JP2010037526A - Process for producing low crystalline cellulose - Google Patents
Process for producing low crystalline cellulose Download PDFInfo
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- JP2010037526A JP2010037526A JP2008205799A JP2008205799A JP2010037526A JP 2010037526 A JP2010037526 A JP 2010037526A JP 2008205799 A JP2008205799 A JP 2008205799A JP 2008205799 A JP2008205799 A JP 2008205799A JP 2010037526 A JP2010037526 A JP 2010037526A
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- cellulose
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- low crystalline
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 177
- 239000001913 cellulose Substances 0.000 title claims abstract description 177
- 238000000034 method Methods 0.000 title abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 71
- 239000002245 particle Substances 0.000 claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 5
- 238000010298 pulverizing process Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 8
- 150000004676 glycans Chemical class 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims 1
- 239000002609 medium Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
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- 238000011049 filling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010903 husk Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 239000002028 Biomass Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229920001131 Pulp (paper) Polymers 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
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- 230000008025 crystallization Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- 229960002218 sodium chlorite Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 235000019698 starch Nutrition 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
本発明は、平均粒径の小さい低結晶性セルロースの製造方法に関する。 The present invention relates to a method for producing a low crystalline cellulose having a small average particle size.
パルプ等のセルロース含有原料を粉砕して得られるセルロースは、セルロースエーテルの原料、化粧品、食品、バイオマス材料等の工業原料として用いられる。これらの工業原料としては、セルロース結晶構造が低結晶化されたセルロースが特に有用である。
例えば、シート状パルプを粉砕機で機械的に処理して、粉末状パルプを製造する方法が知られている（特許文献１及び２参照）。しかし、これらの特許文献にはセルロースの結晶化度についての記載はない。
また、パルプを粉砕機で機械的に処理して、セルロースの結晶化度を低減する方法が知られている（特許文献３〜６参照）。
特許文献３の実施例１及び４には、シート状パルプを振動ボールミル又は二軸押出機で処理する方法が開示されており、特許文献４の実施例１〜３には、パルプをボールミルで処理する方法が開示されている。
特許文献５の実施例１及び２には、パルプを加水分解等の化学的処理をして得られたセルロース粉体を、ボールミルさらには気流式粉砕機で処理する方法が開示されており、特許文献６には、パルプを水に分散させた状態で振動ボールミル等の媒体ミルで処理する方法が開示されている。
しかし、これらの方法は、セルロースの結晶化度及び平均粒径を低減させるにあたり、効率性及び生産性において満足できるものではない。
Cellulose obtained by pulverizing cellulose-containing raw materials such as pulp is used as industrial raw materials such as cellulose ether raw materials, cosmetics, foods, and biomass materials. As these industrial raw materials, cellulose having a low crystallized cellulose crystal structure is particularly useful.
For example, a method is known in which sheet-like pulp is mechanically processed by a pulverizer to produce powdered pulp (see Patent Documents 1 and 2). However, these patent documents do not describe the crystallinity of cellulose.
Moreover, the method of processing a pulp mechanically with a grinder and reducing the crystallinity degree of a cellulose is known (refer patent documents 3-6).
Examples 1 and 4 of Patent Document 3 disclose a method of treating sheet pulp with a vibrating ball mill or a twin screw extruder, and Examples 1 to 3 of Patent Document 4 treat pulp with a ball mill. A method is disclosed.
Examples 1 and 2 of Patent Document 5 disclose a method in which cellulose powder obtained by chemical treatment such as hydrolysis of pulp is treated with a ball mill or an airflow pulverizer. Document 6 discloses a method of treating a pulp with a medium mill such as a vibration ball mill in a state where the pulp is dispersed in water.
However, these methods are not satisfactory in terms of efficiency and productivity in reducing the crystallinity and average particle size of cellulose.
本発明は、セルロース含有原料からセルロースＩ型結晶化度及びセルロースの平均粒径を低減させた低結晶性セルロースを効率的に得ることができる、生産性に優れた製造方法を提供することを課題とする。 It is an object of the present invention to provide a production method excellent in productivity capable of efficiently obtaining low crystalline cellulose in which cellulose I-type crystallinity and average cellulose particle size are reduced from a cellulose-containing raw material. And
本発明者らは、特定のセルロース含有原料を粉砕助剤と共に粉砕機で処理することにより、前記課題を解決できることを見出した。
すなわち、本発明は、下記式（１）で示されるセルロースのセルロースＩ型結晶化度が３３％を超えるセルロース含有原料から平均粒径１０〜２００μｍの低結晶性セルロースを製造する方法であって、該セルロース含有原料から水を除いた残余の成分中のセルロース含有量が２０質量％以上であって、該セルロース含有原料を粉砕助剤と共に粉砕機で処理して、該セルロースＩ型結晶化度を３３％以下に低減する、低結晶性セルロースの製造方法である。
セルロースＩ型結晶化度（％）＝〔（Ｉ22.6−Ｉ18.5）／Ｉ22.6〕×１００ （１）
〔式中、Ｉ22.6は、Ｘ線回折における格子面（００２面）（回折角２θ＝２２．６°）の回折強度、及びＩ18.5は、アモルファス部（回折角２θ＝１８．５°）の回折強度を示す。〕
The present inventors have found that the above-mentioned problems can be solved by treating a specific cellulose-containing raw material together with a grinding aid with a grinding machine.
That is, the present invention is a method for producing low crystalline cellulose having an average particle size of 10 to 200 μm from a cellulose-containing raw material having a cellulose I-type crystallinity of 33% or more represented by the following formula (1), The cellulose content in the remaining components obtained by removing water from the cellulose-containing raw material is 20% by mass or more, and the cellulose-containing raw material is treated with a pulverization aid by a pulverizer to obtain the cellulose I-type crystallinity. This is a method for producing low crystalline cellulose, which is reduced to 33% or less.
Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] × 100 (1)
[Wherein I 22.6 is the diffraction intensity of the grating plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I 18.5 is the amorphous portion (diffraction angle 2θ = 18.5 °). The diffraction intensity is shown. ]
本発明の低結晶性セルロースの製造方法によれば、セルロース含有原料から、セルロースＩ型結晶化度及びセルロースの平均粒径を低減させた低結晶性セルロースを効率的に、生産性よく得ることができる。 According to the method for producing low crystalline cellulose of the present invention, low crystalline cellulose in which cellulose I-type crystallinity and the average particle size of cellulose are reduced can be efficiently obtained from a cellulose-containing raw material with high productivity. it can.
本発明の低結晶性セルロースの製造方法は、上記式（１）で示されるセルロースのセルロースＩ型結晶化度が３３％を超えるセルロース含有原料から平均粒径１０〜２００μｍの低結晶性セルロースを製造する方法であって、該セルロース含有原料から水を除いた残余の成分中のセルロース含有量が２０質量％以上であって、該セルロース含有原料を粉砕助剤と共に粉砕機で処理して、該セルロースＩ型結晶化度を３３％以下に低減することを特徴とする。 The method for producing low crystalline cellulose of the present invention produces low crystalline cellulose having an average particle size of 10 to 200 μm from a cellulose-containing raw material having a cellulose I-type crystallinity exceeding 33% represented by the formula (1). The cellulose content in the remaining components obtained by removing water from the cellulose-containing raw material is 20% by mass or more, and the cellulose-containing raw material is treated with a grinding aid in a pulverizer, and the cellulose The type I crystallinity is reduced to 33% or less.
〔セルロース含有原料〕
セルロースには幾つかの結晶構造が知られており、結晶領域（アモルファス部と結晶部）の全量に対する結晶部の割合から、一般に結晶化度が算出される。
本発明に用いられるセルロース含有原料は、上記式（１）で示されるセルロースのセルロースＩ型結晶化度が３３％を超えるものである。一般的な市販パルプは、該結晶化度が概ね６０％以上のいわゆる結晶性のセルロースである。
また、本発明に用いられるセルロース含有原料は、該原料から水を除いた残余の成分中のセルロース含有量が２０質量％以上、好ましくは４０質量％以上、より好ましくは６０質量％以上のものである。ここで、セルロース含有量とはセルロース量及びヘミセルロース量の合計量を意味する。
市販のパルプの場合、水を除いた残余の成分中のセルロース含有量は、一般には７５〜９９質量％であり、他の成分はリグニン等を含む。
[Cellulose-containing raw material]
Several crystal structures are known for cellulose, and the crystallinity is generally calculated from the ratio of crystal parts to the total amount of crystal regions (amorphous part and crystal part).
In the cellulose-containing raw material used in the present invention, the cellulose I-type crystallinity of the cellulose represented by the above formula (1) exceeds 33%. A common commercial pulp is so-called crystalline cellulose having a crystallinity of approximately 60% or more.
Further, the cellulose-containing raw material used in the present invention has a cellulose content in the remaining components excluding water from the raw material of 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more. is there. Here, the cellulose content means the total amount of cellulose and hemicellulose.
In the case of commercially available pulp, the cellulose content in the remaining components excluding water is generally 75 to 99% by mass, and other components include lignin and the like.
前記セルロース含有原料には特に制限はなく、各種木材チップ；木材から製造されるウッドパルプ、綿の種子の周囲の繊維から得られるコットンリンターパルプ等のパルプ類；新聞紙、ダンボール、雑誌、上質紙等の紙類；稲わら、とうもろこし茎等の植物茎・葉類；籾殻、パーム殻、ココナッツ殻等の植物殻類等が挙げられる。
セルロース含有原料中の水分含量は、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下が更に好ましい。セルロース含有原料中の水分含量が２０質量％以下であれば、容易に粉砕できるとともに、粉砕処理により結晶化度を容易に低減させることができる。
There is no restriction | limiting in particular in the said cellulose containing raw material, Various wood chips; Pulp, such as wood pulp manufactured from wood, the cotton linter pulp obtained from the fiber around cotton seeds; Newspaper, corrugated cardboard, magazine, fine paper, etc. Paper stalks; plant stems and leaves such as rice straw and corn stalks; plant shells such as rice husks, palm husks and coconut husks.
The water content in the cellulose-containing raw material is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. If the water content in the cellulose-containing raw material is 20% by mass or less, it can be easily pulverized and the crystallinity can be easily reduced by pulverization.
セルロース含有原料の嵩密度は、好ましくは１００ｋｇ／ｍ3以上、より好ましくは１２０ｋｇ／ｍ3以上、更に好ましくは１５０ｋｇ／ｍ3以上である。該嵩密度が１００ｋｇ／ｍ3以上であれば、セルロース含有原料が適度な容積を有するために取扱い性が向上し、また、粉砕機へ原料仕込み量を多くすることができるので処理能力が向上する。一方、該嵩密度の上限は、取扱い性及び生産性の観点から、好ましくは５００ｋｇ／ｍ3以下、より好ましくは４００ｋｇ／ｍ3以下、更に好ましくは３５０ｋｇ／ｍ3以下である。これらの観点から、該嵩密度は、好ましくは１００〜５００ｋｇ／ｍ3、より好ましくは１２０〜４００ｋｇ／ｍ3、更に好ましくは１５０〜３５０ｋｇ／ｍ3である。
嵩密度が１００ｋｇ／ｍ3未満のセルロース含有原料を用いる場合には、後述するように前処理を行うことが好ましい。
The bulk density of the cellulose-containing raw material is preferably 100 kg / m 3 or more, more preferably 120 kg / m 3 or more, still more preferably 150 kg / m 3 or more. When the bulk density is 100 kg / m 3 or more, the cellulose-containing raw material has an appropriate volume, so that the handleability is improved, and the processing capacity is improved because the raw material charge amount can be increased to the pulverizer. . On the other hand, the upper limit of the bulk density is preferably 500 kg / m 3 or less, more preferably 400 kg / m 3 or less, and still more preferably 350 kg / m 3 or less from the viewpoints of handleability and productivity. From these viewpoints, the bulk density is preferably 100 to 500 kg / m 3 , more preferably 120 to 400 kg / m 3 , and still more preferably 150 to 350 kg / m 3 .
When a cellulose-containing raw material having a bulk density of less than 100 kg / m 3 is used, pretreatment is preferably performed as described later.
また、セルロース含有原料の平均粒径は、好ましくは１ｍｍ以下、より好ましくは０．７ｍｍ以下、更に好ましくは０．５ｍｍ以下である。該平均粒径が１ｍｍ以下であれば、粉砕機中に供給する際に、粉砕機中にセルロース含有原料を効率的に分散させることができ、長時間を要することなく所定の粒径に到達することができる。一方、該平均粒径の下限は、生産性の観点から、好ましくは０．０１ｍｍ以上、より好ましくは０．０５ｍｍ以上である。これらの観点から、該平均粒径は、好ましくは０．０１〜１ｍｍ、より好ましくは０．０１〜０．７ｍｍ、更に好ましくは０．０５〜０．５ｍｍである。
なお、セルロース含有原料の嵩密度及び平均粒径は、実施例に記載の方法により測定することができる。
The average particle size of the cellulose-containing raw material is preferably 1 mm or less, more preferably 0.7 mm or less, and still more preferably 0.5 mm or less. When the average particle size is 1 mm or less, the cellulose-containing raw material can be efficiently dispersed in the pulverizer when it is fed into the pulverizer, and reaches a predetermined particle size without requiring a long time. be able to. On the other hand, the lower limit of the average particle diameter is preferably 0.01 mm or more, more preferably 0.05 mm or more, from the viewpoint of productivity. From these viewpoints, the average particle diameter is preferably 0.01 to 1 mm, more preferably 0.01 to 0.7 mm, and still more preferably 0.05 to 0.5 mm.
In addition, the bulk density and average particle diameter of a cellulose containing raw material can be measured by the method as described in an Example.
〔低結晶性セルロース〕
本発明方法により製造される低結晶性セルロースは、セルロースＩ型結晶化度を３３％以下に低減させたものである。
一般的な市販パルプは、結晶化度が概ね６０％以上のいわゆる結晶性セルロースであるが、本発明により得られるセルロースは低結晶性セルロースである。
ここで、本発明における結晶化度とは、天然セルロースの結晶構造に由来するＩ型の結晶化度を意味し、粉末Ｘ線結晶回折スペクトル法による回折強度値からＳｅｇａｌ法により算出したもので、下記式（１）により定義される。
セルロースＩ型結晶化度（％）＝〔（Ｉ22.6−Ｉ18.5）／Ｉ22.6〕×１００ （１）
〔式中、Ｉ22.6は、Ｘ線回折における格子面（００２面）（回折角２θ＝２２．６°）の回折強度、及びＩ18.5は、アモルファス部（回折角２θ＝１８．５°）の回折強度を示す。〕
また、「低結晶性」とは、セルロースの結晶構造においてアモルファス部の割合が多い状態を示し、具体的には上記式（１）から算出されるセルロースＩ型結晶化度が３３％以下であることを意味し、該結晶化度が０％の完全非晶化の場合を含む。
なお、本明細書において、セルロースのセルロースＩ型結晶化度を単に「結晶化度」ということがある。
[Low crystalline cellulose]
The low crystalline cellulose produced by the method of the present invention has a cellulose I-type crystallinity reduced to 33% or less.
A general commercial pulp is a so-called crystalline cellulose having a crystallinity of approximately 60% or more, but the cellulose obtained by the present invention is a low crystalline cellulose.
Here, the crystallinity in the present invention means the crystallinity of type I derived from the crystal structure of natural cellulose, and is calculated by the Segal method from the diffraction intensity value by the powder X-ray crystal diffraction spectrum method, It is defined by the following formula (1).
Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] × 100 (1)
[Wherein I 22.6 is the diffraction intensity of the grating plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I 18.5 is the amorphous portion (diffraction angle 2θ = 18.5 °). The diffraction intensity is shown. ]
Further, “low crystallinity” indicates a state in which the ratio of the amorphous part is large in the crystal structure of cellulose, and specifically, the cellulose I-type crystallinity calculated from the above formula (1) is 33% or less. This includes the case where the crystallinity is 0%.
In the present specification, the cellulose type I crystallinity of cellulose is sometimes simply referred to as “crystallinity”.
結晶化度は、セルロースの物理的、化学的性質とも関係し、その値が大きいほど、セルロースの結晶性が高く、非結晶部分が少ないため、硬度、密度等は増すが、伸び、柔軟性、水や溶媒に対する溶解性、化学反応性は低下する。結晶化度が３３％以下であれば、セルロースの化学反応性が十分であり、例えば、セルロースエーテルの製造において、アルカリを加えた際にアルカリセルロース化が容易に進行し、結果としてセルロースエーテル化反応の反応転化率を向上させることができる。この観点から、結晶化度は、２５％以下が好ましく、１５％以下がより好ましく、分析でＩ型結晶が検出されない０％が特に好ましい。なお、式（１）で定義されたセルロースＩ型結晶化度では計算上マイナスの値になる場合があるが、マイナスの値の場合はセルロースＩ型結晶化度は０％とする。 The degree of crystallinity is also related to the physical and chemical properties of cellulose, and the larger the value, the higher the crystallinity of the cellulose and the less non-crystalline parts. Solubility and chemical reactivity in water and solvent decrease. If the degree of crystallinity is 33% or less, the chemical reactivity of cellulose is sufficient. For example, in the production of cellulose ether, alkali celluloseation proceeds easily when an alkali is added, resulting in cellulose etherification reaction. The reaction conversion rate can be improved. From this viewpoint, the degree of crystallinity is preferably 25% or less, more preferably 15% or less, and particularly preferably 0% at which no type I crystal is detected by analysis. The cellulose I type crystallinity defined by the formula (1) may be a negative value in calculation, but in the case of a negative value, the cellulose I type crystallinity is 0%.
本発明により得られる低結晶性セルロースの平均粒径は、低結晶性セルロースを工業原料として用いる際の化学反応性及び取扱い性の観点から、１０〜２００μｍであり、好ましくは１２〜１５０μｍ、より好ましくは１４〜１００μｍ、更に好ましくは１５〜７５μｍ、特に好ましくは１５〜６０μｍである。特に平均粒径が１０μｍ以上であれば、低結晶性セルロースを水などの液体と接触させたときに「ママコ」になることを抑えることができる。 The average particle size of the low crystalline cellulose obtained by the present invention is 10 to 200 μm, preferably 12 to 150 μm, more preferably from the viewpoint of chemical reactivity and handling when using low crystalline cellulose as an industrial raw material. Is 14 to 100 μm, more preferably 15 to 75 μm, and particularly preferably 15 to 60 μm. In particular, when the average particle size is 10 μm or more, it is possible to suppress the occurrence of “maco” when low crystalline cellulose is brought into contact with a liquid such as water.
〔低結晶性セルロースの製造〕
〔粉砕助剤〕
本発明方法において用いられる粉砕助剤は、多糖類、無機塩、有機酸、有機物、脂肪酸、及び多価アルコールから選ばれる１種以上の化合物である。これらの化合物は、セルロースに対して親和性を有することが好ましい。
多糖類としては、ペンタエリスリトール、グルコース、トレハロース、澱粉等が挙げられ、無機塩としては、炭酸水素ナトリウム、炭酸ナトリウム、硫酸ナトリウム、亜硫酸ナトリウム、塩化ナトリウム等が挙げられる。
有機酸としては、フマル酸、リンゴ酸、コハク酸、アスコルビン酸等が挙げられる。有機物としては、ベントナイト、ポリ乳酸等が挙げられ、脂肪酸としては、ステアリン酸、ラウリル酸等が挙げられ、多価アルコールとしては、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール等が挙げられる。
上記の粉砕助剤の中では、多糖類、無機塩がより好ましい。
本発明の粉砕助剤中のセルロースの濃度は、セルロースの凝集抑制の観点から、好ましくは１０〜９７質量％、より好ましくは５０〜９７質量％、更に好ましくは７５〜９５質量％である。
[Production of low crystalline cellulose]
[Crushing aid]
The grinding aid used in the method of the present invention is one or more compounds selected from polysaccharides, inorganic salts, organic acids, organic substances, fatty acids, and polyhydric alcohols. These compounds preferably have an affinity for cellulose.
Examples of the polysaccharide include pentaerythritol, glucose, trehalose, and starch, and examples of the inorganic salt include sodium hydrogen carbonate, sodium carbonate, sodium sulfate, sodium sulfite, and sodium chloride.
Examples of the organic acid include fumaric acid, malic acid, succinic acid, ascorbic acid and the like. Examples of the organic substance include bentonite and polylactic acid, examples of the fatty acid include stearic acid and lauric acid, and examples of the polyhydric alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol.
Among the above grinding aids, polysaccharides and inorganic salts are more preferable.
The concentration of cellulose in the grinding aid of the present invention is preferably 10 to 97% by mass, more preferably 50 to 97% by mass, and still more preferably 75 to 95% by mass, from the viewpoint of suppressing cellulose aggregation.
〔前処理〕
本発明において、嵩密度が１００ｋｇ／ｍ3未満のセルロース含有原料を用いる場合は、前処理を行い、嵩密度を１００〜５００ｋｇ／ｍ3にすることが好ましい。
前処理としては、必要に応じて、粗粉砕処理、押出機処理を行い、セルロース含有原料を適度な嵩密度を有する粉末状にすることができる。
粗粉砕処理は、セルロース含有原料を押出機に投入する前に、チップ状に粗粉砕する処理である。この粗粉砕処理を予め行うことにより、押出機処理をより効率的に行うことができる。押出機に供給するセルロース含有原料の大きさは、好ましくは１〜５０ｍｍ角、より好ましくは１〜３０ｍｍ角のチップ状である。
〔Preprocessing〕
In the present invention, when a cellulose-containing raw material having a bulk density of less than 100 kg / m 3 is used, it is preferable to perform a pretreatment so that the bulk density is 100 to 500 kg / m 3 .
As the pretreatment, if necessary, a coarse pulverization treatment and an extruder treatment can be performed to make the cellulose-containing raw material into a powder having an appropriate bulk density.
The coarse pulverization process is a process of coarsely pulverizing the cellulose-containing raw material into chips before putting it into the extruder. By performing this rough pulverization process in advance, the extruder process can be performed more efficiently. The size of the cellulose-containing raw material supplied to the extruder is preferably 1 to 50 mm square, more preferably 1 to 30 mm square.
セルロース含有原料をチップ状に粗粉砕する方法としては、シュレッダー、ロータリーカッター等を使用する方法が挙げられる。ロータリーカッターを使用する場合、得られるチップ状セルロース含有原料の大きさは、スクリーンの目開きを変えることにより、制御することができる。スクリーンの目開きは、１〜５０ｍｍが好ましく、１〜３０ｍｍがより好ましい。スクリーンの目開きが１ｍｍ以上であれば、セルロース含有原料が綿状化することがなく、後の押出機処理に用いるセルロース含有原料として適度な嵩高さを有するために取扱い性が向上する。スクリーンの目開きが５０ｍｍ以下であれば、後の押出機処理に用いるセルロース含有原料として適度な大きさを有するために押出機処理において負荷を低減することができる。 Examples of the method of roughly pulverizing the cellulose-containing raw material into chips include a method using a shredder, a rotary cutter, or the like. When using a rotary cutter, the magnitude | size of the chip-shaped cellulose containing raw material obtained can be controlled by changing the opening of a screen. The opening of the screen is preferably 1 to 50 mm, more preferably 1 to 30 mm. If the opening of the screen is 1 mm or more, the cellulose-containing raw material does not become flocculent, and the handleability is improved because the cellulose-containing raw material has an appropriate bulkiness for use in subsequent extruder processing. If the opening of the screen is 50 mm or less, since it has an appropriate size as a cellulose-containing raw material used in the subsequent extruder processing, the load in the extruder processing can be reduced.
〔押出機処理〕
前記セルロース含有原料を押出機で処理することにより、所望の嵩密度を有するセルロース含有原料を得ることができる。更に押出機で処理することにより、セルロース含有原料に圧縮せん断力を作用させ、セルロースの結晶構造を破壊して粉末化させることができる。
従来よく用いられる衝撃式の粉砕機、例えば、カッターミル、ハンマーミル、ピンミル等は、圧縮せん断力を作用させて機械的に粉砕する装置であるが、これらの粉砕機で処理するとセルロース含有原料が綿状化して嵩高くなり、取扱い性を損ない、質量ベースの処理能力が低下する。これに対して、押出機処理すれば、所望の嵩密度及び平均粒径を有するセルロース含有原料が効率的に得られ、取扱い性が向上する。
(Extruder processing)
By processing the cellulose-containing raw material with an extruder, a cellulose-containing raw material having a desired bulk density can be obtained. Furthermore, by processing with an extruder, a compressive shearing force can be applied to the cellulose-containing raw material, and the crystal structure of cellulose can be destroyed and pulverized.
Conventionally used impact type pulverizers, such as a cutter mill, a hammer mill, and a pin mill, are mechanically pulverized by applying a compressive shear force. It becomes fluffy and bulky, impairing handleability, and lowering the mass-based processing capacity. On the other hand, if it processes with an extruder, the cellulose containing raw material which has a desired bulk density and an average particle diameter will be obtained efficiently, and handleability will improve.
押出機としては、単軸、二軸のどちらの形式でもよいが、搬送能力を高める等の観点から、二軸押出機が好ましい。
二軸押出機としては、シリンダの内部に２本のスクリューが回転自在に挿入された公知の押出機を使用することができる。２本のスクリューの回転方向は、同一でも逆方向でもよいが、搬送能力を高める観点から、同一方向の回転が好ましい。
また、スクリューの噛み合い条件としては、完全噛み合い、部分噛み合い、非噛み合いの各形式の押出機のいずれでもよいが、処理能力を向上させる観点から、完全噛み合い型、部分噛み合い型が好ましい。
The extruder may be either a single-screw type or a twin-screw type, but a twin-screw extruder is preferable from the viewpoint of increasing the conveyance capability.
As the twin screw extruder, a known extruder in which two screws are rotatably inserted into a cylinder can be used. The rotation directions of the two screws may be the same or opposite directions, but the rotation in the same direction is preferable from the viewpoint of increasing the conveyance capability.
Further, as the meshing conditions of the screw, any of full-engagement, partial meshing, and non-meshing extruders may be used, but from the viewpoint of improving the processing capability, the complete meshing type and the partial meshing type are preferable.
押出機としては、強い圧縮せん断力を加える観点から、スクリューのいずれかの部分に、いわゆるニーディングディスク部を備えることが好ましい。
ニーディングディスク部とは、複数のニーディングディスクで構成され、これらを連続して、一定の位相でずらしながら組み合わせたものである。例えば３〜２０、好ましくは６〜１６のニーディングディスクを９０°ずつ互い違いにずらしながら組み合わせたものが挙げられる。ニーディングディスク部は、スクリューの回転にともなって、その狭い隙間にセルロース含有原料を強制的に通過させることで極めて強いせん断力を付与することができる。
押出機のスクリューの構成としては、ニーディングディスク部と複数のスクリューセグメントとを交互に配置することが好ましい。また、二軸押出機の場合は、２本のスクリューを同一の構成とすることが好ましい。
As an extruder, it is preferable to provide what is called a kneading disk part in any part of a screw from a viewpoint of applying a strong compressive shear force.
The kneading disc portion is composed of a plurality of kneading discs, which are combined while being shifted at a constant phase. For example, 3-20, preferably 6-16 kneading discs may be combined while being staggered by 90 °. The kneading disk portion can impart a very strong shearing force by forcibly passing the cellulose-containing raw material through the narrow gap as the screw rotates.
As a configuration of the screw of the extruder, it is preferable to alternately arrange the kneading disk portions and the plurality of screw segments. In the case of a twin screw extruder, it is preferable that the two screws have the same configuration.
処理方法としては、セルロース含有原料、好ましくは前記チップ状セルロース含有原料を押出機に投入し、連続的に処理する方法が好ましい。せん断速度としては、１０ｓｅｃ-1以上が好ましく、２０〜３００００ｓｅｃ-1がより好ましく、５０〜３０００ｓｅｃ-1が更に好ましい。せん断速度が１０ｓｅｃ-1以上であれば、有効に高嵩密度化が進行する。その他の処理条件に特に制限はなく、処理温度は好ましくは５〜２００℃である。
また、押出機処理によるパス回数としては、１パスでも十分効果を得ることができるが、セルロース含有原料を高嵩密度化する観点から、１パスで不十分な場合は、２パス以上行うことが好ましい。生産性の観点からは、１〜１０パスが好ましい。処理回数を重ねることにより、粗大粒子が粉砕され、粒径のばらつきが少ない粉末状セルロース含有原料を得ることができる。２パス以上行う場合は、生産能力を考慮し、複数の押出機を直列に並べて処理を行ってもよい。
As a treatment method, a method in which a cellulose-containing raw material, preferably the chip-like cellulose-containing raw material is charged into an extruder and continuously processed is preferable. The shear rate is preferably 10 sec −1 or more, more preferably 20 to 30000 sec −1, and still more preferably 50 to 3000 sec −1 . If the shear rate is 10 sec −1 or more, the bulk density is effectively increased. There is no restriction | limiting in particular in other process conditions, Preferably process temperature is 5-200 degreeC.
Moreover, as the number of passes by the extruder treatment, a sufficient effect can be obtained even with one pass, but from the viewpoint of increasing the bulk density of the cellulose-containing raw material, two passes or more may be performed if one pass is insufficient. preferable. From the viewpoint of productivity, 1 to 10 passes are preferable. By repeating the treatment, coarse particles are pulverized and a powdery cellulose-containing raw material with little variation in particle size can be obtained. When performing two or more passes, the processing may be performed by arranging a plurality of extruders in series in consideration of production capacity.
〔粉砕機処理（低結晶化処理）〕
本発明においては、必要に応じて、前記の前処理、押出機処理を行い、セルロース含有原料から水を除いた残余の成分中のセルロース含有量が２０質量％以上であるセルロース含有原料を、粉砕助剤と共に粉砕機で処理して、該セルロースの結晶化度を３３％以下に低減し、平均粒径を１０〜２００μｍに調整する。
なお、前記のとおり、粉砕機に供給するセルロース含有原料の嵩密度は好ましくは１００〜５００ｋｇ／ｍ3であり、その平均粒径は好ましくは０．０１〜１ｍｍであり、かかるセルロース含有原料を粉砕助剤と共に粉砕機で粉砕処理することにより、結晶化度及び平均粒径を低減させ、セルロースを効率的に低結晶化させることができる。
[Crusher treatment (low crystallization treatment)]
In the present invention, if necessary, the pretreatment and the extruder treatment are performed, and the cellulose-containing raw material in which the cellulose content in the remaining components obtained by removing water from the cellulose-containing raw material is 20% by mass or more is pulverized. By processing with a pulverizer together with an auxiliary agent, the crystallinity of the cellulose is reduced to 33% or less, and the average particle size is adjusted to 10 to 200 μm.
As described above, the bulk density of the cellulose-containing raw material supplied to the pulverizer is preferably 100 to 500 kg / m 3 , and the average particle diameter is preferably 0.01 to 1 mm, and the cellulose-containing raw material is pulverized. By pulverizing with an auxiliary agent in a pulverizer, the crystallinity and the average particle size can be reduced, and cellulose can be efficiently reduced in crystallization.
粉砕機としては媒体式粉砕機を好ましく用いることができる。媒体式粉砕機には容器駆動式粉砕機と媒体撹拌式粉砕機とがある。
容器駆動式粉砕機としては、転動ミル、振動ミル、遊星ミル、遠心流動ミル等が挙げられるが、粉砕効率、生産性の観点から、振動ミルが好ましい。
媒体撹拌式粉砕機としては、タワーミル等の塔型粉砕機；アトライター、アクアマイザー、サンドグラインダー等の撹拌槽型粉砕機；ビスコミル、パールミル等の流通槽型粉砕機；流通管型粉砕機；コボールミル等のアニュラー型粉砕機；連続式のダイナミック型粉砕機等が挙げられるが、粉砕効率、生産性の観点から、撹拌槽型粉砕機が好ましい。媒体攪拌式粉砕機を用いる場合の攪拌翼の先端の周速は、好ましくは０．５〜２０ｍ／ｓ、より好ましくは１〜１５ｍ／ｓである。
粉砕機については「化学工学の進歩 第３０集 微粒子制御」（社団法人 化学工学会東海支部編、１９９６年１０月１０日発行、槇書店）を参照することができる。
処理方法としては、バッチ式、連続式のどちらでもよい。
As the pulverizer, a medium pulverizer can be preferably used. The medium type pulverizer includes a container driven pulverizer and a medium stirring pulverizer.
Examples of the container-driven pulverizer include a rolling mill, a vibration mill, a planetary mill, a centrifugal fluid mill, and the like. From the viewpoint of pulverization efficiency and productivity, a vibration mill is preferable.
As the medium agitating pulverizer, a tower-type pulverizer such as a tower mill; an agitating tank-type pulverizer such as an attritor, an aquamizer, and a sand grinder; a distribution tank-type pulverizer such as a visco mill and a pearl mill; a distribution pipe-type pulverizer; And the like, and a continuous dynamic type pulverizer are preferable. From the viewpoint of pulverization efficiency and productivity, a stirred tank pulverizer is preferable. In the case of using a medium stirring pulverizer, the peripheral speed of the tip of the stirring blade is preferably 0.5 to 20 m / s, more preferably 1 to 15 m / s.
Regarding the pulverizer, reference can be made to “Progress of Chemical Engineering, No. 30, Fine Particle Control” (Chemical Engineering Society, Tokai Branch, issued October 10, 1996, Sakai Shoten).
The processing method may be either a batch type or a continuous type.
粉砕機に充填する媒体の材質としては、特に制限はなく、例えば、鉄、ステンレス、アルミナ、ジルコニア、チタニア、炭化珪素、チッ化珪素、ガラス等が挙げられる。
粉砕機が振動ミル等の容器駆動式粉砕機であって媒体がボールの場合、ボールの外径は、効率的にセルロースの結晶化度を低減させる観点から、好ましくは０．１〜１００ｍｍ、より好ましくは０．５〜５０ｍｍである。媒体の形状としては、ボール、ロッド、チューブ等を用いることができる。
媒体の充填率は、媒体式粉砕機の機種により好適な充填率が異なるが、好ましくは１０〜９７％、より好ましくは１５〜９５％の範囲である。充填率がこの範囲内であれば、セルロース含有原料とボール、ロッド等の媒体との接触頻度が向上するとともに、媒体の動きを妨げずに、粉砕効率を向上させることができる。ここで充填率とは、媒体式粉砕機の攪拌部の容積に対する媒体の見かけの体積をいう。
There is no restriction | limiting in particular as a material of the medium with which a grinder is filled, For example, iron, stainless steel, an alumina, a zirconia, a titania, a silicon carbide, silicon nitride, glass etc. are mentioned.
When the pulverizer is a container-driven pulverizer such as a vibration mill and the medium is a ball, the outer diameter of the ball is preferably 0.1 to 100 mm from the viewpoint of efficiently reducing the crystallinity of cellulose. Preferably it is 0.5-50 mm. As the shape of the medium, a ball, a rod, a tube, or the like can be used.
The medium filling rate varies depending on the model of the medium type pulverizer, but is preferably in the range of 10 to 97%, more preferably 15 to 95%. When the filling rate is within this range, the contact frequency between the cellulose-containing raw material and a medium such as a ball or a rod can be improved, and the pulverization efficiency can be improved without hindering the movement of the medium. Here, the filling rate refers to the apparent volume of the medium relative to the volume of the stirring unit of the medium type pulverizer.
上記の媒体式粉砕機の中では、特にロッドを充填した振動ミルがより好ましい。
ロッドとは棒状の媒体であり、ロッドの断面が四角形、六角形等の多角形、円形、楕円形等のものを用いることができる。その材質、媒体の充填率は前記と同じである。
ロッドの外径は、好ましくは０．５〜２００ｍｍ、より好ましくは１〜１００ｍｍ、更に好ましくは５〜５０ｍｍであり、ロッドの長さは、粉砕機の容器の長さよりも短いものであれば特に限定されない。ロッドの大きさが上記の範囲であれば、所望の粉砕力が得られ、効率的にセルロースを低非晶化させることができる。
なお、振動ミルとしては、中央化工機株式会社製の振動ミル、ユーラステクノ株式会社製のバイブロミル、株式会社吉田製作所製の小型振動ロッドミル、ドイツのフリッチュ社製の振動カップミル、日陶科学株式会社製の小型振動ミル等が挙げられる。
Among the above-mentioned medium type pulverizers, a vibration mill filled with a rod is particularly preferable.
The rod is a rod-shaped medium, and a rod having a cross section of a quadrangle, a polygon such as a hexagon, a circle, or an ellipse can be used. The material and the filling rate of the medium are the same as described above.
The outer diameter of the rod is preferably 0.5 to 200 mm, more preferably 1 to 100 mm, still more preferably 5 to 50 mm, and the length of the rod is particularly shorter than the length of the container of the pulverizer. It is not limited. If the size of the rod is in the above range, a desired pulverization force can be obtained, and cellulose can be efficiently made low amorphous.
In addition, as a vibration mill, a vibration mill manufactured by Chuo Kakki Co., Ltd., a vibro mill manufactured by Eurus Techno Co., Ltd., a small vibration rod mill manufactured by Yoshida Manufacturing Co., Ltd., a vibration cup mill manufactured by Fritsch, Germany, and manufactured by Nissho Science And a small vibration mill.
粉砕処理時間は、粉砕機の種類や、粉砕機に充填する媒体の種類、大きさ及び充填率等により適宜調整しうるが、結晶化度を低減させる観点から、好ましくは０．０１〜５０ｈｒ、より好ましくは０．０５〜２０ｈｒ、より好ましくは０．１〜１０ｈｒ、更に好ましくは０．１〜５ｈｒ、特に好ましくは０．１〜３．５ｈｒである。粉砕処理温度は、特に制限はないが、熱劣化を防ぐ観点から、好ましくは５〜２５０℃、より好ましくは１０〜２００℃、更に好ましくは１５〜１５０℃である。
上記の処理方法により、セルロース含有原料を出発原料として、セルロースＩ型結晶化度が３３％以下の低結晶性セルロースを効率よく得ることができ、また、粉砕機処理の際に、粉砕機の内部にセルロース含有原料が固着せずに、乾式にて処理することができる。
本発明の製造方法によれば、平均粒径の小さい低結晶性セルロースを効率的に、生産性よく製造することができる。
The pulverization time can be appropriately adjusted according to the type of pulverizer, the type, size, and filling rate of the medium filled in the pulverizer, but preferably from 0.01 to 50 hr from the viewpoint of reducing the crystallinity. More preferably, it is 0.05-20 hr, More preferably, it is 0.1-10 hr, More preferably, it is 0.1-5 hr, Most preferably, it is 0.1-3.5 hr. The pulverization temperature is not particularly limited, but is preferably 5 to 250 ° C, more preferably 10 to 200 ° C, and still more preferably 15 to 150 ° C from the viewpoint of preventing thermal deterioration.
By the above processing method, a low crystalline cellulose having a cellulose I-type crystallinity of 33% or less can be efficiently obtained using a cellulose-containing raw material as a starting raw material. The cellulose-containing raw material does not adhere to the substrate and can be processed by a dry method.
According to the production method of the present invention, low crystalline cellulose having a small average particle size can be produced efficiently and with good productivity.
実施例及び比較例で使用した又は得られたセルロース含有原料又は低結晶性セルロースの平均粒径、嵩密度、結晶化度、水分含量及びセルロース含有量の測定は、下記に記載の方法で行った。
（１）平均粒径の測定
平均粒径は、レーザー回折／散乱式粒度分布測定装置「ＬＡ−９２０」（株式会社堀場製作所製）を用いて測定した。測定条件は、粒径測定前に超音波で１分間処理し、測定時の分散媒体として水を用い、体積基準のメジアン径を、温度２５℃にて測定した。
（２）嵩密度の測定
嵩密度は、ホソカワミクロン株式会社製の「パウダーテスター」を用いて測定した。測定は、ふるいを振動させて、サンプルをシュートを通じ落下させ、規定の容器（容量１００ｍＬ）に受け、該容器中のサンプルの質量を測定することにより算出した。ただし綿状化したサンプルについては、ふるいを通さずにシュートを通じ落下させ、規定の容器（容量１００ｍＬ）に受け、該容器中のサンプルの質量を測定することにより算出した。
The average particle size, bulk density, crystallinity, moisture content and cellulose content of the cellulose-containing raw materials or low crystalline cellulose used or obtained in Examples and Comparative Examples were measured by the methods described below. .
(1) Measurement of average particle diameter The average particle diameter was measured using a laser diffraction / scattering particle size distribution measuring apparatus “LA-920” (manufactured by Horiba, Ltd.). The measurement conditions were ultrasonic treatment for 1 minute before particle size measurement, water was used as a dispersion medium during measurement, and the volume-based median diameter was measured at a temperature of 25 ° C.
(2) Measurement of bulk density The bulk density was measured using "Powder Tester" manufactured by Hosokawa Micron Corporation. The measurement was calculated by vibrating the sieve, dropping the sample through a chute, receiving it in a specified container (capacity 100 mL), and measuring the mass of the sample in the container. However, the cotton-like sample was calculated by dropping through a chute without passing through a sieve, receiving it in a specified container (capacity 100 mL), and measuring the mass of the sample in the container.
（３）結晶化度の算出
セルロースＩ型結晶化度は、サンプルのＸ線回折強度を、株式会社リガク製の「Rigaku RINT 2500VC X-RAY diffractometer」を用いて以下の条件で測定し、前記式（１）に基づいて算出した。
測定条件は、Ｘ線源：Ｃｕ／Ｋα−radiation、管電圧：４０ｋｖ、管電流：１２０ｍＡ、測定範囲：回折角２θ＝５〜４５°で測定した。測定用サンプルは面積３２０ｍｍ2×厚さ１ｍｍのペレットを圧縮し作製した。Ｘ線のスキャンスピードは１０°／ｍｉｎで測定した。
（４）水分含量の測定
水分含量は、赤外線水分計（株式会社ケット科学研究所製、「ＦＤ−６１０」）を使用し、１５０℃にて測定を行った。
（５）セルロース含有量の測定
セルロース含有量は、社団法人日本分析化学会編、分析化学便覧（改訂四版、平成３年１１月３０日、丸善株式会社発行）の１０８１頁〜１０８２頁に記載のホロセルロース定量法により測定した。より具体的には、以下の方法で行った。
粉砕した試料をエタノール・ベンゼン混合溶剤（１：１）で６時間ソックスレー抽出を行い、さらにエタノールで４時間ソックスレー抽出を行って、抽出後の試料を６０℃で真空乾燥した。得られた試料２．５gに水１５０ｍＬ、亜塩素酸ナトリウム１．０ｇ及び酢酸０．２ｍＬを加え、７０〜８０℃で１時間加温した。引き続き亜塩素酸ナトリウム及び酢酸を加えて加温する操作を繰り返し行い、試料が白く脱色するまで３〜４回処理を繰り返した。得られた白色の残渣をグラスフィルター（１Ｇ−３）でろ過し、冷水及びアセトンで洗浄した後、１０５℃で恒量になるまで乾燥し、残渣重量を求め、下記式によりセルロース含有量（％）を算出した。
セルロース含有量（％）＝〔残渣重量(g)／真空乾燥後の試料重量(g)〕×１００
(3) Calculation of crystallinity The cellulose I type crystallinity is measured by measuring the X-ray diffraction intensity of a sample using the “Rigaku RINT 2500VC X-RAY diffractometer” manufactured by Rigaku Corporation under the following conditions. Calculated based on (1).
The measurement conditions were X-ray source: Cu / Kα-radiation, tube voltage: 40 kv, tube current: 120 mA, measurement range: diffraction angle 2θ = 5-45 °. The measurement sample was prepared by compressing a pellet having an area of 320 mm 2 × thickness of 1 mm. The X-ray scan speed was measured at 10 ° / min.
(4) Measurement of moisture content The moisture content was measured at 150 ° C using an infrared moisture meter ("FD-610", manufactured by Kett Scientific Laboratory).
(5) Measurement of cellulose content The cellulose content is described in pages 1081 to 1082 of the Japan Analytical Chemistry Society, Analytical Chemistry Handbook (4th revised edition, published on November 30, 1991, Maruzen Co., Ltd.). This was measured by the holocellulose quantitative method. More specifically, the following method was used.
The pulverized sample was subjected to Soxhlet extraction with ethanol / benzene mixed solvent (1: 1) for 6 hours, further subjected to Soxhlet extraction with ethanol for 4 hours, and the sample after extraction was vacuum-dried at 60 ° C. To 2.5 g of the obtained sample, 150 mL of water, 1.0 g of sodium chlorite and 0.2 mL of acetic acid were added, and the mixture was heated at 70 to 80 ° C. for 1 hour. Subsequently, an operation of adding sodium chlorite and acetic acid and heating was repeated, and the treatment was repeated 3 to 4 times until the sample was decolorized white. The obtained white residue was filtered through a glass filter (1G-3), washed with cold water and acetone, dried at 105 ° C. until a constant weight was obtained, the residue weight was determined, and the cellulose content (%) by the following formula: Was calculated.
Cellulose content (%) = [residue weight (g) / sample weight after vacuum drying (g)] × 100
実施例１
（１）シュレッダー処理（前処理）
セルロース含有原料として、シート状木材パルプ（Borregard社製「Blue Bear Ultra Ether」、８００ｍｍ×６００ｍｍ×１．５ｍｍ、結晶化度８１％、セルロース含有量９６質量％（セルロース含有原料から水を除いた残余の成分中の含有量。以下同じ。）、水分含量７質量％）、をシュレッダー（株式会社明光商会製、「ＭＳＸ２０００−ＩＶＰ４４０Ｆ」）にかけ、約１０ｍｍ×５ｍｍ×１．５ｍｍのチップ状パルプを得た。
（２）押出機処理
上記（１）で得られたチップ状パルプを二軸押出機（株式会社スエヒロＥＰＭ製、「ＥＡ−２０」、完全噛み合い型同方向回転）に２ｋｇ／ｈｒで投入し、せん断速度６６０ｓｅｃ-1、スクリュー回転数３００ｒｐｍ、外部から冷却水を流しながら、１パス処理した。
二軸押出機の処理温度は発熱により３０〜７０℃であり、得られたパルプは、平均粒径１２０μｍ、嵩密度２１９ｋｇ／ｍ3であった。
なお、前記二軸押出機は、スクリュー径４０ｍｍのスクリュー部と、互い違い（９０°）に１２ブロックを組み合わせたニーディングディスク部とを有し、２本のスクリューは、同じ構成を有するものである。
（３）粉砕機処理（振動ミル処理）
上記（２）で得られたパルプとグルコース（粉砕助剤）を混合し、その混合物１００ｇを振動ミル（中央化工機株式会社製、「ＭＢ−１」、容器全容量３．５Ｌ）に投入し、ロッド（断面形状：円形、直径：３０ｍｍ、長さ：２１８ｍｍ、材質：ステンレス）１１本を振動ミルに充填（充填率４９％）して、振幅８ｍｍ、回転数１２００ｃｐｍの条件で０．５時間処理を行った。得られた低結晶性セルロース（粉末パルプ）の結晶化度は２２％、平均粒径は５６μｍであり、その温度は、粉砕処理に伴う発熱により４０℃であった。
粉砕処理終了後、振動ミル内の壁面や底部にパルプの固着物等はみられなかった。結果を表１に示す。
Example 1
(1) Shredder processing (pre-processing)
As a cellulose-containing raw material, a sheet-like wood pulp (“Blue Bear Ultra Ether” manufactured by Borregard, 800 mm × 600 mm × 1.5 mm, crystallinity 81%, cellulose content 96% by mass (residue obtained by removing water from the cellulose-containing raw material) And the moisture content of 7% by mass) are subjected to a shredder (“MSX2000-IVP440F” manufactured by Meiko Shokai Co., Ltd.) to obtain a chip-like pulp of about 10 mm × 5 mm × 1.5 mm. It was.
(2) Extruder treatment The chip-like pulp obtained in the above (1) was charged at 2 kg / hr into a twin-screw extruder (Suehiro EPM Co., Ltd., “EA-20”, complete meshing type rotation in the same direction), One-pass treatment was performed with a shear rate of 660 sec −1 , a screw rotation speed of 300 rpm, and cooling water flowing from the outside.
The treatment temperature of the twin screw extruder was 30 to 70 ° C. due to heat generation, and the obtained pulp had an average particle size of 120 μm and a bulk density of 219 kg / m 3 .
The twin-screw extruder has a screw part with a screw diameter of 40 mm and a kneading disk part in which 12 blocks are combined alternately (90 °), and the two screws have the same configuration. .
(3) Crusher processing (vibration mill processing)
The pulp obtained in (2) above and glucose (grinding aid) are mixed, and 100 g of the mixture is put into a vibration mill (Chuo Kako Co., Ltd., “MB-1”, container total capacity 3.5 L). , 11 rods (cross-sectional shape: circular, diameter: 30 mm, length: 218 mm, material: stainless steel) were filled into a vibration mill (filling rate 49%), 0.5 hours under conditions of amplitude 8 mm and rotation speed 1200 cpm Processed. The obtained low crystalline cellulose (powder pulp) had a crystallinity of 22% and an average particle size of 56 μm, and its temperature was 40 ° C. due to heat generated by the pulverization treatment.
After completion of the pulverization treatment, no fixed matter of pulp was found on the wall surface or bottom of the vibration mill. The results are shown in Table 1.
実施例２〜６
粉末助剤の種類及び粉砕機処理時間を変えた以外は、実施例１と同様に操作して低結晶性セルロース（粉末パルプ）を得た。結果を表１に示す。
実施例７〜８
粉末助剤の種類と添加量、及び粉砕機の種類と処理時間を変えた以外は、実施例１と同様に操作して低結晶性セルロース（粉末パルプ）を得た。結果を表１に示す。
Examples 2-6
A low crystalline cellulose (powder pulp) was obtained in the same manner as in Example 1 except that the type of powder auxiliary and the pulverizer treatment time were changed. The results are shown in Table 1.
Examples 7-8
A low crystalline cellulose (powder pulp) was obtained in the same manner as in Example 1 except that the type and amount of powder auxiliary, and the type and processing time of the pulverizer were changed. The results are shown in Table 1.
比較例１
粉砕助剤を添加せず、粉砕機処理も行わなかった以外は、実施例１と同様に操作した結果、低結晶性セルロースは得られず、いわゆる結晶性セルロース（粉末パルプ）が得られた。結果を表１に示す。
比較例２
粉砕助剤を添加しなかった以外は、実施例１と同様に操作した結果、結晶性セルロース（粉末パルプ）が得られた。結果を表１に示す。
比較例３
押出機処理を行わず、粉砕助剤を添加しなかった以外は、実施例１と同様に操作した結果、結晶性セルロース（粉末パルプ）が得られた。結果を表１に示す。
比較例４
実施例１と同様にシュレッダー処理、次いで二軸押出機処理を行った後、得られたパルプと澱粉（粉砕助剤）の混合物１００ｇを、粉砕機を用いる代わりにカッターミル（株式会社ダルトン製、「Ｐ−０２Ｓ型」）に投入し、回転数３０００ｒｐｍの条件で０．５時間処理した。
その結果、低結晶性セルロースではなく結晶性セルロース（粉末パルプ）が得られた。その結晶化度は７４％、平均粒径は１２６μｍであり、その温度は、処理に伴う発熱により３５℃であった。結果を表１に示す。
比較例５
実施例１と同様にシュレッダー処理、次いで二軸押出機処理を行った。得られた押出機処理したパルプとペンタエリスリトール（砕助剤）の混合物１００ｇを、粉砕機を用いる代わりにカッターミル（株式会社ダルトン製、「Ｐ−０２Ｓ型」）に投入し、回転数３０００ｒｐｍの条件で０．５時間処理を行った。
その結果、低結晶性セルロースではなく結晶性セルロース（粉末パルプ）が得られた。その結晶化度は７５％、平均粒径は１５４μｍであり、その温度は、処理に伴う発熱により３１℃であった。結果を表１に示す。
Comparative Example 1
As a result of operating in the same manner as in Example 1 except that the pulverization aid was not added and the pulverizer treatment was not performed, low crystalline cellulose was not obtained, and so-called crystalline cellulose (powder pulp) was obtained. The results are shown in Table 1.
Comparative Example 2
Crystalline cellulose (powder pulp) was obtained as a result of the same operation as in Example 1 except that no grinding aid was added. The results are shown in Table 1.
Comparative Example 3
Crystalline cellulose (powder pulp) was obtained as a result of the same operation as in Example 1 except that the extruder treatment was not performed and the grinding aid was not added. The results are shown in Table 1.
Comparative Example 4
After performing shredder treatment and then twin screw extruder treatment in the same manner as in Example 1, 100 g of a mixture of the obtained pulp and starch (grinding aid) was used instead of using a grinder. "P-02S type") and treated for 0.5 hours under the condition of a rotational speed of 3000 rpm.
As a result, crystalline cellulose (powder pulp) was obtained instead of low crystalline cellulose. The crystallinity was 74%, the average particle size was 126 μm, and the temperature was 35 ° C. due to heat generated by the treatment. The results are shown in Table 1.
Comparative Example 5
A shredder process and then a twin screw extruder process were performed in the same manner as in Example 1. Instead of using a pulverizer, 100 g of a mixture of the obtained extruder-treated pulp and pentaerythritol (grinding aid) was put into a cutter mill (Dalton Co., Ltd., “P-02S type”) and rotated at 3000 rpm. The treatment was performed for 0.5 hours under the conditions.
As a result, crystalline cellulose (powder pulp) was obtained instead of low crystalline cellulose. The crystallinity was 75%, the average particle size was 154 μm, and the temperature was 31 ° C. due to heat generated by the treatment. The results are shown in Table 1.
表１から、実施例１〜８の方法によれば、比較例１〜５の方法に比べて、セルロースの結晶化度及び平均粒径を低減させた低結晶性セルロースを効率的に得ることができ、生産性に優れていることが分かる。 From Table 1, according to the method of Examples 1-8, compared with the method of Comparative Examples 1-5, the low crystalline cellulose which reduced the crystallinity degree and average particle diameter of the cellulose can be obtained efficiently. It can be seen that it is excellent in productivity.
本発明の低結晶性セルロースの製造方法は、セルロースＩ型結晶化度を３３％以下に低減させた、平均粒径１０〜２００μｍの低結晶性セルロースを効率的に、生産性よく得ることができる。得られた低結晶性セルロースは、セルロースエーテルの原料、化粧品、食品、バイオマス材料等の工業原料として特に有用である。 The method for producing a low crystalline cellulose of the present invention can efficiently obtain a low crystalline cellulose having an average particle size of 10 to 200 μm with a cellulose I-type crystallinity reduced to 33% or less and high productivity. . The obtained low crystalline cellulose is particularly useful as a raw material for cellulose ethers, industrial raw materials such as cosmetics, foods, and biomass materials.
Claims (8)
セルロースＩ型結晶化度（％）＝〔（Ｉ22.6−Ｉ18.5）／Ｉ22.6〕×１００ （１）
〔式中、Ｉ22.6は、Ｘ線回折における格子面（００２面）（回折角２θ＝２２．６°）の回折強度、及びＩ18.5は、アモルファス部（回折角２θ＝１８．５°）の回折強度を示す。〕 A method for producing low crystalline cellulose having an average particle size of 10 to 200 μm from a cellulose-containing raw material having a cellulose I-type crystallinity of more than 33% represented by the following formula (1), wherein water is produced from the cellulose-containing raw material. The cellulose content in the remaining components excluding the slag is 20% by mass or more, and the cellulose-containing raw material is treated with a pulverization aid by a pulverizer to reduce the cellulose I-type crystallinity to 33% or less. The manufacturing method of a low crystalline cellulose.
Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] × 100 (1)
[Wherein I 22.6 is the diffraction intensity of the grating plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I 18.5 is the amorphous portion (diffraction angle 2θ = 18.5 °). The diffraction intensity is shown. ]
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010134560A1 (en) * | 2009-05-21 | 2010-11-25 | 花王株式会社 | Process for producing non-crystalline cellulose |
| JP2013256640A (en) * | 2012-05-16 | 2013-12-26 | Kao Corp | Method for producing cellulose ether |
| JP5924722B1 (en) * | 2015-03-31 | 2016-05-25 | 日本山村硝子株式会社 | Method for producing cellulose-containing olefin resin composition |
| WO2016157564A1 (en) * | 2015-03-31 | 2016-10-06 | 日本山村硝子株式会社 | Process for producing cellulose-containing olefin-based resin composition |
| WO2018123959A1 (en) | 2016-12-27 | 2018-07-05 | 花王株式会社 | Method for producing low crystallinity cellulose, and resin composition |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4856746A (en) * | 1971-11-20 | 1973-08-09 | ||
| JPS62236801A (en) * | 1986-04-08 | 1987-10-16 | Asahi Chem Ind Co Ltd | Production of soluble cellulose |
| JPH0610287A (en) * | 1992-06-24 | 1994-01-18 | New Oji Paper Co Ltd | Production of fine fibrous cellulose |
| JPH08232189A (en) * | 1994-12-28 | 1996-09-10 | Kao Corp | Absorbent paper and its production |
| JPH10245401A (en) * | 1997-03-04 | 1998-09-14 | Agency Of Ind Science & Technol | New aggregate natural polymer particulates, and its production |
| JP2000314941A (en) * | 1999-03-03 | 2000-11-14 | Fuji Photo Film Co Ltd | Production of base for recording material and base for recording material |
| JP2003064184A (en) * | 2001-08-24 | 2003-03-05 | Toray Ind Inc | Method for producing cellulose solution and thermoplastic cellulose ester |
| JP2004230719A (en) * | 2003-01-30 | 2004-08-19 | National Institute Of Advanced Industrial & Technology | Novel cellulose particle and method for manufacturing it |
| JP2004331918A (en) * | 2003-05-12 | 2004-11-25 | Asahi Kasei Chemicals Corp | Amorphous cellulose fine powder |
| JP2005537347A (en) * | 2002-07-26 | 2005-12-08 | エフ エム シー コーポレーション | Production of microcrystalline cellulose |
| WO2008099929A1 (en) * | 2007-02-16 | 2008-08-21 | Kao Corporation | Process for producing noncrystalline cellulose |
-
2008
- 2008-08-08 JP JP2008205799A patent/JP5426121B2/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4856746A (en) * | 1971-11-20 | 1973-08-09 | ||
| JPS62236801A (en) * | 1986-04-08 | 1987-10-16 | Asahi Chem Ind Co Ltd | Production of soluble cellulose |
| JPH0610287A (en) * | 1992-06-24 | 1994-01-18 | New Oji Paper Co Ltd | Production of fine fibrous cellulose |
| JPH08232189A (en) * | 1994-12-28 | 1996-09-10 | Kao Corp | Absorbent paper and its production |
| JPH10245401A (en) * | 1997-03-04 | 1998-09-14 | Agency Of Ind Science & Technol | New aggregate natural polymer particulates, and its production |
| JP2000314941A (en) * | 1999-03-03 | 2000-11-14 | Fuji Photo Film Co Ltd | Production of base for recording material and base for recording material |
| JP2003064184A (en) * | 2001-08-24 | 2003-03-05 | Toray Ind Inc | Method for producing cellulose solution and thermoplastic cellulose ester |
| JP2005537347A (en) * | 2002-07-26 | 2005-12-08 | エフ エム シー コーポレーション | Production of microcrystalline cellulose |
| JP2004230719A (en) * | 2003-01-30 | 2004-08-19 | National Institute Of Advanced Industrial & Technology | Novel cellulose particle and method for manufacturing it |
| JP2004331918A (en) * | 2003-05-12 | 2004-11-25 | Asahi Kasei Chemicals Corp | Amorphous cellulose fine powder |
| WO2008099929A1 (en) * | 2007-02-16 | 2008-08-21 | Kao Corporation | Process for producing noncrystalline cellulose |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010134560A1 (en) * | 2009-05-21 | 2010-11-25 | 花王株式会社 | Process for producing non-crystalline cellulose |
| JP2013256640A (en) * | 2012-05-16 | 2013-12-26 | Kao Corp | Method for producing cellulose ether |
| JP5924722B1 (en) * | 2015-03-31 | 2016-05-25 | 日本山村硝子株式会社 | Method for producing cellulose-containing olefin resin composition |
| WO2016157564A1 (en) * | 2015-03-31 | 2016-10-06 | 日本山村硝子株式会社 | Process for producing cellulose-containing olefin-based resin composition |
| WO2018123959A1 (en) | 2016-12-27 | 2018-07-05 | 花王株式会社 | Method for producing low crystallinity cellulose, and resin composition |
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