JP3982269B2 - Composition used for producing spherical cellulose - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、チオシアン酸カルシウム水溶液に粉末状のセルロースを加えて製造されたセルロース溶解液から特定粒径の球状セルロ−スを高収率で製造するのに適した、ハロゲン化炭化水素と特定の界面活性剤を含有する組成物に関する。
【０００２】
【従来の技術】
従来より、特定の粒径をもつセルロースを得ることは検討されている。例えば、特開平１０―１９５１０３号公報には、ソルビタンモノオレートを含むO―ジクロロベンゼンを溶媒として用いる多孔性球状セルロースの製造方法が開示されている。しかしながら、これら従来の方法では、粒径が３００〜５００μｍの球状セルロースを、高い収率で得ることが困難であるという問題点がある。
【０００３】
【発明が解決しようとする課題】
本発明者らは、上記課題を解決するため鋭意研究した。その結果、チオシアン酸カルシウム水溶液に粉末状のセルロースを加えて製造されたセルロース溶解液から粒径３００〜５００μｍの球状セルロースを製造する際に、ハロゲン化炭化水素と特定の界面活性剤を含有する組成物を用いると、該粒径を有する球状セルロ−スを高収率で得ることができることを見出し、この知見に基づいて本発明を完成した。以上の記述から明らかなように、本発明の目的は、該セルロース溶解液から粒径が３００〜５００μｍの球状セルロースを製造する際に、該粒径の球状セルロ−スを高収率で得るのに適した組成物を提供することである。
【０００４】
【課題を解決するための手段】
本発明は以下のように構成されている。
（１）チオシアン酸カルシウム水溶液に粉末状のセルロースを加えて製造されたセルロース溶解液から球状セルロ−スを製造する際に用いる組成物であり、ハロゲン化炭化水素と、疎水基としてメチルポリシロキサン及び親水基としてポリオキシエチレンを有する構造のポリオキシエチレン・メチルポリシロキサン共重合体であり、親水性親油性バランスが４〜６の界面活性剤とが含有された組成物。
【０００５】
（２）界面活性剤の含有量が、組成物に対して、０．００１重量％〜５重量％である前記（１）項記載の組成物。
【０００６】
（３）ハロゲン化炭化水素がジクロロエタン、ジクロロベンゼン、オルトジクロロベンゼンもしくはこれらの１種以上の混合物である前記（１）または（２）項記載の組成物。
【０００７】
（４）前記（１）〜（３）項のいずれか１項記載の組成物に、チオシアン酸カルシウム水溶液に粉末状のセルロースを加えて攪拌した後に昇温して得られた透明のセルロース溶解液を、攪拌しながら滴下し、滴下終了後のセルロース溶解液と組成物の混合液に、メタノールを添加し、濾過にてセルロース粒子を分離し、分離されたセルロース粒子を更に精製水にて洗浄し、得られたセルロース粒子を篩いに掛け目的とする粒径の球状セルロースを得る、球状セルロースの製造方法。
【００１０】
【発明の実施の形態】
以下に本発明を詳細に説明する。本発明のセルロース溶解液から球状セルロ−スを製造する際に用いる組成物には、水に対して親和性を持たないか、もしくは水に溶解せず、得られる特定粒径の球状セルロースの収率を高める点で、ハロゲン化炭化水素が用いられる。ハロゲン化炭化水素としては、好ましくは、ジクロロエタン、ジクロロベンゼン、オルトジクロロベンゼンを例示することができ、該オルトジクロロベンゼンは、例えば市販品として和光純薬工業株式会社製、三井化学株式会社製のものを用いることができる。
【００１１】
本発明に用いる界面活性剤は、疎水基としてメチルポリシロキサンおよび親水基としてポリオキシエチレンを有する構造の界面活性剤である。
【００１３】
かかる界面活性剤としては、ポリオキシエチレン・メチルポリシロキサン共重合体であるエマレックスSS-5050K（商標、日本エマルジョン株式会社製）、エマレックスSS-8020K（商標、日本エマルジョン株式会社製）を具体的に例示することができる。
【００１４】
該界面活性剤の親水性親油性バランスとしては、特定粒径の球状セルロースが高い収率で得られる点から、４〜６が好ましく、更に好ましくは４．５〜５．５の界面活性剤である。
【００１５】
次に界面活性剤の親水性親油性バランスについて説明する。
界面活性剤が示す乳化、分散、洗浄、起泡などの種々の作用のいずれもが２相の界面において、界面活性剤がもつ親水基と親油基がそれぞれの相に対して示す親水性、親油性のバランスによって決まると考えられており、その要求されるバランスの度合いは上記諸現象でそれぞれ異なり、その最適条件は各界面活性剤に与えられた一つの数字を、現象の要求する定まった数の領域と一致させることで実現させることができる。このような考えに従って、界面活性剤分子の親水基と親油基のバランスから決められた数字を親水性親油性バランス、いわゆるエイチ・エル・ビー（ＨＬＢ）と呼んでいる。このような計算から目的に適した界面活性剤およびびその組成を決めるシステムの仕組みをＨＬＢシステムと呼ぶこともある。該ＨＬＢは油の乳化実験から経験的に１〜４０までの数値に分類されており、数が小さいほど親油性が大きいことを示す。
【００１６】
本発明のセルロース溶解液から球状セルロ−スを製造する際に用いる組成物は、上述のハロゲン化炭化水素に上述の界面活性剤が含有された組成物であり、高収率で特定粒径の球状セルロ−スが得られる点から、界面活性剤を組成物に対して、０．００１重量％〜５重量％含有した組成物が好ましく、更に好ましくは０．００５重量％〜１重量％、より好ましくは０．０１重量％〜０．５重量％含有した組成物である。
【００１７】
該組成物の製造方法としては、該ハロゲン化炭化水素に該界面活性剤を添加し、攪拌混合することにより得る方法を例示できる。
【００１８】
次に特定粒径の球状セルロ−スを製造するための本発明の組成物を用いた例について説明する。
【００１９】
チオシアン酸カルシウム水溶液に粉末状のセルロースを加えたセルロース溶解液を製造し、２５℃で30〜60分間、攪拌する。その後、90℃まで昇温し、そのまま30分間保持させた後110℃まで昇温し、該溶解液が透明になっている事を確認する。別途、ハロゲン化炭化水素に界面活性剤を添加し攪拌混合して本発明の組成物を調製し、その後、攪拌を続けながら130℃まで昇温する。次いで、攪拌羽根の回転速度を約250rpmの条件下で該組成物を攪拌しながら、上記のセルロース溶解液を該組成物に滴下する。滴下終了後に、セルロース溶解液と組成物の混合液を40℃まで冷却し、更にメタノールを添加し、濾過にて溶液とセルロース粒子を分離する。分離されたセルロース粒子を更に精製水にて洗浄する。得られたセルロース粒子を目開き３００μｍの篩いに掛け、その後目開き５００μｍの篩いに掛けて、目的とする粒径が３００〜５００μｍの球状セルロースを得る。
【００２０】
【実施例】
以下、実施例により本発明をより詳細に説明する。
実施例に用いた評価方法を下記に示す。
（１）収率
製造に用いた粉末状のセルロースと得られた粒径が３００〜５００μｍの球状セルロース粒子の各重量の百分率を求め収率とした。
【００２１】
（２）粒径測定
株式会社堀場製作所製 レーザー回析／散乱式粒度分布測定装置 LA―９１０を用いて得られたセルロ−ス粒子の中の３００μ〜５００μの粒径の重量を測定した。
【００２２】
（３）水分率（重量％）
水分を含有しているセルロースを１０分以上吸引濾過した後に、正確に１０ｇを計量し、８０℃中に２４時間放置し、水分を蒸発させる。このセルロースの重量を計量して、セルロース中に含有する水分の百分率を求め、水分率とした。
【００２３】
実施例１
６０重量％チオシアン酸カルシウム水溶液２５０ｍｌ中に平均分子量１万、水分率９０．５重量％の粉末状のセルロース２５０ｇを加えたセルロース溶解液を製造し、２５℃で４５分間攪拌し、その後90℃まで昇温した。９０℃で30分保持させた後、110℃まで昇温し、該溶解液が透明になっている事を目視にて確認した。別途、ハロゲン化炭化水素として、オルトジクロロベンゼン2000ｇ中に、親水性親油性バランスが５のエマレックスSS-5050K（商標、日本エマルジョン株式会社製）の界面活性剤を2ｇ添加して攪拌混合し、本発明の組成物を製造し、その後、攪拌を続けながら130℃まで昇温する。攪拌羽根の回転速度265rpmの条件下で、上記で製造した組成物に、上記で製造したセルロース溶解液を滴下した。滴下終了後に、セルロース溶解液および組成物の混合液を40℃まで冷却し、更にメタノールを添加し、濾過により、溶液とセルロースとを分離した。分離されたセルロースを更にメタノールで３回、精製水で３回洗浄した。得られたセルロースを目開き５００μｍの篩いに掛け、次いで目開き３００μｍの篩いに掛けて、粒径が３００〜５００μｍ、水分率９０．３重量％の球状セルロース８０ｇを得た。収率は３２重量％であった。
【００２４】
実施例２
界面活性剤の添加量を6ｇに変更した以外は、上記実施例１に準拠して、粒径が３００〜５００μｍ、水分率が９０．４重量％の球状セルロース５５ｇを得た。収率は２２重量％であった。
【００２５】
実施例３
界面活性剤の添加量を1ｇに変更した以外は、実施例１に準拠して、粒径が３００〜５００μｍ、水分率９０．２重量％の球状セルロース４７．５ｇを得た。収率は１９重量％であった。
【００２６】
比較例１
界面活性剤を、ソルビタンモノオレエート（日本油脂株式会社製、）に変更した以外は、上記実施例１に準拠して、粒径が３００〜５００μｍ、水分率９０．６重量％の球状セルロース２２．５ｇを得た。収率は９重量％であった。
【００２７】
比較例２
界面活性剤を、ステアリン酸ステアリル（日本エマルジョン株式会社製）に変更した以外は、上記実施例１に準拠してセルロ−スを製造した。粒径が１ｍｍ以上の球状セルロースしか得られず、結果的に粒径が３００〜５００μｍの球状セルロースは得られなかった。
【００２８】
比較例３
界面活性剤を、ラウロイルグルタミン酸ジオクチルドデシル（日本エマルジョン株式会社製）に変更した以外は、上記実施例１に準拠してセルロ−スを製造した。粒径が１ｍｍ以上の球状セルロースしか得られず、結果的に粒径が３００〜５００μｍの球状セルロースは得られなかった。
【００２９】
【発明の効果】
本発明の組成物を、球状セルロースを製造する際に使用すると、粒径が３００〜５００μｍの球状セルロース粒子を高い収率で得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a halogenated hydrocarbon suitable for producing a spherical cellulose having a specific particle size in a high yield from a cellulose solution produced by adding powdered cellulose to an aqueous calcium thiocyanate solution . The present invention relates to a composition containing a surfactant.
[0002]
[Prior art]
Conventionally, obtaining a cellulose having a specific particle size has been studied. For example, JP-A-10-195103 discloses a method for producing porous spherical cellulose using O-dichlorobenzene containing sorbitan monooleate as a solvent. However, these conventional methods have a problem that it is difficult to obtain spherical cellulose having a particle size of 300 to 500 μm in a high yield.
[0003]
[Problems to be solved by the invention]
The present inventors have intensively studied to solve the above problems. As a result, a composition containing a halogenated hydrocarbon and a specific surfactant when producing spherical cellulose having a particle size of 300 to 500 μm from a cellulose solution prepared by adding powdered cellulose to an aqueous calcium thiocyanate solution. It was found that a spherical cellulose having the particle size can be obtained in a high yield when the product is used, and the present invention has been completed based on this finding. As apparent from the above description, an object of the present invention, when the particle size of the cellulose solution to produce a spherical cellulose 300 to 500 [mu] m, spherical cellulose of the particle diameter - to obtain a scan with a high yield It is providing the composition suitable for.
[0004]
[Means for Solving the Problems]
The present invention is configured as follows.
(1) A composition used for producing spherical cellulose from a cellulose solution prepared by adding powdery cellulose to an aqueous calcium thiocyanate solution , and comprising a halogenated hydrocarbon, methylpolysiloxane as a hydrophobic group, and A composition comprising a polyoxyethylene / methylpolysiloxane copolymer having a structure having polyoxyethylene as a hydrophilic group, and a surfactant having a hydrophilic / lipophilic balance of 4 to 6.
[0005]
(2) The composition according to item (1), wherein the content of the surfactant is 0.001% by weight to 5% by weight with respect to the composition.
[0006]
(3) The composition according to (1) or (2) above, wherein the halogenated hydrocarbon is dichloroethane, dichlorobenzene, orthodichlorobenzene, or a mixture of one or more thereof.
[0007]
(4) the (1) to (3) in the composition according to any one of claim, transparent cellulose dissolution obtained was heated to agitated with addition of powdered cellulose thiocyanate aqueous solution of calcium the liquid was added dropwise with 攪拌, a mixture of cellulose solution and the composition after completion of the dropwise addition, methanol was added, the cellulose particles were separated by filtration, with purified water separated cellulose particles A method for producing spherical cellulose, which is obtained by washing and sieving the obtained cellulose particles to obtain spherical cellulose having a target particle size.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below. Spherical cellulose solution of the present invention cellulose - in the composition used in producing the scan or no affinity for water, or not soluble in water, the spherical cellulose in certain particle size obtained yield in terms of increasing the rate, halogenated hydrocarbons are used. Preferred examples of the halogenated hydrocarbon include dichloroethane, dichlorobenzene, and orthodichlorobenzene. The orthodichlorobenzene is, for example, a commercially available product manufactured by Wako Pure Chemical Industries, Ltd. and Mitsui Chemicals. Can be used.
[0011]
Surfactant used in the present invention, Ru surfactant der structure having a polyoxyethylene as methyl polysiloxane and a hydrophilic group as a hydrophobic group.
[0013]
Specific examples of such surfactants include Emulex SS-5050K (trademark, manufactured by Nihon Emulsion Co., Ltd.) and Emarex SS-8020K (trademark, manufactured by Nihon Emulsion Co., Ltd.), which are polyoxyethylene / methylpolysiloxane copolymers. Can be exemplified.
[0014]
The hydrophilic / lipophilic balance of the surfactant is preferably 4-6, more preferably 4.5-5.5, from the viewpoint that spherical cellulose having a specific particle size is obtained in a high yield. is there.
[0015]
Next, the hydrophilic / lipophilic balance of the surfactant will be described.
Each of the various actions such as emulsification, dispersion, washing and foaming exhibited by the surfactant is a two-phase interface. It is considered that the degree of balance required varies depending on the above phenomena, and the optimum condition depends on the number required for each surfactant. This can be realized by matching the number of regions. In accordance with this idea, the number determined from the balance between the hydrophilic group and the lipophilic group of the surfactant molecule is called the hydrophilic / lipophilic balance, so-called HLB (HLB). The system mechanism that determines the surfactant and the composition suitable for the purpose from such a calculation is sometimes called an HLB system. The HLB is empirically classified into numerical values from 1 to 40 based on oil emulsification experiments, and the smaller the number, the higher the lipophilicity.
[0016]
The composition used when producing spherical cellulose from the cellulose solution of the present invention is a composition in which the above-mentioned surfactant is contained in the above-mentioned halogenated hydrocarbon , and has a specific particle size in a high yield. From the viewpoint of obtaining spherical cellulose, a composition containing 0.001 to 5% by weight of a surfactant with respect to the composition is preferable, more preferably 0.005 to 1% by weight, and more. A composition containing 0.01% to 0.5% by weight is preferred.
[0017]
Examples of the method for producing the composition include a method obtained by adding the surfactant to the halogenated hydrocarbon and stirring and mixing.
[0018]
Then spherical cellulose in certain particle size - example will be described using a set formed of the present invention for producing a scan.
[0019]
To produce a cellulose scan solution was added powdered cellulose thiocyanate aqueous solution of calcium, for 30-60 minutes at 25 ° C., stirred. Thereafter, the temperature is raised to 90 ° C., kept as it is for 30 minutes, and then raised to 110 ° C. to confirm that the solution is transparent. Separately, a surfactant is added to the halogenated hydrocarbon and mixed by stirring to prepare the composition of the present invention, and then the temperature is raised to 130 ° C. while continuing stirring. Next, the cellulose solution is added dropwise to the composition while stirring the composition under the condition that the rotation speed of the stirring blade is about 250 rpm. After completion of dropping, the mixed solution of the cellulose solution and the composition is cooled to 40 ° C., methanol is further added, and the solution and cellulose particles are separated by filtration. The separated cellulose particles are further washed with purified water. The obtained cellulose particles are passed through a sieve having an opening of 300 μm, and then passed through a sieve having an opening of 500 μm to obtain spherical cellulose having a target particle size of 300 to 500 μm.
[0020]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
The evaluation methods used in the examples are shown below.
(1) Yield The percentage of each weight of the powdery cellulose used for production and the obtained spherical cellulose particles having a particle size of 300 to 500 μm was determined and used as the yield.
[0021]
(2) Particle size measurement The weight of the particle size of 300 micrometers-500 micrometers among the cellulose particles obtained using the laser diffraction / scattering type particle size distribution measuring device LA-910 by Horiba, Ltd. was measured.
[0022]
(3) Moisture content (wt%)
After cellulose containing water is suction filtered for 10 minutes or more, 10 g is accurately weighed and left at 80 ° C. for 24 hours to evaporate the water. The weight of this cellulose was measured, the percentage of moisture contained in the cellulose was determined, and the moisture content was determined.
[0023]
Example 1
60 wt% thiocyanate aqueous solution of calcium 250ml average molecular weight of 10,000 during the manufacture water content 90.5% by weight of powdered cellulose scan lysate plus cellulose 250g of stirred for 45 minutes at 25 ° C., then 90 ° C. The temperature was raised to. After maintaining at 90 ° C. for 30 minutes, the temperature was raised to 110 ° C., and it was visually confirmed that the solution was transparent. Separately, 2 g of Emarex SS-5050K (trademark, manufactured by Nihon Emulsion Co., Ltd.) surfactant with a hydrophilic / lipophilic balance of 5 is added to 2000 g of orthodichlorobenzene as a halogenated hydrocarbon , and stirred and mixed. The composition of the present invention is produced, and then the temperature is raised to 130 ° C. while stirring is continued. The cellulose solution produced above was added dropwise to the composition produced above under the condition that the rotation speed of the stirring blade was 265 rpm. After completion of the dropwise addition, the mixed solution of the cellulose solution and the composition was cooled to 40 ° C., methanol was further added, and the solution and the cellulose were separated by filtration. The separated cellulose was further washed 3 times with methanol and 3 times with purified water. The obtained cellulose was passed through a sieve having an opening of 500 μm, and then passed through a sieve having an opening of 300 μm to obtain 80 g of spherical cellulose having a particle size of 300 to 500 μm and a water content of 90.3 wt%. The yield was 32% by weight.
[0024]
Example 2
Except for changing the addition amount of the surfactant to 6 g, 55 g of spherical cellulose having a particle size of 300 to 500 μm and a moisture content of 90.4% by weight was obtained in accordance with Example 1 above. The yield was 22% by weight.
[0025]
Example 3
Except for changing the addition amount of the surfactant to 1 g, 47.5 g of spherical cellulose having a particle size of 300 to 500 μm and a water content of 90.2 wt% was obtained in accordance with Example 1. The yield was 19% by weight.
[0026]
Comparative Example 1
Spherical cellulose 22 having a particle size of 300 to 500 μm and a moisture content of 90.6% by weight is based on Example 1 except that the surfactant is changed to sorbitan monooleate (manufactured by Nippon Oil & Fats Co., Ltd.). .5 g was obtained. The yield was 9% by weight.
[0027]
Comparative Example 2
Cellulose was produced according to Example 1 except that the surfactant was changed to stearyl stearate (manufactured by Nippon Emulsion Co., Ltd.). Only spherical cellulose having a particle size of 1 mm or more was obtained, and as a result, spherical cellulose having a particle size of 300 to 500 μm was not obtained.
[0028]
Comparative Example 3
Cellulose was produced according to Example 1 except that the surfactant was changed to dioctyldodecyl lauroyl glutamate (manufactured by Nippon Emulsion Co., Ltd.). Only spherical cellulose having a particle size of 1 mm or more was obtained, and as a result, spherical cellulose having a particle size of 300 to 500 μm was not obtained.
[0029]
【The invention's effect】
When the composition of the present invention is used in producing spherical cellulose, spherical cellulose particles having a particle size of 300 to 500 μm can be obtained with a high yield.
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