるため、アルカリを添加することにより過剰の酸を中和させる。アルカリとしては、例えば、苛性ソーダ、炭酸ソーダ、重炭酸ソーダ等が挙げられる。これらの中で、液状品である点、強アルカリ性である点から苛性ソーダが好ましい。ＣＭＣ塩水溶液の酸またはアルカリによる調整後のｐＨは、８．０以下であり、７．５以下が好ましい。ｐＨが８．０より大きいと、ＣＭＣ塩の粘度が低下する傾向がある。また、ｐＨの下限は特に限定されないが、６．５以上が好ましく、６．８以上がより好ましい。 In step (b), the pH of the aqueous CMC salt solution is adjusted. In the CMC salt aqueous solution obtained in the step (a), an excessive amount of alkali used for alkali cellulose conversion becomes alkaline, so that an excess of alkali is neutralized by adding an organic acid. Examples of the organic acid include acetic acid, citric acid, malic acid, sulfamic acid, propionic acid, formic acid and the like. Among these, acetic acid is preferable because it is a liquid product and easy to adjust for neutralization. If the etherifying agent used for etherification is an acid and the acid is in an excessive amount, the CMC salt aqueous solution becomes acidic. Therefore, the excess acid is neutralized by adding an alkali. Examples of the alkali include caustic soda, sodium carbonate, sodium bicarbonate and the like. Among these, caustic soda is preferable because it is a liquid product and is strongly alkaline. The pH of the CMC salt aqueous solution after adjustment with acid or alkali is 8.0 or less, preferably 7.5 or less. When the pH is greater than 8.0, the viscosity of the CMC salt tends to decrease. The lower limit of the pH is not particularly limited, but is preferably 6.5 or more, and more preferably 6.8 or more.
工程（ｃ）において、前記工程（ｂ）によりｐＨを調整したＣＭＣ塩水溶液における溶媒を遠心分離によりしぼり、または加熱蒸留等により一部除去することによりＣＭＣ塩を一定の固形分濃度に調整する。工程（ｃ）におけるＣＭＣ塩の固形分濃度は、３０〜８０重量％であり、４０〜７０重量％が好ましく、４５〜６５重量％がより好ましい。固形分濃度が３０重量％より小さいと、部分酸型ＣＭＣを調製するときに添加される酸が均一に混ざらない傾向がある。一方、固形分濃度が８０重量％より大きいと、部分酸型ＣＭＣを調製するときに添加される酸によりＣＭＣ塩が置換する反応速度が低下するため、目標とするＣＭＣ−Ｈが得られにくくなる傾向がある。 In the step (c), the CMC salt is adjusted to a certain solid content concentration by squeezing the solvent in the CMC salt aqueous solution whose pH is adjusted in the step (b) or by partially removing the solution by heating distillation or the like. The solid content concentration of the CMC salt in the step (c) is 30 to 80% by weight, preferably 40 to 70% by weight, and more preferably 45 to 65% by weight. If the solid content concentration is less than 30% by weight, the acid added when preparing the partial acid type CMC tends not to be mixed uniformly. On the other hand, when the solid content concentration is larger than 80% by weight, the reaction rate of substitution of the CMC salt by the acid added when preparing the partial acid type CMC is lowered, so that it becomes difficult to obtain the target CMC-H. Tend.
工程（ｄ）において、前記工程（ｃ）の固形分濃度のＣＭＣ塩水溶液またはスラリーを精製および単離を行わず、未精製のまま酸を添加し、ＣＭＣ塩の一部をＣＭＣ−Ｈにする。工程（ｄ）における酸の添加量は、酸型エーテル化度に必要な酸モル量の１．１〜１．３倍であり、１．１８〜１．２２倍が好ましい。酸の添加量が、１．１倍より小さいと、目標とする酸型ＣＭＣの当量値に至らない傾向がある。一方、酸の添加量が、１．３倍より大きいと、目標とする酸型ＣＭＣの当量値を超える傾向がある。 In the step (d), the CMC salt aqueous solution or slurry having the solid concentration in the step (c) is not purified and isolated, but an acid is added without purification to make a part of the CMC salt CMC-H. . The amount of acid added in the step (d) is 1.1 to 1.3 times, and preferably 1.18 to 1.22 times the molar amount of acid required for the acid type etherification degree. If the amount of acid added is less than 1.1 times, the target equivalent value of acid type CMC tends not to be reached. On the other hand, when the addition amount of the acid is larger than 1.3 times, there is a tendency to exceed the equivalent value of the target acid type CMC.
ＣＭＣ塩を部分酸型ＣＭＣに置換する際に使用される酸としては、特に限定されないが、硫酸、硝酸、塩酸、リン酸、リンゴ酸、スルファミン酸、酢酸、モノクロル酢酸などが挙げられる。これらの中で、強酸でＣＭＣ−ＮａをＣＭＣ−Ｈに置換する効率が高い点で、硫酸、塩酸が好ましい。 The acid used when substituting the CMC salt with the partial acid type CMC is not particularly limited, and examples thereof include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, malic acid, sulfamic acid, acetic acid, and monochloroacetic acid. Among these, sulfuric acid and hydrochloric acid are preferable in that the efficiency of replacing CMC-Na with CMC-H with a strong acid is high.
酸を添加した後の反応温度は、６０〜１１０℃であり、７０〜１０５℃が好ましく、８０〜１０５℃がより好ましい。反応温度が６０℃より低いと、充分にＣＭＣ−Ｈへの置換ができない傾向がある。一方、反応温度が１１０℃より高いと、品質上ＣＭＣの粘度低下が発生し、さらにできあがった部分酸型ＣＭＣはゲル化する傾向がある。また、反応時間は、３０〜６０分間であり、４５〜５５分間が好ましい。反応時間が３０分間より短いと、充分にＣＭＣ−Ｈへの置換ができない傾向がある。一方、反応温度が６０分間より長いと、品質上ＣＭＣの粘度低下が発生し、さらにできあがった部分酸型ＣＭＣはゲル化する傾向がある。 The reaction temperature after adding an acid is 60-110 degreeC, 70-105 degreeC is preferable and 80-105 degreeC is more preferable. When the reaction temperature is lower than 60 ° C., there is a tendency that the substitution to CMC-H cannot be sufficiently performed. On the other hand, when the reaction temperature is higher than 110 ° C., the viscosity of CMC decreases due to the quality, and the completed partial acid type CMC tends to gel. The reaction time is 30 to 60 minutes, preferably 45 to 55 minutes. When the reaction time is shorter than 30 minutes, there is a tendency that the substitution to CMC-H cannot be sufficiently performed. On the other hand, when the reaction temperature is longer than 60 minutes, the viscosity of CMC decreases due to the quality, and the resulting partial acid type CMC tends to gel.
工程（ｄ）により部分酸型ＣＭＣを調製し、そののちに冷却すると副生塩を形成するが、該副生塩は公知のＣＭＣ塩の精製法により部分酸型ＣＭＣを精製することができる。 When the partial acid type CMC is prepared by the step (d) and then cooled, a by-product salt is formed. The by-product salt can be purified by a known CMC salt purification method.
本発明の製造方法によれば、ＣＭＣ塩反応物を単離せず、未精製のままＣＭＣ−Ｎａの製造工程で同一製造設備を用いて、部分酸型ＣＭＣを製造することができる。 According to the production method of the present invention, partial acid CMC can be produced using the same production equipment in the production process of CMC-Na without isolation of the CMC salt reaction product.
前記の製造方法によって得られる部分酸型ＣＭＣとしては、全エーテル化度が０．３０〜２．５０であり、酸型のエーテル化度が全エーテル化度の１．０〜８０．０％である。 The partial acid type CMC obtained by the above production method has a total etherification degree of 0.30 to 2.50 and an acid type etherification degree of 1.0 to 80.0% of the total etherification degree is there.
部分酸型ＣＭＣの全エーテル化度は、０．３０〜２．５０が好ましく、０．５〜１．８がより好ましく、０．６〜１．５がさらに好ましい。全エーテル化度が０．３０より小さいと、ＣＭＣ塩が不溶化するために用途上有用性が少ない傾向がある。一方、全エーテル化度が２．５０より大きいと、高エーテル化度による用途上の有用性が少ない傾向がある。 The total degree of etherification of the partial acid type CMC is preferably 0.30 to 2.50, more preferably 0.5 to 1.8, and still more preferably 0.6 to 1.5. When the total degree of etherification is less than 0.30, the CMC salt is insolubilized, so that it tends to be less useful for applications. On the other hand, when the total degree of etherification is greater than 2.50, there is a tendency that usefulness for use due to the high degree of etherification is low.
酸型のエーテル化度は全エーテル化度の１．０〜８０．０％であり、２０〜６０％が好ましい。酸型のエーテル化度が１．０％より小さいと、酸型にする効果が発揮できない傾向がある。一方、酸型のエーテル化度が８０．０％より大きいと、酸型の進行によるＣＭＣの不溶化が促進され、部分酸型とする効果が失われる傾向がある。 The acid type etherification degree is 1.0 to 80.0% of the total etherification degree, and preferably 20 to 60%. When the degree of etherification of the acid type is less than 1.0%, the effect of converting to the acid type tends to not be exhibited. On the other hand, if the degree of etherification of the acid type is greater than 80.0%, insolubilization of CMC due to the progress of the acid type is promoted, and the effect of the partial acid type tends to be lost.
部分酸型ＣＭＣにおける残余カルボキシメチル基は、前記の工程（ａ）によって用いられたアルカリ金属水酸化物により得られるアルカリ塩が挙げられ、具体的には、ナトリウム塩、カリウム塩、リチウム塩、ルビジウム塩およびセシウム塩等が挙げられる。これらの中で、ナトリウム塩、カリウム塩が、一般的に好ましく用いられる。 Examples of the residual carboxymethyl group in the partial acid type CMC include alkali salts obtained by the alkali metal hydroxide used in the step (a), specifically, sodium salt, potassium salt, lithium salt, rubidium. Examples thereof include salts and cesium salts. Of these, sodium salts and potassium salts are generally preferably used.
本発明の製造方法で得られる部分酸型ＣＭＣは、錠剤の崩壊剤、打錠菓子、ココア飲料などの粘度調整剤、クロスリンク化ＣＭＣの中間原料などの用途に、好ましく利用できる。 The partial acid type CMC obtained by the production method of the present invention can be preferably used for applications such as tablet disintegrating agents, tableting confectionery, viscosity adjusting agents such as cocoa beverages, and intermediate materials for cross-linked CMC.
以下、実施例によって本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
実施例１〜９
＜ＣＭＣ−Ｎａの製造＞
２軸の撹拌翼を備えた容量３リットルのニーダー型反応機に、家庭用ミキサー等で粉砕したパルプ１００ｇを仕込んだ。原料パルプとして、Ｌ−ＤＰＴおよびＮ−ＤＳＰ（日本製紙ケミカル（株）製）を２：１の重量比で配合させたものを使用した。ＩＰＡ：水を７０：３０（重量比）に調整した反応溶媒４００ｇ（ＩＰＡ：水＝２８０ｇ：１２０ｇ）を表１に示した所定量の水酸化ナトリウムを溶解させて４０℃に調整した溶液を反応機内に添加し、６０分間撹拌し、アルカリセルロースを生成した。
Examples 1-9
<Manufacture of CMC-Na>
A kneader reactor having a capacity of 3 liters equipped with biaxial stirring blades was charged with 100 g of pulp pulverized with a home mixer or the like. As the raw material pulp, a mixture of L-DPT and N-DSP (manufactured by Nippon Paper Chemicals Co., Ltd.) at a weight ratio of 2: 1 was used. Reaction of 400 g (IPA: water = 280 g: 120 g) of a reaction solvent in which IPA: water was adjusted to 70:30 (weight ratio) was dissolved in a predetermined amount of sodium hydroxide shown in Table 1 and adjusted to 40 ° C. It added in the machine and stirred for 60 minutes, The alkali cellulose was produced | generated.
そののち、表１に示した所定量のモノクロル酢酸を等重量のＩＰＡに溶解させた溶液を３０〜５０℃で６０分間かけて反応熱を抑えながら仕込んだ。仕込み後、３０分間かけて８５℃に昇温し、７５〜９０℃でエーテル化反応を６０分間行った。反応機には冷却管を設置してＩＰＡの気化発散を防止した。そののち、過剰の水酸化ナトリウムを酢酸で中和してｐＨ６．５〜８とし、スラリー状の中和物を反応機より取り出し、遠心分離してＩＰＡ／水を除去した。固形分を３０〜８０％に調整し、ＣＭＣ−Ｎａ（Ａ）〜（Ｃ）を得た。 After that, a solution prepared by dissolving a predetermined amount of monochloroacetic acid shown in Table 1 in an equal weight of IPA was charged at 30 to 50 ° C. for 60 minutes while suppressing the heat of reaction. After the preparation, the temperature was raised to 85 ° C. over 30 minutes, and the etherification reaction was performed at 75 to 90 ° C. for 60 minutes. The reactor was equipped with a cooling pipe to prevent IPA from evaporating. After that, excess sodium hydroxide was neutralized with acetic acid to pH 6.5-8, and the slurry neutralized product was taken out from the reactor and centrifuged to remove IPA / water. The solid content was adjusted to 30 to 80% to obtain CMC-Na (A) to (C).
＜部分酸型ＣＭＣの製造＞
ＣＭＣ−Ｎａを部分的にＣＭＣ−Ｈとするために、前記の固形分濃度に調整した反応物を取り出し、ＣＭＣ−Ｎａを単離せず未精製のまま、２０％硫酸を表２に示す必要モル数添加し、さらに表２に示す加熱温度および加熱時間で撹拌した。得られたＣＭＣ−Ｎａ／ＣＭＣ−Ｈを７０％メタノール水溶液で洗浄し、副生物の食塩、グリコール酸ナトリウム、酢酸ナトリウムを除去した。
<Production of partial acid type CMC>
In order to partially convert CMC-Na to CMC-H, the reaction product adjusted to the above-mentioned solid content concentration was taken out, and CMC-Na was not isolated and purified with 20% sulfuric acid as shown in Table 2 without purification. A few were added, and the mixture was further stirred at the heating temperature and heating time shown in Table 2. The obtained CMC-Na / CMC-H was washed with a 70% aqueous methanol solution to remove by-product sodium chloride, sodium glycolate, and sodium acetate.
この洗浄操作を２回繰り返した後、メタノール水溶液を遠心分離除去して９０〜１０５℃で４時間乾燥後粉砕して部分酸型ＣＭＣを得た。 After repeating this washing operation twice, the methanol aqueous solution was removed by centrifugation, dried at 90 to 105 ° C. for 4 hours and then pulverized to obtain a partial acid type CMC.
得られた部分酸型ＣＭＣの１％水溶液粘度、全エーテル化度（ＤＳ）、得られた部分酸型ＣＭＣのＣＭＣ−Ｎａ化度およびＣＭＣ−Ｈ化度を下記の方法により測定し、物性を評価した。得られた結果を表２に示す。 The 1% aqueous solution viscosity, total etherification degree (DS) of the obtained partial acid type CMC, the CMC-Na degree and the CMC-H degree of the obtained partial acid type CMC were measured by the following methods, and the physical properties were measured. evaluated. The obtained results are shown in Table 2.
＜１％水溶液粘度＞
１．水分の算出
試料１〜２ｇを秤量ビンに精密にはかりとり、１０５±２℃の低温乾燥機中において４時間乾燥し、デシケーター中に冷却したのちフタをして重さをはかり、その減量から水分を算出した。
<1% aqueous solution viscosity>
1. Calculation of moisture Accurately weigh 1 to 2 g of sample into a weighing bottle, dry in a low-temperature dryer at 105 ± 2 ° C for 4 hours, cool in a desiccator, weigh the lid, and measure the moisture from the weight loss. Was calculated.
２．１％水溶液粘度の測定
３００ｍｌのトールビーカーに約２．５ｇの試料を精秤し、下記式を用いて求めた１％水溶液を得るために必要な溶解水量の水を加え、ガラス棒にて分散させた。
溶解水量（ｇ）＝試料（ｇ）÷（９９−水分（％））
2.1 Measurement of Viscosity of Aqueous Solution About 2.5 g of sample is precisely weighed in a 300 ml tall beaker, and water of the amount necessary for obtaining a 1% aqueous solution obtained using the following formula is added to a glass rod. And dispersed.
Dissolved water amount (g) = sample (g) ÷ (99−water content (%))
得られた水溶液を一昼夜放置し、マグネチックスターラーで約５分間撹拌して完全な溶液としたのち３０分間２５℃の恒温水槽に入れて、溶液を２５℃とした。この溶液をガラス棒でゆるやかにかき混ぜ、ＢＭ型粘度計の適当なローターおよびガードを取り付け、回転数６０ｒｐｍで３分後の目盛りを読み取った。読み取り目盛りから下記式を用いて粘度を求めた。式中、ｋはローターと回転数によって決まる換算乗数である。
粘度（ｍＰａ・ｓ）＝読み取り目盛×ｋ
The obtained aqueous solution was left for a whole day and night, stirred for about 5 minutes with a magnetic stirrer to obtain a complete solution, and then placed in a constant temperature water bath at 25 ° C. for 30 minutes to bring the solution to 25 ° C. The solution was gently stirred with a glass rod, an appropriate rotor and guard of a BM type viscometer were attached, and the scale after 3 minutes was read at a rotational speed of 60 rpm. The viscosity was determined from the reading scale using the following formula. In the equation, k is a conversion multiplier determined by the rotor and the rotational speed.
Viscosity (mPa · s) = Reading scale × k
＜エーテル化度（ＤＳ）＞
（１）全ナトリウム塩型ＣＭＣのＤＳ
試料１ｇ（純分換算）を磁性ルツボに入れて６００℃で灰化し、灰化によって生成した酸化ナトリウムをＮ／１０のＨ2ＳＯ4１００ｍｌを添加して中和した。次に、過剰のＨ2ＳＯ4をＮ／１０のＮａＯＨでフェノールフタレインを指示薬として滴定し、その滴下量Ａｍｌを下記式に入れて計算しＤＳを求めた。
<Degree of etherification (DS)>
(1) DS of total sodium salt type CMC
1 g of sample (in terms of pure content) was put into a magnetic crucible and incinerated at 600 ° C., and sodium oxide produced by incineration was neutralized by adding 100 ml of N / 10 H 2 SO 4 . Next, excess H 2 SO 4 was titrated with N / 10 NaOH using phenolphthalein as an indicator, and the dripping amount Aml was calculated into the following formula to calculate DS.
ここでｆ1：Ｎ／１０のＨ2ＳＯ4の力価
ｆ2：Ｎ／１０のＨａＯＨの力価
Where f 1 : titer of N / 10 H 2 SO 4 f 2 : titer of N / 10 HaOH
（２）得られた部分酸型ＣＭＣのＣＭＣ−Ｎａ化度およびＣＭＣ−Ｈ化度
試料１ｇ（純分換算）を純水２００ｍｌとＮ／１０のＮａＯＨ１００ｍｌが入っているフラスコ中に入れて溶解した。次に、過剰のＮ／１０のＮａＯＨをＮ／１０のＨ2ＳＯ4でフェノールフタレインを支持数として滴定し、その滴下量Ｂｍｌを得た。
(2) CMC-Na conversion degree and CMC-H conversion degree of the obtained partial acid type CMC 1 g (in terms of pure content) of sample was dissolved in a flask containing 200 ml of pure water and 100 ml of N / 10 NaOH. . Next, excess N / 10 NaOH was titrated with N / 10 H 2 SO 4 with phenolphthalein as the supporting number to obtain a dripping amount Bml.
次に、別の試料１ｇ（純分換算）を磁性ルツボに入れて６００℃で灰化し、灰化によって生成した酸化ナトリウムをＮ／１０のＨ2ＳＯ4１００ｍｌを添加して中和した。次に、過剰のＨ2ＳＯ4をＮ／１０のＮａＯＨでフェノールフタレインを指示薬として滴定し、その滴下量Ｃｍｌを得た。 Next, another sample 1 g (in terms of pure content) was put in a magnetic crucible and incinerated at 600 ° C., and sodium oxide produced by incineration was neutralized by adding 100 ml of N / 10 H 2 SO 4 . Next, excess H 2 SO 4 was titrated with N / 10 NaOH using phenolphthalein as an indicator to obtain a dripping amount Cml.
次に、次式によってＣＭＣ−Ｎａ化度およびＣＭＣ−Ｈ化度を求めた。 Next, the degree of CMC-Na and the degree of CMC-H were determined by the following equations.
ここでｆ1：Ｎ／１０のＨ2ＳＯ4の力価
ｆ2：Ｎ／１０のＨａＯＨの力価
Where f 1 : titer of N / 10 H 2 SO 4 f 2 : titer of N / 10 HaOH
比較例１〜３
部分酸型ＣＭＣの製造工程において、加熱時間を３０℃（比較例１）、撹拌時間を１０分（比較例２）、硫酸の添加量を０．３０モル（比較例３）とした以外は、実施例２と同様の方法にて部分酸型ＣＭＣを製造した。
Comparative Examples 1-3
In the production process of the partial acid type CMC, except that the heating time was 30 ° C. (Comparative Example 1), the stirring time was 10 minutes (Comparative Example 2), and the addition amount of sulfuric acid was 0.30 mol (Comparative Example 3), Partial acid type CMC was produced in the same manner as in Example 2.
得られた部分酸型ＣＭＣの各物性を実施例１と同様の方法にて測定し、物性を評価した。得られた結果を表２に示す。 Each physical property of the obtained partial acid type CMC was measured by the same method as in Example 1 to evaluate the physical property. The obtained results are shown in Table 2.
比較例４〜６
部分酸型ＣＭＣの製造工程において、加熱時間を３０℃（比較例４）、撹拌時間を１０分（比較例５）、硫酸の添加量を０．１０モル（比較例６）とした以外は、実施例５と同様の方法にて部分酸型ＣＭＣを製造した。
Comparative Examples 4-6
In the production process of the partial acid type CMC, the heating time was 30 ° C. (Comparative Example 4), the stirring time was 10 minutes (Comparative Example 5), and the addition amount of sulfuric acid was 0.10 mol (Comparative Example 6). Partial acid type CMC was produced in the same manner as in Example 5.
得られた部分酸型ＣＭＣの各物性を実施例１と同様の方法にて測定し、物性を評価した。得られた結果を表２に示す。 Each physical property of the obtained partial acid type CMC was measured by the same method as in Example 1 to evaluate the physical property. The obtained results are shown in Table 2.
比較例７〜８
部分酸型ＣＭＣの製造工程において、加熱時間を３０℃（比較例７）、撹拌時間を１０分（比較例８）とした以外は、実施例８と同様の方法にて部分酸型ＣＭＣを製造した。
Comparative Examples 7-8
In the production process of partial acid type CMC, partial acid type CMC was produced in the same manner as in Example 8, except that the heating time was 30 ° C. (Comparative Example 7) and the stirring time was 10 minutes (Comparative Example 8). did.
得られた部分酸型ＣＭＣの各物性を実施例１と同様の方法にて測定し、物性を評価した。得られた結果を表２に示す。 Each physical property of the obtained partial acid type CMC was measured by the same method as in Example 1 to evaluate the physical property. The obtained results are shown in Table 2.
実施例１〜９において、加熱温度、加熱時間および酸の添加量を限定することにより、あらかじめ設定した酸型エーテル化度と実際に得られた部分酸型ＣＭＣの酸型エーテル化度はほぼ同様の値を示した。 In Examples 1 to 9, by limiting the heating temperature, the heating time, and the amount of acid added, the acid type etherification degree set in advance and the acid type etherification degree of the actually obtained partial acid type CMC were almost the same. The value of was shown.
Claims (3)
（ｂ）該カルボキシメチルセルロース塩水溶液を中和し、ｐＨを８．０以下に調整する工程、
（ｃ）工程（ｂ）でｐＨを調整したカルボキシメチルセルロース塩水溶液における溶媒を一部除去し、カルボキシメチルセルロース塩の固形分濃度を３０〜８０重量％に調整する工程、および
（ｄ）工程（ｃ）で固形分濃度を調整したカルボキシメチルセルロース塩水溶液に、目的とする酸型エーテル化度に必要な理論モル量の１．１〜１．３倍の酸を添加し、撹拌後、６０〜１１０℃で３０〜６０分間加熱および撹拌する工程
を含む部分酸型カルボキシメチルセルロースの製造方法。 (A) alkali pulping raw material pulp and further etherifying to produce an aqueous carboxymethylcellulose salt solution,
(B) a step of neutralizing the aqueous carboxymethyl cellulose salt solution and adjusting the pH to 8.0 or less,
(C) a step of partially removing the solvent in the aqueous carboxymethylcellulose salt solution adjusted in pH in step (b) to adjust the solid content concentration of the carboxymethylcellulose salt to 30 to 80% by weight; and (d) step (c). 1.1 to 1.3 times the theoretical molar amount necessary for the target acid-type etherification degree is added to the carboxymethylcellulose salt aqueous solution whose solid content concentration is adjusted in step 1. After stirring, the acid is added at 60 to 110 ° C. The manufacturing method of the partial acid type carboxymethylcellulose including the process of heating and stirring for 30 to 60 minutes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5727660B1 (en) * | 2014-10-01 | 2015-06-03 | 第一工業製薬株式会社 | Method for producing cellulose nanofiber aqueous dispersion |
| CN105246919A (en) * | 2013-06-04 | 2016-01-13 | 陶氏环球技术有限责任公司 | Process for manufacturing lithium carboxymethyl cellulose |
| CN106496335A (en) * | 2016-11-24 | 2017-03-15 | 泸州北方化学工业有限公司 | A kind of method for preparing carboxymethyl cellulose lithium |
| WO2018116660A1 (en) * | 2016-12-21 | 2018-06-28 | 日本製紙株式会社 | Acid-type carboxymethylated cellulose nanofibers and production method therefor |
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2006
- 2006-03-23 JP JP2006080677A patent/JP2007254588A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105246919A (en) * | 2013-06-04 | 2016-01-13 | 陶氏环球技术有限责任公司 | Process for manufacturing lithium carboxymethyl cellulose |
| JP5727660B1 (en) * | 2014-10-01 | 2015-06-03 | 第一工業製薬株式会社 | Method for producing cellulose nanofiber aqueous dispersion |
| CN106496335A (en) * | 2016-11-24 | 2017-03-15 | 泸州北方化学工业有限公司 | A kind of method for preparing carboxymethyl cellulose lithium |
| WO2018116660A1 (en) * | 2016-12-21 | 2018-06-28 | 日本製紙株式会社 | Acid-type carboxymethylated cellulose nanofibers and production method therefor |
| US11591721B2 (en) | 2016-12-21 | 2023-02-28 | Nippon Paper Industries Co., Ltd. | Acid-type carboxymethylated cellulose nanofiber and production method thereof |
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