JP6098370B2 - Composite material and manufacturing method thereof - Google Patents
Composite material and manufacturing method thereof Download PDFInfo
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- JP6098370B2 JP6098370B2 JP2013110904A JP2013110904A JP6098370B2 JP 6098370 B2 JP6098370 B2 JP 6098370B2 JP 2013110904 A JP2013110904 A JP 2013110904A JP 2013110904 A JP2013110904 A JP 2013110904A JP 6098370 B2 JP6098370 B2 JP 6098370B2
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- fine cellulose
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- pulp
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- 238000004519 manufacturing process Methods 0.000 title claims description 56
- 239000002131 composite material Substances 0.000 title claims description 52
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- 102000004190 Enzymes Human genes 0.000 claims description 94
- 230000000694 effects Effects 0.000 claims description 61
- 239000011159 matrix material Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 37
- 229920002678 cellulose Polymers 0.000 claims description 33
- 239000001913 cellulose Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 12
- 108010059892 Cellulase Proteins 0.000 claims description 9
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- 239000000839 emulsion Substances 0.000 claims description 7
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- 239000004033 plastic Substances 0.000 claims description 7
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- 239000000203 mixture Substances 0.000 claims description 5
- 108010008885 Cellulose 1,4-beta-Cellobiosidase Proteins 0.000 claims description 4
- 229940088598 enzyme Drugs 0.000 description 89
- 239000000835 fiber Substances 0.000 description 62
- 239000006185 dispersion Substances 0.000 description 47
- 239000006228 supernatant Substances 0.000 description 32
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- 239000000243 solution Substances 0.000 description 22
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- 239000002253 acid Substances 0.000 description 17
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- 238000012360 testing method Methods 0.000 description 16
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- 238000011088 calibration curve Methods 0.000 description 14
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- 239000008103 glucose Substances 0.000 description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 3
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- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 239000000872 buffer Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
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- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- 238000010792 warming Methods 0.000 description 2
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 1
- YUDPTGPSBJVHCN-YMILTQATSA-N 4-methylumbelliferyl beta-D-glucoside Chemical compound C1=CC=2C(C)=CC(=O)OC=2C=C1O[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O YUDPTGPSBJVHCN-YMILTQATSA-N 0.000 description 1
- 241001019659 Acremonium <Plectosphaerellaceae> Species 0.000 description 1
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- 241001474374 Blennius Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 235000016496 Panda oleosa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
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- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、微細セルロース繊維とマトリクス材料とを含む複合材料及びその製造方法に関する。 The present invention relates to a composite material containing fine cellulose fibers and a matrix material, and a method for producing the same.
車両、航空機、家電製品、電子機器、事務機器等を構成する材料として、プラスチックやゴム等のマトリクス材料に繊維を配合した複合材料を用いることがある。複合材料に使用される繊維として、繊維径がナノメートルオーダーの微細セルロース繊維を用いることが知られている。
微細セルロース繊維としては、リグノセルロースを、ニトロキシラジカル誘導体、臭化アルカリ及び酸化剤を含む分散媒中で処理して得た繊維が知られている（特許文献１）。また、微細セルロース繊維として、木粉を解繊処理して得た繊維も知られている（特許文献２）。
微細セルロース繊維をマトリクス材料に配合して複合材料を製造する方法としては、微細セルロース繊維を含む分散液をエマルション状マトリクス材料に混合した後、濾過等により脱液する方法が知られている（特許文献３）。
As a material constituting a vehicle, an aircraft, a home appliance, an electronic device, an office device, or the like, a composite material in which fibers are mixed with a matrix material such as plastic or rubber may be used. As a fiber used for the composite material, it is known to use a fine cellulose fiber having a fiber diameter of nanometer order.
As a fine cellulose fiber, a fiber obtained by treating lignocellulose in a dispersion medium containing a nitroxy radical derivative, an alkali bromide and an oxidizing agent is known (Patent Document 1). Moreover, the fiber obtained by defibrating wood powder is also known as a fine cellulose fiber (patent document 2).
As a method for producing a composite material by blending fine cellulose fibers into a matrix material, a method is known in which a dispersion containing fine cellulose fibers is mixed with an emulsion matrix material and then drained by filtration or the like (patent) Reference 3).
しかし、特許文献１，２に記載の微細セルロース繊維を用い、特許文献３に記載の複合材料の製造方法を適用した場合、微細セルロース繊維による補強効果が不充分で、複合材料の機械的物性が充分に高くならないことがあった。
本発明は、機械的物性に優れた複合材料及びその製造方法を提供することを目的とする。
However, when the fine cellulose fibers described in Patent Documents 1 and 2 are used and the method for producing a composite material described in Patent Document 3 is applied, the reinforcing effect of the fine cellulose fibers is insufficient, and the mechanical properties of the composite material are insufficient. Sometimes it was not high enough.
An object of this invention is to provide the composite material excellent in mechanical physical property, and its manufacturing method.
本発明の複合材料は、微細セルロース繊維と、プラスチック及びゴムの少なくとも一方を含むマトリクス材料とを含有し、前記微細セルロース繊維は、エンドグルカナーゼ活性とセロビオヒドロラーゼ活性との比率が０．０６以上のセルロース分解酵素によってセルロース原料が酵素処理され、解繊処理されて得た、重合度が１００〜５００の繊維である。
本発明の複合材料の製造方法は、セルロース原料を、エンドグルカナーゼ活性とセロビオヒドロラーゼ活性との比率が０．０６以上のセルロース分解酵素によって酵素処理して酵素処理セルロースを得る酵素処理工程、前記酵素処理セルロースを、重合度が１００〜５００になるように解繊して微細セルロース繊維を得る解繊処理工程、前記微細セルロース繊維と、プラスチック及びゴムの少なくとも一方を含むマトリクス材料とを混合する混合工程、を有する。
本発明の複合材料の製造方法においては、前記混合工程では、スラリー状の微細セルロース繊維と、エマルション状のマトリクス材料とを混合して混合液を調製し、混合工程の後に、前記混合液を脱液して複合材料を得る脱液工程を有することが好ましい。
The composite material of the present invention contains fine cellulose fibers and a matrix material containing at least one of plastic and rubber, and the fine cellulose fibers have a ratio of endoglucanase activity to cellobiohydrolase activity of 0.06 or more. It is a fiber having a degree of polymerization of 100 to 500, which is obtained by subjecting a cellulose raw material to an enzyme treatment and a fibrillation treatment with a cellulolytic enzyme.
The method for producing a composite material of the present invention includes an enzyme treatment step of obtaining an enzyme-treated cellulose by subjecting a cellulose raw material to enzyme treatment with a cellulose-degrading enzyme having a ratio of endoglucanase activity to cellobiohydrolase activity of 0.06 or more, A defibrating treatment step of defibrating the treated cellulose to obtain a fine cellulose fiber by defibration so that the degree of polymerization is 100 to 500, and a mixing step of mixing the fine cellulose fiber and a matrix material containing at least one of plastic and rubber Have.
In the method for producing a composite material of the present invention, in the mixing step, a slurry-like fine cellulose fiber and an emulsion-like matrix material are mixed to prepare a mixed solution, and the mixed solution is removed after the mixing step. It is preferable to have a liquid removal step for obtaining a composite material by liquid.
本発明の複合材料は、強度や剛性等の機械的物性に優れる。
本発明の複合材料の製造方法によれば、強度や剛性等の機械的物性に優れた複合材料を容易に製造できる。
The composite material of the present invention is excellent in mechanical properties such as strength and rigidity.
According to the method for producing a composite material of the present invention, a composite material having excellent mechanical properties such as strength and rigidity can be easily produced.
「複合材料」
本発明の複合材料は、微細セルロース繊維とマトリクス材料とを含有する。
複合材料における微細セルロース繊維の含有量は、微細セルロース繊維とマトリクス材料の固形分の合計を１００質量部とした際の、０.５〜５０質量部であることが好ましく、１〜４０質量部であることがより好ましく、２〜３０質量部であることがさらに好ましい。微細セルロース繊維の含有量が前記下限値以上であれば、微細セルロース繊維が充分に含まれるため、複合材料の機械的物性をより向上させることができる。しかし、微細セルロース繊維の含有量が前記上限値を超えると、複合材料中に微細セルロース繊維の凝集物を形成して、かえって複合材料の機械的物性を低下させることがある。
"Composite materials"
The composite material of the present invention contains fine cellulose fibers and a matrix material.
The content of the fine cellulose fibers in the composite material is preferably 0.5 to 50 parts by mass, and 1 to 40 parts by mass when the total solid content of the fine cellulose fibers and the matrix material is 100 parts by mass. More preferably, it is more preferably 2 to 30 parts by mass. If the content of the fine cellulose fiber is not less than the lower limit, the fine cellulose fiber is sufficiently contained, so that the mechanical properties of the composite material can be further improved. However, when the content of the fine cellulose fiber exceeds the upper limit, an aggregate of fine cellulose fibers may be formed in the composite material, which may lower the mechanical properties of the composite material.
＜微細セルロース繊維＞
本発明で使用される微細セルロース繊維は、通常製紙用途で用いるパルプ繊維よりもはるかに細く且つ短いＩ型結晶構造のセルロース繊維あるいは棒状粒子である。
微細セルロース繊維がＩ型結晶構造を有していることは、グラファイトで単色化したＣｕＫα（λ＝１．５４１８Å）を用いた広角Ｘ線回折写真より得られる回折プロファイルにおいて、２θ＝１４〜１７°付近と２θ＝２２〜２３°付近の２箇所の位置に典型的なピークを有することで同定することができる。
微細セルロース繊維の、Ｘ線回折法によって求められる結晶化度は、好ましくは６５％以上、より好ましくは７０％以上、さらに好ましくは７５％以上、最も好ましくは８０％超である。結晶化度が前記下限値以上であれば、弾性率、耐熱性、低線熱膨張率発現の点でさらに優れた性能が期待できる。結晶化度については、Ｘ線回折プロファイルを測定し、そのパターンから常法により求めることができる（Ｓｅｇａｌら、Ｔｅｘｔｉｌｅ Ｒｅｓｅａｒｃｈ Ｊｏｕｒｎａｌ、２９巻、７８６ページ、１９５９年）。
<Fine cellulose fiber>
The fine cellulose fibers used in the present invention are cellulose fibers or rod-like particles having an I-type crystal structure that is much finer and shorter than pulp fibers usually used in papermaking applications.
The fact that the fine cellulose fiber has a type I crystal structure is that 2θ = 14 to 17 ° in a diffraction profile obtained from a wide-angle X-ray diffraction photograph using CuKα (λ = 1.5418４) monochromatized with graphite. It can be identified by having typical peaks in the vicinity and two positions near 2θ = 22 to 23 °.
The degree of crystallinity of the fine cellulose fibers determined by the X-ray diffraction method is preferably 65% or more, more preferably 70% or more, still more preferably 75% or more, and most preferably more than 80%. If the crystallinity is equal to or higher than the lower limit, further excellent performance can be expected in terms of elastic modulus, heat resistance, and low linear thermal expansion. The degree of crystallinity can be obtained by measuring an X-ray diffraction profile and using a conventional method (Segal et al., Textile Research Journal, 29, 786, 1959).
（繊維幅）
本発明で使用される微細セルロース繊維は、電子顕微鏡で観察して求めた平均繊維幅が２〜１０００ｎｍのセルロースである。微細セルロース繊維の平均繊維幅は２〜１００ｎｍが好ましく、２〜５０ｎｍがより好ましく、２〜３０ｎｍがさらに好ましく、２〜１５ｎｍが特に好ましい。微細セルロース繊維の平均繊維幅が前記上限値を超えると、微細セルロース繊維としての特性（高強度や高剛性、高寸法安定性、マトリクス材料と複合化した際の高分散性、透明性）を得ることが困難になる。微細セルロース繊維の平均繊維幅が前記下限値未満であると、セルロース分子として分散媒に溶解してしまうため、微細セルロース繊維としての特性（高強度や高剛性、高寸法安定性）を得ることが困難になる。
(Fiber width)
The fine cellulose fiber used in the present invention is cellulose having an average fiber width of 2 to 1000 nm determined by observation with an electron microscope. The average fiber width of the fine cellulose fibers is preferably 2 to 100 nm, more preferably 2 to 50 nm, further preferably 2 to 30 nm, and particularly preferably 2 to 15 nm. When the average fiber width of the fine cellulose fibers exceeds the above upper limit, the characteristics as the fine cellulose fibers (high strength, high rigidity, high dimensional stability, high dispersibility when combined with a matrix material, transparency) are obtained. It becomes difficult. If the average fiber width of the fine cellulose fibers is less than the lower limit value, the cellulose molecules are dissolved in the dispersion medium, so that characteristics (high strength, high rigidity, high dimensional stability) as fine cellulose fibers can be obtained. It becomes difficult.
微細セルロース繊維の電子顕微鏡観察による平均繊維幅の測定は以下のようにして行う。微細セルロース繊維含有スラリーを調製し、該スラリーを親水化処理したカーボン膜被覆グリッド上にキャストして透過型電子顕微鏡（ＴＥＭ）観察用試料とする。幅広の繊維を含む場合には、ガラス上にキャストした表面の操作型電子顕微鏡（ＳＥＭ）像を観察してもよい。構成する繊維の幅に応じて１０００倍、５０００倍、１００００倍、２００００倍、５００００倍あるいは１０００００倍のいずれかの倍率で電子顕微鏡画像による観察を行う。但し、試料、観察条件や倍率は下記の条件を満たすように調整する。
（１）観察画像内の任意箇所に一本の直線Ｘを引き、該直線Ｘに対し、２０本以上の繊維が交差する。
（２）同じ画像内で該直線Ｘと垂直に交差する直線Ｙを引き、該直線Ｙに対し、２０本以上の繊維が交差する。
上記のような電子顕微鏡観察画像に対して、直線Ｘに交錯する繊維、直線Ｙに交錯する繊維の各々について少なくとも２０本（すなわち、合計が少なくとも４０本）の幅（繊維の短径）を読み取る。こうして上記のような電子顕微鏡画像を少なくとも３組以上観察し、少なくとも４０本×３組（すなわち、少なくとも１２０本）の繊維幅を読み取る。このように読み取った繊維幅を平均して平均繊維幅を求める。この平均繊維幅は数平均繊維径と等しい。
Measurement of the average fiber width by observation with an electron microscope of fine cellulose fibers is performed as follows. A slurry containing fine cellulose fibers is prepared, and the slurry is cast on a carbon film-coated grid that has been subjected to a hydrophilization treatment to obtain a transmission electron microscope (TEM) observation sample. When wide fibers are included, an operation electron microscope (SEM) image of the surface cast on glass may be observed. Observation by an electron microscope image is performed at any magnification of 1000 times, 5000 times, 10000 times, 20000 times, 50000 times or 100,000 times depending on the width of the constituent fibers. However, the sample, observation conditions, and magnification are adjusted to satisfy the following conditions.
(1) One straight line X is drawn at an arbitrary location in the observation image, and 20 or more fibers intersect the straight line X.
(2) A straight line Y perpendicularly intersecting the straight line X is drawn in the same image, and 20 or more fibers intersect the straight line Y.
For the electron microscope observation image as described above, the width (minor axis of the fiber) of at least 20 fibers (that is, at least 40 in total) is read for each of the fibers intersecting with the straight line X and the fibers intersecting with the straight line Y. . In this way, at least three or more sets of electron microscope images as described above are observed, and the fiber width of at least 40 × 3 sets (that is, at least 120 sets) is read. The fiber widths thus read are averaged to obtain the average fiber width. This average fiber width is equal to the number average fiber diameter.
（重合度）
微細セルロース繊維の重合度は１００〜５００であり、２００〜４７０であることが好ましく、２５０〜４４０であることがより好ましい。微細セルロース繊維の重合度が前記下限値未満であると、「繊維状」とはいえず、マトリクス材料の補強剤として使用することが困難になる。一方、微細セルロース繊維の重合度が前記上限値を超えると、微細セルロース繊維をスラリー化したときの流動性が低下し、スラリー粘度が高くなりすぎて分散安定性が低くなる。また、マトリクス材料と混合した際に凝集物を形成することもある。
微細セルロース繊維の重合度は、以下の方法により測定する。
微細セルロース繊維（遠心分離後の上澄み液、濃度約０．１質量％）をポリ四フッ化エチレン製シャーレ上に展開し、６０℃にて乾燥して、ドライシートを得る。得られたドライシートを分散媒に分散させて、Ｔａｐｐｉ Ｔ２３０に従い、パルプ粘度を測定する。また、前記分散媒のみで粘度を測定してブランクテストを行い、ブランク粘度を測定する。パルプ粘度をブランク粘度で割った数値から１を引いて比粘度（ηsp）とし、下記式を用いて、固有粘度（[η]）を算出する。
［η］＝ηsp／（ｃ（１＋０．２８×ηsp））
式中のｃは、粘度測定時のセルロース濃度を示す。
そして、下記式から本発明における重合度（ＤＰ）を算出する。
ＤＰ＝１．７５×[η]
この重合度は、粘度法によって測定された平均重合度であることから、「粘度平均重合度」と称されることもある。
(Degree of polymerization)
The degree of polymerization of the fine cellulose fibers is 100 to 500, preferably 200 to 470, and more preferably 250 to 440. If the degree of polymerization of the fine cellulose fibers is less than the lower limit, it cannot be said to be “fibrous” and it becomes difficult to use as a reinforcing agent for the matrix material. On the other hand, when the degree of polymerization of the fine cellulose fibers exceeds the upper limit, the fluidity when the fine cellulose fibers are slurried decreases, the slurry viscosity becomes too high, and the dispersion stability becomes low. Aggregates may also be formed when mixed with the matrix material.
The degree of polymerization of the fine cellulose fibers is measured by the following method.
Fine cellulose fibers (the supernatant after centrifugation, concentration of about 0.1% by mass) are developed on a polytetrafluoroethylene petri dish and dried at 60 ° C. to obtain a dry sheet. The obtained dry sheet is dispersed in a dispersion medium, and the pulp viscosity is measured according to Tappi T230. Moreover, a blank test is performed by measuring the viscosity only with the dispersion medium, and the blank viscosity is measured. By subtracting 1 from the value obtained by dividing the pulp viscosity by the blank viscosity, the specific viscosity (ηsp) is obtained, and the intrinsic viscosity ([η]) is calculated using the following formula.
[Η] = ηsp / (c (1 + 0.28 × ηsp))
C in a formula shows the cellulose concentration at the time of a viscosity measurement.
Then, the degree of polymerization (DP) in the present invention is calculated from the following formula.
DP = 1.75 × [η]
Since this degree of polymerization is an average degree of polymerization measured by a viscosity method, it may be referred to as “viscosity average degree of polymerization”.
（平均繊維長）
微細セルロース繊維の平均繊維長は、０．０３〜５μｍが好ましく、０．１〜２μｍがさらに好ましい。平均繊維長が前記下限値以上であれば、微細セルロース繊維をマトリクス材料に配合した際の機械的物性をより向上させることができる。平均繊維長が前記上限値以下であれば、微細セルロース繊維をマトリクス材料に配合した際の分散性が良好となる。
平均繊維長は、前記平均繊維幅を測定する際に使用した電子顕微鏡観察画像を解析することにより求めることができる。すなわち、上記のような電子顕微鏡観察画像に対して、直線Ｘに交錯する繊維、直線Ｙに交錯する繊維の各々について少なくとも２０本（すなわち、合計が少なくとも４０本）の繊維長を読み取る。こうして上記のような電子顕微鏡画像を少なくとも３組以上観察し、少なくとも４０本×３組（すなわち、少なくとも１２０本）の繊維長を読み取る。このように読み取った繊維長を平均して平均繊維長を求める。
(Average fiber length)
The average fiber length of the fine cellulose fibers is preferably 0.03 to 5 μm, and more preferably 0.1 to 2 μm. If average fiber length is more than the said lower limit, the mechanical physical property at the time of mix | blending a fine cellulose fiber with a matrix material can be improved more. If average fiber length is below the said upper limit, the dispersibility at the time of mix | blending a fine cellulose fiber with a matrix material will become favorable.
The average fiber length can be determined by analyzing the electron microscope observation image used when measuring the average fiber width. That is, at least 20 fibers (that is, a total of at least 40 fibers) are read for each of the fibers intersecting with the straight line X and the fibers intersecting with the straight line Y with respect to the electron microscope observation image as described above. In this way, at least three or more sets of electron microscope images as described above are observed, and the fiber length of at least 40 × 3 sets (that is, at least 120 sets) is read. The average fiber length is obtained by averaging the fiber lengths thus read.
（アスペクト比）
微細セルロースのアスペクト比は１０〜３００の範囲内であることが好ましく、２５〜２５０の範囲内であることがより好ましく、５０〜２００の範囲がさらに好ましい。アスペクト比が前記下限値以上であれば、マトリクス材料の補強剤として、より好適になる。アスペクト比が前記上限値以下であれば、スラリー化したときの粘度がより低くなる。
平均アスペクト比は、以下の方法により求める。
すなわち、前記電子顕微鏡画像から観察された各々の繊維についてランダムに４０本を選んで、各々のアスペクト比、つまり（繊維長）／（繊維幅）を求める。このアスペクト比は、前記４０本のアスペクト比の平均値である。
(aspect ratio)
The aspect ratio of the fine cellulose is preferably in the range of 10 to 300, more preferably in the range of 25 to 250, and still more preferably in the range of 50 to 200. If the aspect ratio is equal to or higher than the lower limit value, it is more suitable as a reinforcing agent for the matrix material. If an aspect ratio is below the said upper limit, the viscosity when made into a slurry will become lower.
The average aspect ratio is obtained by the following method.
That is, 40 fibers are randomly selected for each fiber observed from the electron microscope image, and each aspect ratio, that is, (fiber length) / (fiber width) is obtained. This aspect ratio is an average value of the 40 aspect ratios.
（酸基含有量）
微細セルロース繊維における酸基の含有量は０．１ｍｍｏｌ／ｇ以下であることが好ましく、０．０６ｍｍｏｌ／ｇ以下であることがより好ましい。酸基の含有量が前記上限値を超えると、水を保持しやすくなり、濾水性が不充分になり、微細セルロース繊維をシート化する場合には生産性が低くなり、シート化が困難になる。また、酸基の含有量が前記上限値を超えると、黄変が生じやすくなる。
(Acid group content)
The content of acid groups in the fine cellulose fiber is preferably 0.1 mmol / g or less, and more preferably 0.06 mmol / g or less. If the content of the acid group exceeds the upper limit, water tends to be retained, the drainage becomes insufficient, and when the fine cellulose fiber is made into a sheet, the productivity is lowered and the sheeting becomes difficult. . Moreover, when content of an acid group exceeds the said upper limit, it will become easy to produce yellowing.
前記酸基とは、カルボン酸基、リン酸基、スルホン酸基など、酸性を示す官能基のことである。セルロースは、カルボキシ基を導入する処理を施さなくても、少量（具体的には０．１ｍｍｏｌ／ｇ以下）のカルボキシ基を有している。したがって、微細セルロース繊維における酸基の含有量が０．１ｍｍｏｌ／ｇ以下とは、セルロースに実質的に新たに酸基が導入されていないことを意味する。なお、リン酸基は、セルロースに、少なくとも（ＨＰＯ４）２−を有するリンオキソ酸またはその塩を作用させることにより導入される。スルホン酸基は、セルロースに、少なくとも（ＨＳＯ３）−を有する硫黄オキソ酸またはその塩を作用させることにより導入される。 The acid group is a functional group showing acidity, such as a carboxylic acid group, a phosphoric acid group, or a sulfonic acid group. Cellulose has a small amount (specifically, 0.1 mmol / g or less) of carboxy groups even without a treatment for introducing carboxy groups. Therefore, the content of acid groups in the fine cellulose fiber of 0.1 mmol / g or less means that substantially no new acid groups have been introduced into the cellulose. Incidentally, the phosphate group, the cellulose, is introduced by the action of phosphorus oxo acid or a salt thereof with a 2-least (HPO 4). The sulfonic acid group is introduced by allowing a sulfur oxo acid having at least (HSO 3 ) − or a salt thereof to act on cellulose.
酸基の含有量は、米国ＴＡＰＰＩの「Ｔｅｓｔ Ｍｅｔｈｏｄ Ｔ２３７ ｃｍ−０８（２００８）：Ｃａｒｂｏｘｙｌ Ｃｏｎｔｅｎｔ ｏｆ ｐｕｌｐ」の方法を用いて求める。酸基の含有量をより広範囲まで測定可能にするために、前記試験方法に用いる試験液のうち、炭酸水素ナトリウム（ＮａＨＣＯ３）／塩化ナトリウム（ＮａＣｌ）＝０．８４ｇ／５．８５ｇを蒸留水で１０００ｍｌに溶解希釈した試験液について、前記試験液の濃度が実質的に４倍となるように、水酸化ナトリウム１．６０ｇに変更した以外は、ＴＡＰＰＩ Ｔ２３７ ｃｍ−０８（２００８）に準じる。また、酸基を導入した場合には、酸基導入前後のセルロース繊維における測定値の差を実質的な酸基含有量とする。なお、測定試料とする絶乾セルロース繊維は、加熱乾燥の際の加熱によって起こる可能性があるセルロースの変質を避けるため、凍結乾燥により得たものを使用する。
当該酸基含有量測定方法は、１価の酸性基（カルボキシ基）についての測定方法であることから、定量対象の酸基が多価の場合には、前記１価の酸基含有量として得られた値を、酸価数で除した数値を酸基含有量とする。
The content of the acid group is determined using a method of “Test Method T237 cm-08 (2008): Carboxyl Content of pull” of TAPPI, USA. In order to make it possible to measure the content of acid groups in a wider range, among the test solutions used in the test method, sodium hydrogen carbonate (NaHCO 3 ) / sodium chloride (NaCl) = 0.84 g / 5.85 g was distilled water. According to TAPPI T237 cm-08 (2008), except that the test solution dissolved and diluted in 1000 ml was changed to 1.60 g of sodium hydroxide so that the concentration of the test solution was substantially 4-fold. Moreover, when an acid group is introduced, the difference between the measured values of cellulose fibers before and after the introduction of the acid group is regarded as a substantial acid group content. In addition, the absolutely dry cellulose fiber used as a measurement sample is one obtained by freeze-drying in order to avoid alteration of cellulose that may occur due to heating during heat drying.
Since the acid group content measurement method is a measurement method for a monovalent acidic group (carboxy group), when the acid group to be quantified is multivalent, it is obtained as the monovalent acid group content. The value obtained by dividing the obtained value by the acid value is defined as the acid group content.
（微細セルロース繊維の製造方法）
上記微細セルロース繊維は、セルロース原料を酵素処理し、解繊処理して得たものである。
(Method for producing fine cellulose fiber)
The fine cellulose fiber is obtained by subjecting a cellulose raw material to an enzyme treatment and a fibrillation treatment.
［セルロース原料］
セルロース原料としては、製紙用パルプ、コットンリンターやコットンリントなどの綿系パルプ、麻、麦わら、バガスなどの非木材系パルプ、ホヤや海草などから単離されるセルロースなどが挙げられる。これらの中でも、入手のしやすさという点で、製紙用パルプが好ましい。製紙用パルプとしては、広葉樹クラフトパルプ（晒クラフトパルプ（ＬＢＫＰ）、未晒クラフトパルプ（ＬＵＫＰ）、酸素漂白クラフトパルプ（ＬＯＫＰ）など）、針葉樹クラフトパルプ（晒クラフトパルプ（ＮＢＫＰ）、未晒クラフトパルプ（ＮＵＫＰ）、酸素漂白クラフトパルプ（ＮＯＫＰ）など）、サルファイトパルプ（ＳＰ）、ソーダパルプ（ＡＰ）等の化学パルプ、セミケミカルパルプ（ＳＣＰ）、ケミグラウンドウッドパルプ（ＣＧＰ）等の半化学パルプ、砕木パルプ（ＧＰ）、サーモメカニカルパルプ（ＴＭＰ、ＢＣＴＭＰ）等の機械パルプ、楮、三椏、麻、ケナフ等を原料とする非木材パルプ、古紙を原料とする脱墨パルプが挙げられる。これらの中でも、より入手しやすいことから、クラフトパルプ、脱墨パルプ、サルファイトパルプが好ましい。
セルロース原料は１種を単独で用いてもよいし、２種以上混合して用いてもよい。
[Cellulose raw material]
Examples of the cellulose raw material include paper pulp, cotton pulp such as cotton linter and cotton lint, non-wood pulp such as hemp, straw and bagasse, cellulose isolated from sea squirts and seaweeds, and the like. Among these, paper pulp is preferable in terms of availability. Paper pulp includes hardwood kraft pulp (bleached kraft pulp (LBKP), unbleached kraft pulp (LUKP), oxygen bleached kraft pulp (LOKP), etc.), softwood kraft pulp (bleached kraft pulp (NBKP), unbleached kraft pulp) (NUCKP, oxygen bleached kraft pulp (NOKP), etc.), sulfite pulp (SP), chemical pulp such as soda pulp (AP), semi-chemical pulp (SCP), semi-chemical pulp such as chemiground wood pulp (CGP) In addition, mechanical pulp such as groundwood pulp (GP) and thermomechanical pulp (TMP, BCTMP), non-wood pulp using raw material such as cocoon, sardine, hemp, kenaf and the like, and deinked pulp using raw paper as a raw material. Among these, kraft pulp, deinked pulp, and sulfite pulp are preferable because they are more easily available.
A cellulose raw material may be used individually by 1 type, and may be used in mixture of 2 or more types.
酵素反応効率を向上させるために、酵素処理の前に、セルロース原料に機械的破砕処理を施すことが好ましい。粉砕方法は乾式、湿式のいずれでもよい。
粉砕処理に用いる粉砕機としては、グラインダー、圧力ホモジナイザー、シュレッダー、カッターミルなどのせん断式粉砕機、ジョークラッシャーやコーンクラッシャーなどの圧縮式粉砕機、インパクトクラッシャーなどの衝撃式粉砕機、あるいはロールミル、スタンプミル、エッジランナーミル、ロッドミルなどの中砕機等が挙げられる。これらの中から、最終の用途やコストの点から適宜選択することができる。
また、粉砕機として、パルプを離解する離解機あるいは、パルプを叩解するリファイナーを使用することもできる。
In order to improve the enzyme reaction efficiency, it is preferable to subject the cellulose raw material to mechanical crushing before the enzyme treatment. The pulverization method may be either dry or wet.
As the pulverizer used for the pulverization treatment, a shearing pulverizer such as a grinder, a pressure homogenizer, a shredder and a cutter mill, a compression pulverizer such as a jaw crusher and a cone crusher, an impact pulverizer such as an impact crusher, a roll mill, a stamp Examples include a grinding machine such as a mill, an edge runner mill, and a rod mill. From these, it can select suitably from the point of the final use and cost.
Further, as the pulverizer, a disintegrator that disaggregates pulp or a refiner that beats pulp can also be used.
また、酵素処理の前には、セルロース原料を分散媒で希釈して、セルロース濃度が０．２〜２０質量％の分散液にすることが好ましい。分散媒としては水、有機溶剤のいずれも使用できるが、水が好ましい。
有機溶剤としては、アルコール系溶剤（メタノール、エタノール、プロパノール、ブタノール等）、ケトン系溶剤（アセトン、メチルエチルケトン等）、エーテル系溶剤（ジエチルエーテル、エチレングリコールジメチルエーテル、テトラヒドロフラン等）、アセテート系溶剤（酢酸エチル等）等の極性溶剤が好ましい。
Moreover, before the enzyme treatment, it is preferable to dilute the cellulose raw material with a dispersion medium to obtain a dispersion having a cellulose concentration of 0.2 to 20% by mass. Either water or an organic solvent can be used as the dispersion medium, but water is preferred.
Organic solvents include alcohol solvents (methanol, ethanol, propanol, butanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, etc.), acetate solvents (ethyl acetate, etc.) Etc.) are preferred.
［酵素処理］
酵素処理では、セルロース原料を、セルロース分解酵素によって酵素処理して酵素処理セルロースを得る。
酵素処理で使用するセルロース分解酵素は、非晶部に対する分解活性であるエンドグルカナーゼ活性（以下、「ＥＧ活性」という。）と、結晶部に対する分解活性であるセロビオヒドロラーゼ活性（以下、「ＣＢＨＩ活性」という。）を有する酵素である。
該セルロース分解酵素は、ＥＧ活性とＣＢＨＩ活性の比（ＥＧ活性／ＣＢＨＩ活性）が０．０６以上であり、０．１以上であることが好ましく、１．０以上であることがより好ましい。ＥＧ活性とＣＢＨＩ活性の比が前記下限値未満であると、酵素処理後のセルロース繊維のアスペクト比が小さくなり、得られる微細セルロース繊維が補強材として適さないものになる。
ＥＧ活性とＣＢＨＩ活性の比は２０以下が好ましく、１０以下がより好ましく、６以下がさらに好ましい。
[Enzyme treatment]
In the enzyme treatment, the cellulose raw material is enzymatically treated with a cellulolytic enzyme to obtain enzyme-treated cellulose.
Cellulose-degrading enzymes used in the enzyme treatment include an endoglucanase activity (hereinafter referred to as “EG activity”) that is a degrading activity on the amorphous part and a cellobiohydrolase activity (hereinafter referred to as “CBHI activity”) that is a degrading activity on the crystal part. ").).
The cellulolytic enzyme has a ratio of EG activity to CBHI activity (EG activity / CBHI activity) of 0.06 or more, preferably 0.1 or more, and more preferably 1.0 or more. If the ratio of the EG activity to the CBHI activity is less than the lower limit, the aspect ratio of the cellulose fiber after the enzyme treatment becomes small, and the resulting fine cellulose fiber becomes unsuitable as a reinforcing material.
The ratio of EG activity to CBHI activity is preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less.
上記ＥＧ活性は下記のように測定され、定義される。
濃度１％（Ｗ／Ｖ）のカルボキシルメチルセルロース（ＣＭＣＮａ High viscosity; Cat No 150561, MP Biomedicals, Inc.）の基質溶液（濃度１００ｍＭ、ｐＨ５．０の酢酸−酢酸ナトリウム緩衝液含有）を調製する。測定用酵素を予め緩衝液（前記同様）で希釈する。希釈倍率は下記酵素溶液の吸光度が下記グルコース標準液から得られた検量線に入ればよい。９０μｌの前記基質溶液に前記希釈して得られた酵素溶液１０μｌを添加し、３７℃、３０分間反応させる。
検量線を作成するために、イオン交換水（ブランク）、グルコース標準液（濃度０．５〜５．６ｍＭから少なくとも濃度が異なる標準液４点）を選択し、それぞれ１００μｌを用意し、３７℃、３０分間保温する。
前記反応後の酵素含有溶液、検量線用ブランクおよびグルコース標準液に、それぞれ３００μｌのＤＮＳ発色液（１．６質量％のＮａＯＨ、１質量％の３，５−ジニトロサリチル酸、３０質量％の酒石酸カリウムナトリウム）を加えて、５分間煮沸し発色させる。発色後直ちに氷冷し、２ｍｌのイオン交換水を加えてよく混合する。３０分間静置した後、１時間以内に吸光度を測定する。
吸光度の測定は９６穴マイクロウェルプレート（２６９６２０、ＮＵＮＣ社製）に２００μｌを分注し、マイクロプレートリーダー（ｉｎｆｉｎｉｔｅＭ２００、ＴＥＣＡＮ社製）を用い、５４０ｎｍの吸光度を測定する。
ブランクの吸光度を差し引いた各グルコース標準液の吸光度とグルコース濃度を用い検量線を作成する。酵素溶液中のグルコース相当生成量は酵素溶液の吸光度からブランクの吸光度を引いてから検量線を用いて算出する。酵素溶液の吸光度が検量線に入らない場合は前記緩衝液で酵素を希釈する際の希釈倍率を変えて再測定を行う。１分間に１μｍｏｌｅのグルコース等量の還元糖を生成する酵素量を１単位と定義し、下記式からＥＧ活性を求める。
ＥＧ活性＝緩衝液で希釈して得られた酵素溶液１ｍｌのグルコース相当生成量（μｍｏｌｅ）／３０分×希釈倍率
［福井作蔵,“生物化学実験法（還元糖の定量法）第二版”,学会出版センター、ｐ２３〜２４（１９９０年）参照]
The EG activity is measured and defined as follows.
A substrate solution of carboxymethylcellulose (CMCNa High viscosity; Cat No 150561, MP Biomedicals, Inc.) at a concentration of 1% (W / V) (containing 100 mM, pH 5.0 acetate-sodium acetate buffer) is prepared. The enzyme for measurement is previously diluted with a buffer solution (as described above). The dilution rate may be such that the absorbance of the following enzyme solution falls within a calibration curve obtained from the following glucose standard solution. 10 μl of the enzyme solution obtained by the dilution is added to 90 μl of the substrate solution and reacted at 37 ° C. for 30 minutes.
In order to prepare a calibration curve, ion-exchanged water (blank) and glucose standard solution (4 standard solutions having different concentrations from at least 0.5 to 5.6 mM) are selected, and 100 μl each is prepared, 37 ° C., Incubate for 30 minutes.
To the enzyme-containing solution, the calibration curve blank and the glucose standard solution after the reaction, 300 μl of a DNS coloring solution (1.6% by weight NaOH, 1% by weight 3,5-dinitrosalicylic acid, 30% by weight potassium tartrate, respectively) Add sodium) and boil for 5 minutes to develop color. Immediately after color development, cool with ice, add 2 ml of ion-exchanged water, and mix well. After standing for 30 minutes, the absorbance is measured within 1 hour.
Absorbance is measured by dispensing 200 μl into a 96-well microwell plate (269620, manufactured by NUNC), and measuring the absorbance at 540 nm using a microplate reader (infiniteM200, manufactured by TECAN).
A calibration curve is prepared using the absorbance and glucose concentration of each glucose standard solution obtained by subtracting the absorbance of the blank. The amount corresponding to glucose in the enzyme solution is calculated using a calibration curve after subtracting the absorbance of the blank from the absorbance of the enzyme solution. If the absorbance of the enzyme solution does not fall within the calibration curve, repeat the measurement by changing the dilution factor when the enzyme is diluted with the buffer solution. The amount of enzyme that produces 1 μmole glucose equivalent of reducing sugar per minute is defined as 1 unit, and EG activity is obtained from the following formula.
EG activity = 1 ml of enzyme solution obtained by diluting with buffer solution (μmole) / 30 minutes x dilution factor
[Refer to Sakuzo Fukui, “Biochemical Experimental Method (Quantitative Method for Reducing Sugar) Second Edition”, Academic Publishing Center, p23-24 (1990)]
上記ＣＢＨＩ活性は下記のように測定され、定義される。
９６穴マイクロウェルプレート（２６９６２０、ＮＵＮＣ社製）に１．２５ｍＭの４−メチル−ウンベリフェリル−セルロビオサイド（濃度１２５ｍＭ、ｐＨ５．０の酢酸−酢酸ナトリウム緩衝液に溶解した）３２μｌを分注し、１００ｍＭのグルコノ−１，５−ラクトン４μｌを添加する。さらに、前記同様の緩衝液で希釈（希釈倍率は下記酵素溶液の蛍光発光度が下記標準液から得られた検量線に入ればよい）した測定用酵素液４μｌを加え、３７℃、３０分間反応させた後、５００ｍＭのグリシン−ＮａＯＨ緩衝液（ｐＨ１０．５）２００μｌを添加し、反応を停止させる。
前記同様の９６穴マイクロウェルプレートに検量線の標準液として４−メチル−ウンベリフェロン標準溶液４０μｌ（濃度０〜５０μＭの少なくとも濃度が異なる標準液４点）を分注し、３７℃、３０分間加温した後、５００ｍＭのグリシン−ＮａＯＨ緩衝液（ｐＨ１０．５）２００μｌを添加する。
マイクロプレートリーダー（ＦｌｕｏｒｏｓｋａｎＡｓｃｅｎｔＦＬ、Ｔｈｅｒｍｏ−Ｌａｂｓｙｓｔｅｍｓ社製）を用い、３５０ｎｍ（励起光４６０ｎｍ）における蛍光発光度を測定する。標準液のデータから作成した検量線を用い、酵素溶液中の４−メチル−ウンベリフェロン生成量を算出する（酵素溶液の蛍光発光度が検量線に入らない場合は希釈率を変えて再測定を行う）。１分間に１μｍｏｌの４−メチル−ウンベリフェロンを生成する酵素の量を１単位とし、下記式からＣＢＨＩ活性を求める。
ＣＢＨＩ活性＝希釈後酵素溶液１ｍｌの４−メチル−ウンベリフェロン生成量（μｍｏｌｅ）／３０分×希釈倍率
The CBHI activity is measured and defined as follows.
Dispense 32 μl of 1.25 mM 4-methyl-umbelliferyl-cellulobioside (dissolved in acetic acid-sodium acetate buffer solution with a concentration of 125 mM, pH 5.0) into a 96-well microwell plate (269620, manufactured by NUNC). 4 μl of 100 mM glucono-1,5-lactone is then added. Furthermore, 4 μl of the enzyme solution for measurement diluted with the same buffer as above (dilution ratio should be within the calibration curve obtained from the following standard solution with the fluorescence emission degree of the enzyme solution below) is added and reacted at 37 ° C. for 30 minutes. After that, 200 μl of 500 mM glycine-NaOH buffer (pH 10.5) is added to stop the reaction.
Dispense 40 μl of 4-methyl-umbelliferone standard solution (4 standard solutions with different concentrations of 0 to 50 μM) as standard solutions for the calibration curve into the same 96-well microwell plate as above, at 37 ° C. for 30 minutes. After warming, 200 μl of 500 mM glycine-NaOH buffer (pH 10.5) is added.
Using a microplate reader (Fluoroskan Ascent FL, manufactured by Thermo-Labsystems), the fluorescence intensity at 350 nm (excitation light: 460 nm) is measured. Calculate the amount of 4-methyl-umbelliferone produced in the enzyme solution using the calibration curve created from the data of the standard solution (if the fluorescence intensity of the enzyme solution does not fall within the calibration curve, change the dilution rate and re-measure I do). CBHI activity is determined from the following formula, assuming that the amount of enzyme that produces 1 μmol of 4-methyl-umbelliferone per minute is 1 unit.
CBHI activity = diluted enzyme solution 1 ml 4-methyl-umbelliferone production (μmole) / 30 minutes × dilution ratio
酵素処理で使用するセルロース分解酵素は、各種セルロース分解酵素を、夫々の活性を有する酵素を適宜の量で混合して調製してもよいが、市販のセルラーゼ製剤を用いてもよい。
市販のセルラーゼ製剤としては、トリコデルマ（Ｔｒｉｃｈｏｄｅｒｍａ）属、アクレモニウム属（Ａｃｒｅｍｏｎｉｕｍ）属、アスペルギルス（Ａｓｐｅｒｇｉｌｌｕｓ）属、ファネロケエテ（Ｐｈａｎｅｒｏｃｈａｅｔｅ）属、トラメテス属（Ｔｒａｍｅｔｅｓ）、フーミコラ（Ｈｕｍｉｃｏｌａ）属、バチルス（Ｂａｃｉｌｌｕｓ）属などに由来するセルラーゼ製剤が挙げられる。このようなセルラーゼ製剤の市販品としては、全て商品名で、例えば、セルロイシンＴ２（エイチピィアイ社製）、メイセラーゼ（明治製菓社製）、ノボザイム１８８（ノボザイム社製）、マルティフェクトＣＸ１０Ｌ（ジェネンコア社製）が挙げられる
また、酵素処理では、酵素として、ヘミセルラーゼ系酵素を単独でまたはセルラーゼ系酵素と組み合わせて使用してもよい、ヘミセルラーゼ系酵素の中でも、キシランを分解する酵素であるキシラナーゼ（ｘｙｌａｎａｓｅ）、マンナンを分解する酵素であるマンナーゼ（ｍａｎｎａｓｅ）、アラバンを分解する酵素であるアラバナーゼ（ａｒａｂａｎａｓｅ）を使用することが好ましい。また、ペクチンを分解する酵素であるペクチナーゼもヘミセルラーゼ系酵素として使用することができる。
The cellulolytic enzyme used in the enzyme treatment may be prepared by mixing various cellulolytic enzymes with appropriate amounts of enzymes having respective activities, but commercially available cellulase preparations may also be used.
Commercial cellulase preparations include Trichoderma, Acremonium, Aspergillus, Phanerocheet, Trametes, Humicola, and Humicola. Cellulase preparations derived from the above. Commercially available products of such cellulase preparations are all trade names, for example, cellulosin T2 (manufactured by HIPI), mecerase (manufactured by Meiji Seika Co., Ltd.), Novozyme 188 (manufactured by Novozyme), multifect CX10L (manufactured by Genencor) In the enzyme treatment, a hemicellulase enzyme may be used alone or in combination with a cellulase enzyme as an enzyme. Among hemicellulase enzymes, xylanase (xylanase) is an enzyme that degrades xylan. ), Mannanase which is an enzyme degrading mannan, and arabanase which is an enzyme decomposing araban are preferably used. In addition, pectinase, which is an enzyme that degrades pectin, can also be used as a hemicellulase-based enzyme.
また、該酵素処理で使用するセルロース分解酵素は、二糖を切断するベータグルコシダーゼ活性（以下、「ＢＧＬ活性」という。）をほとんど有さない。
具体的に、該酵素処理で使用するセルロース分解酵素は、ＢＧＬ活性とＣＢＨＩ活性との比率（ＢＧＬ活性／ＣＢＨＩ活性）が０．１以下であることが好ましく、０であることが最も好ましい。ＢＧＬ活性とＣＢＨ活性との比率が前記上限値以下であると、高アスペクト比で補強材として適した微細セルロース繊維が得られやすくなる。
In addition, the cellulolytic enzyme used in the enzyme treatment has little beta-glucosidase activity (hereinafter referred to as “BGL activity”) that cleaves disaccharides.
Specifically, the cellulolytic enzyme used in the enzyme treatment preferably has a ratio of BGL activity to CBHI activity (BGL activity / CBHI activity) of 0.1 or less, and most preferably 0. When the ratio between the BGL activity and the CBH activity is not more than the above upper limit value, it becomes easy to obtain fine cellulose fibers suitable as a reinforcing material with a high aspect ratio.
上記ＢＧＬ活性は下記のように測定され、定義される。
９６穴マイクロウェルプレート（２６９６２０、ＮＵＮＣ社製）に１．２５ｍＭの４−メチル−ウンベリフェリル−グルコサイド（濃度１００ｍＭ、ｐＨ５．０の酢酸−酢酸ナトリウム緩衝液に溶解した）１６μｌを分注する。これに前期同様の緩衝液で希釈（希釈倍率は下記酵素溶液の蛍光発光度が下記標準液から得られた検量線に入ればよい）した測定用酵素液４μｌを加え、３７℃で３０分間反応させた後、５００ｍＭのグリシン−ＮａＯＨ緩衝液（ｐＨ１０．５）１００μｌを反応液に添加し、反応を停止させる。
前期同様の９６穴マイクロウェルプレートに検量線の標準液として４−メチル−ウンベリフェロン標準溶液４０μｌ（濃度０〜５０μＭの少なくとも濃度が異なる標準液４点）を分注し、３７℃、３０分間加温した後、５００ｍＭのグリシン−ＮａＯＨ緩衝液（ｐＨ１０．５）２００μｌを添加する。
マイクロプレートリーダー（ＦｌｕｏｒｏｓｋａｎＡｓｃｅｎｔＦＬ、Ｔｈｅｒｍｏ−Ｌａｂｓｙｓｔｅｍｓ社製）を用い、３５０ｎｍ（励起光４６０ｎｍ）における蛍光発光度を測定する。標準液のデータから作成した検量線を用い、酵素溶液中の４−メチル−ウンベリフェロン生成量を算出する（酵素溶液の蛍光発光度が検量線に入らない場合は希釈率を変えて再測定を行う）。１分間に１μｍｏｌの４−メチル−ウンベリフェロンを生成する酵素の量を１単位とし、下記式からＢＧＬ活性を求める。
ＢＧＬ活性＝希釈後酵素溶液１ｍｌの４−メチル−ウンベリフェロン生成量（μｍｏｌｅ）／３０分×希釈倍率
The BGL activity is measured and defined as follows.
Dispense 16 μl of 1.25 mM 4-methyl-umbelliferyl-glucoside (dissolved in acetic acid-sodium acetate buffer solution at a concentration of 100 mM, pH 5.0) into a 96-well microwell plate (269620, manufactured by NUNC). . To this was added 4 μl of the enzyme solution for measurement diluted with the same buffer as in the previous period (dilution ratio should be within the calibration curve obtained from the standard solution shown below), and reacted at 37 ° C. for 30 minutes. Then, 100 μl of 500 mM glycine-NaOH buffer (pH 10.5) is added to the reaction solution to stop the reaction.
Dispense 40 μl of 4-methyl-umbelliferone standard solution (4 standard solutions with different concentrations of 0 to 50 μM) as standard solutions for a calibration curve into the same 96-well microwell plate as in the previous period, at 37 ° C. for 30 minutes. After warming, 200 μl of 500 mM glycine-NaOH buffer (pH 10.5) is added.
Using a microplate reader (Fluoroskan Ascent FL, manufactured by Thermo-Labsystems), the fluorescence intensity at 350 nm (excitation light: 460 nm) is measured. Calculate the amount of 4-methyl-umbelliferone produced in the enzyme solution using the calibration curve created from the data of the standard solution (if the fluorescence intensity of the enzyme solution does not fall within the calibration curve, change the dilution rate and re-measure I do). BGL activity is calculated from the following formula using the amount of enzyme that produces 1 μmol of 4-methyl-umbelliferone per minute as 1 unit.
BGL activity = diluted enzyme solution 1 ml 4-methyl-umbelliferone production (μmole) / 30 minutes × dilution ratio
酵素処理の際の分散液のｐＨは、使用する酵素の活性が高くなる範囲に保つことが好ましい。例えば、トリコデルマ起源の市販の酵素の場合、ｐＨは４〜８の間が好ましい。
また、酵素処理の際の分散液の温度は、使用する酵素の活性が高くなる範囲に保つことが好ましい。例えば、トリコデルマ起源の市販の酵素の場合、温度は４０〜６０℃が好ましい。温度が前記下限値未満では酵素活性が低下して処理時間が長くなり、前記上限値を超えると酵素が失活するおそれがある。
酵素処理の処理時間は１０分〜２４時間の範囲が好ましい。１０分未満では酵素処理の効果が発現しにくい。２４時間を超えると酵素によりセルロース繊維の分解が進みすぎて、得られる微細セルロース繊維の平均繊維長が短くなりすぎるおそれがある。
The pH of the dispersion during the enzyme treatment is preferably maintained in a range where the activity of the enzyme used is high. For example, in the case of a commercially available enzyme derived from Trichoderma, the pH is preferably between 4-8.
Further, the temperature of the dispersion during the enzyme treatment is preferably maintained within a range in which the activity of the enzyme used is increased. For example, in the case of a commercially available enzyme derived from Trichoderma, the temperature is preferably 40 to 60 ° C. If the temperature is less than the lower limit, the enzyme activity decreases and the treatment time becomes longer. If the temperature exceeds the upper limit, the enzyme may be deactivated.
The treatment time for the enzyme treatment is preferably in the range of 10 minutes to 24 hours. If it is less than 10 minutes, the effect of the enzyme treatment is hardly exhibited. If it exceeds 24 hours, the decomposition of the cellulose fiber is too advanced by the enzyme, and the average fiber length of the resulting fine cellulose fiber may be too short.
なお、所定時間以上に酵素が活性なままで残留していると前記のようにセルロースの分解が進み過ぎるため、所定の酵素処理が終了した際には、酵素反応の停止処理を施すことが好ましい。酵素反応の停止処理としては、酵素処理を施した分散液を水洗し、酵素を除去する方法、酵素処理を施した分散液に水酸化ナトリウムをｐＨが１２程度になるように添加して酵素を失活させる方法、酵素処理を施した分散液の温度を温度９０℃まで上昇させて酵素を失活させる方法が挙げられる。 It should be noted that when the enzyme remains active for a predetermined time or longer, the decomposition of cellulose proceeds excessively as described above. Therefore, when the predetermined enzyme treatment is completed, it is preferable to perform an enzyme reaction stop process. . The enzyme reaction is stopped by washing the enzyme-treated dispersion with water, removing the enzyme, adding sodium hydroxide to the enzyme-treated dispersion to a pH of about 12, and then adding the enzyme. Examples thereof include a method for inactivation and a method for inactivating the enzyme by raising the temperature of the dispersion treated with the enzyme to a temperature of 90 ° C.
［解繊処理］
解繊処理では、前記上記酵素処理で得た酵素処理セルロースを、重合度が１００〜５００になるように解繊して微細セルロース繊維を得る。
微細化する前のセルロースは、水で希釈されて、セルロース濃度が０．１〜１０質量％の分散液にされることが好ましい。微細化前の分散液のセルロース濃度は、０．２〜５質量％であることがより好ましく、０．３〜３質量％であることがさらに好ましい。微細化前の分散液のセルロース濃度が前記下限値以上であれば、解繊効率が高くなり、前記上限値以下であれば、解繊処理中の粘度の上昇を防ぐことができる。
微細セルロース繊維の重合度は、解繊条件によって調整することができる。例えば、解繊時のせん断力を強くする程、解繊時間を長くする程、重合度は小さくなる。
[Defibration processing]
In the defibrating treatment, the enzyme-treated cellulose obtained by the enzyme treatment is defibrated so as to have a polymerization degree of 100 to 500 to obtain fine cellulose fibers.
The cellulose before being refined is preferably diluted with water to obtain a dispersion having a cellulose concentration of 0.1 to 10% by mass. The cellulose concentration of the dispersion before refining is more preferably 0.2 to 5% by mass, and further preferably 0.3 to 3% by mass. If the cellulose concentration of the dispersion before refinement is not less than the lower limit, the defibrating efficiency is increased, and if it is not more than the upper limit, an increase in viscosity during the defibrating treatment can be prevented.
The degree of polymerization of the fine cellulose fibers can be adjusted according to the defibrating conditions. For example, the degree of polymerization becomes smaller as the shearing force at the time of defibration is increased and the defibration time is increased.
微細化方法としては、各種粉砕装置を用いる方法が挙げられる。粉砕装置としては、高速解繊機、グラインダー（石臼型粉砕機）、高圧ホモジナイザーや超高圧ホモジナイザー、高圧衝突型粉砕機、ボールミル、ビーズミル、ディスク型リファイナー、コニカルリファイナー、二軸混練機、振動ミル、高速回転下でのホモミキサー、超音波分散機、ビーターなど、湿式粉砕する装置等を適宜使用することができる。これらのなかでも、特に、高圧ホモジナイザー、高速回転型解繊機あるいは両者併用が好ましい。 Examples of the miniaturization method include a method using various pulverizers. High-speed defibrator, grinder (stone mortar-type pulverizer), high-pressure homogenizer and ultra-high-pressure homogenizer, high-pressure collision type pulverizer, ball mill, bead mill, disk type refiner, conical refiner, twin-screw kneader, vibration mill, high speed A wet milling apparatus such as a homomixer under rotation, an ultrasonic disperser, or a beater can be used as appropriate. Among these, a high-pressure homogenizer, a high-speed rotation type defibrator, or a combination of both is particularly preferable.
高圧ホモジナイザーは、酵素処理した分散液を加圧し、その加圧した分散液を急激に減圧することにより微細化する装置である。高圧ホモジナイザー処理は１回でもよいが、複数回繰り返すことにより、微細化度をさらに上げて所望の繊維幅の微細セルロース繊維を容易に得ることができる。繰り返し数が多い程、微細化の程度を上げることができるが、繰り返し数が多すぎると、コスト高となる。
高圧ホモジナイザーの具体例としては、スギノマシン社製の「スターバースト」、イズミフードマシナリ社製の「高圧ホモゲナイザー」、Ｒａｎｎｉｅ社製の「ミニラボ８．３Ｈ型」に代表されるホモバルブ式の高圧ホモジナイザー、Ｍｉｃｒｏｆｌｕｉｄｉｃｓ社製の「マイクロフルイダイザー」、吉田機械興業社製の「ナノマイザー」、スギノマシン社製の「アルティマイザー」、白水化学社製の「ジーナスＰＹ」、日本ビーイーイー社製の「ＤｅＢＥＥ２０００」、ＮｉｒｏＳｏａｖｉ社の「Ａｒｉｅｔｅシリーズ」等のチャンバー式の高圧ホモジナイザー等が挙げられる。
A high-pressure homogenizer is a device that pressurizes an enzyme-treated dispersion and refines it by rapidly depressurizing the pressurized dispersion. The high-pressure homogenizer treatment may be performed once, but by repeating a plurality of times, it is possible to easily obtain fine cellulose fibers having a desired fiber width by further increasing the degree of fineness. As the number of repetitions increases, the degree of miniaturization can be increased. However, when the number of repetitions is too large, the cost increases.
Specific examples of the high-pressure homogenizer include “Starburst” manufactured by Sugino Machine, “High-Pressure Homogenizer” manufactured by Izumi Food Machinery, and a homovalve-type high-pressure homogenizer typified by “Minilab 8.3H type” manufactured by Rannie, "Microfluidizer" manufactured by Microfluidics, "Nanomizer" manufactured by Yoshida Kikai Kogyo Co., Ltd., "Ultimizer" manufactured by Sugino Machine Co., Ltd., "Genus PY" manufactured by Shiramizu Chemical Co., Ltd., "DeBEE2000" manufactured by BB Japan, NiroSoavi Chamber type high-pressure homogenizers such as “Ariete series” of the company are listed.
高速回転型解繊機は、酵素処理した分散液を高速回転させながら狭い空隙を通すことにより高いせん断速度を発生させる装置である。高速回転型解繊機としては、回転体と固定部の間の空隙に処理対象となる分散液を通過させるタイプのものが挙げられる。また、高速回転型解繊機としては、一定方向に回転する内側回転体と、内側回転体の外側を内側回転体とは逆に回転する外側回転体とを有し、内側回転体と外側回転体の間の空隙に処理対象となるパルプ繊維を通過させて分散させるタイプのものが挙げられる。
高速回転型解繊機としては、例えば、エム・テクニック社製の「クレアミックス」、プライミクス社製の「ＴＫロボミクス」、「フィルミックス」、大平洋機工社製の「マイルダー」、「キャビトロン」、「シャープフローミル」等が挙げられる。
The high-speed rotating defibrator is a device that generates a high shear rate by passing a narrow gap while rotating the enzyme-treated dispersion at high speed. Examples of the high-speed rotation type defibrator include a type that allows the dispersion liquid to be processed to pass through the gap between the rotating body and the fixed part. The high-speed rotation type defibrator includes an inner rotating body that rotates in a fixed direction, and an outer rotating body that rotates the outer side of the inner rotating body opposite to the inner rotating body. The pulp fiber to be treated is passed through and dispersed in the gaps between them.
Examples of high-speed defibrating machines include “Clairemix” manufactured by M Technique, “TK Robotics” and “Filmix” manufactured by Primics, “Milder”, “Cabitron” and “Cabitron” manufactured by Taihei Koki. Sharp flow mill ".
解繊処理の後には、平均繊維径および最大繊維径が小さい微細セルロース繊維が容易に得られることから、解繊処理した分散液を遠心分離することが好ましい。 After the defibrating treatment, fine cellulose fibers having a small average fiber diameter and a maximum fiber diameter can be easily obtained. Therefore, it is preferable to centrifuge the defibrated dispersion liquid.
＜マトリクス材料＞
マトリクス材料は、プラスチック及びゴムの少なくとも一方を含む。
ゴムとしては、天然ゴム、ブタジエン重合体、スチレン−ブタジエン共重合体、（メタ）アクリロニトリル−ブタジエン共重合体、ポリイソプレン、ポリクロロプレン、スチレン−ブタジエン−メチルメタクリレート共重合体、（メタ）アクリル酸アルキルエステル共重合体等が挙げられる。
プラスチックとしては、熱可塑性プラスチック、熱硬化性プラスチックのいずれであってもよい。
熱可塑性プラスチックとしては、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ酢酸ビニル、エチレン−酢酸ビニル共重合体、ポリ（メタ）アクリル酸アルキルエステル重合体、（メタ）アクリル酸アルキルエステル共重合体、ポリエステル、ポリカーボネート、ポリアミド、ポリアセタール、ポリフェニレンオキシド等が挙げられる。
熱硬化性プラスチックとしては、ポリウレタン、エポキシ樹脂、オキセタン樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、珪素樹脂、ジアリルフタレート樹脂等が挙げられる。
複合材料に含有させるマトリクス材料は、１種であってもよいし、２種類以上であってもよい。
<Matrix material>
The matrix material includes at least one of plastic and rubber.
As rubber, natural rubber, butadiene polymer, styrene-butadiene copolymer, (meth) acrylonitrile-butadiene copolymer, polyisoprene, polychloroprene, styrene-butadiene-methyl methacrylate copolymer, alkyl (meth) acrylate An ester copolymer etc. are mentioned.
The plastic may be either a thermoplastic plastic or a thermosetting plastic.
Thermoplastics include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, poly (meth) acrylic acid alkyl ester polymer, (meth) acrylic acid alkyl ester. Examples thereof include copolymers, polyesters, polycarbonates, polyamides, polyacetals, and polyphenylene oxides.
Examples of the thermosetting plastic include polyurethane, epoxy resin, oxetane resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, silicon resin, diallyl phthalate resin and the like.
The matrix material contained in the composite material may be one kind or two or more kinds.
マトリクス材料には、必要に応じて、酸化防止剤、紫外線吸収剤、熱安定剤、充填剤、顔料、染料等の添加剤が含まれてもよい。 The matrix material may contain additives such as an antioxidant, an ultraviolet absorber, a heat stabilizer, a filler, a pigment, and a dye as necessary.
「複合材料の製造方法」
複合材料は、微細セルロース繊維とマトリクス材料とを混合することにより製造することができる。
好ましい複合材料の製造方法としては、微細セルロース繊維を含むスラリー状の微細セルロース繊維分散液とエマルション状マトリクス材料とを混合して混合液を得る混合工程と、前記混合液を脱液して、固形分である複合材料を得る脱液工程とを有する方法が挙げられる。この製造方法によれば、マトリクス材料中での微細セルロース繊維の分散性をより向上させることができ、複合材料の機械的物性をより向上させることができる。
"Production method of composite materials"
The composite material can be produced by mixing fine cellulose fibers and a matrix material.
As a preferable method for producing a composite material, a mixing step of mixing a slurry-like fine cellulose fiber dispersion containing fine cellulose fibers and an emulsion matrix material to obtain a mixed solution, and dehydrating the mixed solution to obtain a solid And a liquid removal step of obtaining a composite material that is a minute. According to this manufacturing method, the dispersibility of the fine cellulose fibers in the matrix material can be further improved, and the mechanical properties of the composite material can be further improved.
エマルション状マトリクス材料とは、分散媒中で乳化した、体積平均粒子径が０．００１〜１０μｍのマトリクス材料の粒子である。エマルション状マトリクス材料の製造方法としては、例えば、マトリクス材料を乳化重合する方法、マトリクス材料を後乳化法によってエマルション化する方法が挙げられる。
微細セルロース繊維分散液に含まれる分散媒としては、取り扱い性やコストの点から、水が好ましいが、有機溶剤を水と併用しても構わないし、有機溶剤を単独で使用しても構わない。有機溶剤としては、アルコール系溶剤（メタノール、エタノール、プロパノール、ブタノール等）、ケトン系溶剤（アセトン、メチルエチルケトン等）、エーテル系溶剤（ジエチルエーテル、エチレングリコールジメチルエーテル、テトラヒドロフラン等）、アセテート系溶剤（酢酸エチル等）等の極性溶剤が好ましい。
微細セルロース繊維分散液における微細セルロース繊維の含有量は、分散安定性の点から、６質量％以下であることが好ましく、３質量％以下であることがより好ましい。微細セルロース繊維分散液の微細セルロース繊維含有量は、複合材料の生産性の点から、０．２質量％以上であることが好ましく、０．５質量％以上であることがより好ましい。
微細セルロース繊維分散液には、必要に応じて、防腐剤、顔料、紫外線吸収剤、酸化防止剤などが含まれてもよい。
The emulsion-like matrix material is a matrix material particle emulsified in a dispersion medium and having a volume average particle diameter of 0.001 to 10 μm. Examples of the method for producing an emulsion matrix material include a method of emulsion polymerization of a matrix material and a method of emulsifying a matrix material by a post-emulsification method.
The dispersion medium contained in the fine cellulose fiber dispersion is preferably water from the viewpoints of handleability and cost, but an organic solvent may be used in combination with water, or an organic solvent may be used alone. Organic solvents include alcohol solvents (methanol, ethanol, propanol, butanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, etc.), acetate solvents (ethyl acetate, etc.) Etc.) are preferred.
The content of fine cellulose fibers in the fine cellulose fiber dispersion is preferably 6% by mass or less, and more preferably 3% by mass or less from the viewpoint of dispersion stability. The fine cellulose fiber content of the fine cellulose fiber dispersion is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more from the viewpoint of productivity of the composite material.
The fine cellulose fiber dispersion may contain a preservative, a pigment, an ultraviolet absorber, an antioxidant, and the like, if necessary.
微細セルロース繊維分散液とエマルション状マトリクス材料との混合方法としては、容器に微細セルロース繊維分散液およびエマルション状マトリクス材料を入れホモミキサー等の攪拌機を用いて攪拌する方法、微細セルロース繊維分散液およびエマルション状マトリクス材料をラインミキサーに通す方法が挙げられる。
脱液方法としては、濾紙、濾布、樹脂製フィルタ等の濾材を用いて濾過する方法、加熱により分散媒を蒸発させる方法が挙げられる。
As a method of mixing the fine cellulose fiber dispersion and the emulsion matrix material, a method in which the fine cellulose fiber dispersion and the emulsion matrix material are put in a container and stirred using a stirrer such as a homomixer, the fine cellulose fiber dispersion and the emulsion And a method of passing the matrix material through a line mixer.
Examples of the liquid removal method include a method of filtering using a filter medium such as filter paper, filter cloth, and resin filter, and a method of evaporating the dispersion medium by heating.
複合材料は、上記製造方法以外の方法でも製造することができる。例えば、微細セルロース繊維分散液と固形状のマトリクス材料とを混合し、攪拌した後、脱液する方法、分散液化されていない微細セルロース繊維と固形状のマトリクス材料とを混合し、攪拌する方法等によって複合材料を得てもよい。 The composite material can be manufactured by a method other than the above manufacturing method. For example, a method of mixing and stirring a fine cellulose fiber dispersion and a solid matrix material, a method of draining, a method of mixing and stirring fine cellulose fibers that are not dispersed and a solid matrix material, etc. A composite material may be obtained.
＜作用効果＞
ＥＧ活性／ＣＢＨＩ活性が上記特定範囲にあるセルロース分解酵素を用いて酵素処理した得た微細セルロース繊維は重合度が容易に低くなる。そのため、マトリクス材料中での分散性を向上させることができる。
また、ＥＧ活性／ＣＢＨＩ活性が上記特定範囲にあるセルロース分解酵素を用いて酵素処理した得た微細セルロース繊維は繊維幅が容易に小さくなり、アスペクト比が高くなる。アスペクト比が高い微細セルロース繊維同士は、マトリクス材料中にて、少ない繊維量で交わりやすくなる。そのため、マトリクス材料中で微細セルロース繊維のネットワークが効率的に形成されやすくなり、補強効果に優れる。
したがって、上記酵素処理して得た微細セルロース繊維とマトリクス材料とを含有する複合材料は、機械的物性に優れる。
<Effect>
The degree of polymerization of the fine cellulose fibers obtained by the enzyme treatment using the cellulolytic enzyme having the EG activity / CBHI activity in the specific range is easily lowered. Therefore, dispersibility in the matrix material can be improved.
Moreover, the fine cellulose fiber obtained by carrying out the enzyme process using the cellulolytic enzyme which has EG activity / CBHI activity in the said specific range becomes easy for fiber width to become small, and an aspect ratio becomes high. Fine cellulose fibers having a high aspect ratio easily cross each other with a small amount of fibers in the matrix material. For this reason, a network of fine cellulose fibers is easily formed efficiently in the matrix material, and the reinforcing effect is excellent.
Therefore, the composite material containing the fine cellulose fiber obtained by the enzyme treatment and the matrix material is excellent in mechanical properties.
以下に本発明の実施例を示すが、本発明は実施例に限定されるものではない。また、以下の例において、「％」は「質量％」のことである。 Examples of the present invention are shown below, but the present invention is not limited to the examples. In the following examples, “%” means “mass%”.
（製造例１）
化学パルプとしてＮＢＫＰ（王子ホールディングス社製、ベイマツ品）を用い、ナイアガラビーター（容量２３リットル、東西精器社製）で２００分間叩解し、パルプ分散液（Ａ）（パルプ濃度２％、叩解後の加重平均繊維長：１．６１ｍｍ）を得た。
パルプ分散液（Ａ）を脱水して濃度３％にし、０．１％硫酸でｐＨ６までに調整し、５０℃になるまで水浴で温めた後、酵素ОｐｔｉｍａｓｅＣＸ７Ｌ（ＥＧ活性／ＣＢＨＩ活性＝３、Ｇｅｎｅｎｃｏｒ社製)をパルプ（固形分換算）に対して３％添加し、５０℃、１時間撹拌しながら反応させて、パルプ分散液（Ｂ）を得た。
次いで、パルプ分散液（Ｂ）を９５℃以上、２０分間加熱し、酵素を失活させて、パルプ分散液（Ｃ）を得た。
次いで、パルプ分散液（Ｃ）を１％パルプ液の電導度を所定値以下（１０μＳ/ｃｍ）になるまで、前記パルプ分散液（Ｃ）をイオン交換水で洗浄しながら減圧濾過を行った（Ｎｏ．２濾紙使用、アドバンテック社）。この濾過により得られたシートをイオン交換水に入れて攪拌し、０．５％の分散液を調製した。その分散液を、高速回転型解繊機（エムテクニック社製「クレアミックス」）を用いて、２１，５００回転、３０分間微細化処理（解繊）して、微細繊維含有分散液（Ｄ）を得た。次いで、該微細繊維含有分散液（Ｄ）を０．２％に薄め、１２，０００Ｇ×１０分間遠心分離（コクサン社製「Ｈ−２００ＮＲ」）して、上澄み液（Ｅ−１）を得た。
(Production Example 1)
NBKP (manufactured by Oji Holdings Co., Ltd., Bay Pine) is used as a chemical pulp and beaten for 200 minutes with a Niagara beater (capacity 23 liters, manufactured by Tozai Seiki Co., Ltd.), and a pulp dispersion (A) (pulp concentration 2%, after beating Weighted average fiber length: 1.61 mm) was obtained.
The pulp dispersion (A) is dehydrated to a concentration of 3%, adjusted to pH 6 with 0.1% sulfuric acid, warmed to 50 ° C. in a water bath, and then enzyme Optimase CX7L (EG activity / CBHI activity = 3, Genencor 3%) was added to the pulp (in terms of solid content) and reacted with stirring at 50 ° C. for 1 hour to obtain a pulp dispersion (B).
Next, the pulp dispersion (B) was heated at 95 ° C. or higher for 20 minutes to deactivate the enzyme, thereby obtaining a pulp dispersion (C).
Subsequently, the pulp dispersion liquid (C) was filtered under reduced pressure while washing the pulp dispersion liquid (C) with ion-exchanged water until the conductivity of the 1% pulp liquid was below a predetermined value (10 μS / cm) ( No. 2 filter paper, Advantech). The sheet obtained by this filtration was placed in ion-exchanged water and stirred to prepare a 0.5% dispersion. Using a high-speed rotation type defibrating machine (“CLEAMIX” manufactured by M Technique Co., Ltd.), the dispersion is refined (disentangled) for 21,500 rotations for 30 minutes to obtain a fine fiber-containing dispersion (D). Obtained. Next, the fine fiber-containing dispersion (D) was diluted to 0.2% and centrifuged (“H-200NR” manufactured by Kokusan Co., Ltd.) for 12,000 G × 10 minutes to obtain a supernatant (E-1). .
（製造例２）
製造例１において、高速回転型解繊機による微細化処理の代わりに、高圧ホモジナイザー（ＮｉｒｏＳｏａｖｉ社「Ｐａｎｄａ Ｐｌｕｓ ２０００」）を用い、操作圧力１２０ＭＰａの条件で、２回微細化処理した以外は全て製造例１と同様にして、上澄み液（Ｅ−２）を得た。
(Production Example 2)
In Production Example 1, instead of using a high-speed rotating type defibrator, a high-pressure homogenizer (“Panda Plus 2000” manufactured by NiroSoavi) was used, and all production examples except that the treatment was performed twice under the condition of an operation pressure of 120 MPa. In the same manner as in Example 1, a supernatant (E-2) was obtained.
（製造例３）
製造例２において、高圧ホモジナイザーによる微細化処理回数を４回にした以外は全て製造例１と同様にして、上澄み液（Ｅ−３）を得た。
(Production Example 3)
In Production Example 2, a supernatant (E-3) was obtained in the same manner as in Production Example 1 except that the number of times of the fine treatment by the high-pressure homogenizer was changed to 4.
（製造例４）
製造例２において、高圧ホモジナイザーによる微細化処理の操作圧力を７０ＭＰａで２回にした以外は全て製造例１と同様にして、上澄み液（Ｅ−４）を得た。
(Production Example 4)
In Production Example 2, a supernatant (E-4) was obtained in the same manner as in Production Example 1 except that the operation pressure for the micronization treatment with the high-pressure homogenizer was changed to 70 MPa twice.
（製造例５）
製造例１において、酵素としてＥｃｏｐｕｌｐＲ（ＥＧ活性／ＣＢＨＩ活性＝１．２、ＡＢｅｎｚｙｍｅ社製）を使用した以外は全て製造例１と同様にして、上澄み液（Ｅ−５）を得た。
(Production Example 5)
A supernatant liquid (E-5) was obtained in the same manner as in Production Example 1 except that Ecopulp R (EG activity / CBHI activity = 1.2, manufactured by Abenzyme) was used as the enzyme in Production Example 1.
（製造例６）
製造例１において、酵素としてエンチロン（ＥＧ活性／ＣＢＨＩ活性＝０．１２、洛東化成社製）を使用した以外は全て製造例１と同様にして、上澄み液（Ｅ−６）を得た。
(Production Example 6)
In Production Example 1, a supernatant liquid (E-6) was obtained in the same manner as in Production Example 1 except that enchilon (EG activity / CBHI activity = 0.12, manufactured by Tohto Kasei Co., Ltd.) was used as the enzyme.
（製造例７）
製造例１において、酵素としてＧＣ２２０（ＥＧ活性／ＣＢＨＩ活性＝０．０５、Ｇｅｎｅｎｃｏｒｅ社製）を使用した以外は全て製造例１と同様にして、上澄み液（Ｅ−７）を得た。
(Production Example 7)
In Production Example 1, a supernatant (E-7) was obtained in the same manner as in Production Example 1 except that GC220 (EG activity / CBHI activity = 0.05, manufactured by Genencore) was used as the enzyme.
（製造例８）
製造例１において、酵素としてアクセレラーゼＤｕｅｔ（ＥＧ活性／ＣＢＨＩ活性＝０．０３、Ｇｅｎｅｎｃｏｒｅ社製）を使用した以外は全て製造例１と同様にして、上澄み液（Ｅ−８）を得た。
(Production Example 8)
A supernatant liquid (E-8) was obtained in the same manner as in Production Example 1 except that Accelerase Duet (EG activity / CBHI activity = 0.03, manufactured by Genencore) was used as the enzyme in Production Example 1.
（製造例９）
ＮＢＫＰパルプ（王子ホールディングス社製 水分５０％ フリーネス（ＣＳＦ）６００ｍＬ）１００部に水１１５０部を加えた後、ディスインテグレーターで解繊し、次いで、パルプ濃度を２〜３％に調整し、リファイナーで処理した。リファイナーで処理したパルプのフリーネス（ＣＳＦ）は３００ｍＬであった。リファイナーで処理したパルプに、パルプ濃度が０．５〜０．７％の間になるように水を加え、石臼型分散機（増幸産業社製「スーパーマスコロイダー」、石臼タイプＧ）を用いて、７回分散処理を行って微細繊維含有分散液を得た。得られた微細繊維含有分散液を製造例１と同様に遠心分離して、上澄み液（Ｅ−９）を得た。
(Production Example 9)
After adding 1150 parts of water to 100 parts of NBKP pulp (Oji Holdings Co., Ltd., water 50% freeness (CSF) 600 mL), the fiber is defibrated with a disintegrator, and then the pulp concentration is adjusted to 2-3% and treated with a refiner. did. The freeness (CSF) of the pulp treated with the refiner was 300 mL. Water is added to the pulp treated with the refiner so that the pulp concentration is between 0.5 and 0.7%, and a stone mill type disperser ("Supermass colloider" manufactured by Masuko Sangyo Co., Ltd., stone mill type G) is used. Then, the dispersion process was performed 7 times to obtain a dispersion containing fine fibers. The obtained fine fiber-containing dispersion was centrifuged in the same manner as in Production Example 1 to obtain a supernatant (E-9).
（製造例１０）
リン酸二水素ナトリウム二水和物１０．１４ｇ、リン酸水素二ナトリウム１．７９ｇを１９．２７ｇの水に溶解させ、リン酸系化合物の水溶液（以下、「リン酸化試薬」という。）を得た。このリン酸化試薬のｐＨは２５℃で４．７３であった。
針葉樹晒クラフトパルプ（ＮＢＫＰ、王子製紙社製、水分５０％、ＪＩＳ Ｐ８１２１に準じて測定されるカナダ標準濾水度（ＣＳＦ）５５０ｍｌ）に、濃度４％になるように水を加えた後、ダブルディスクリファイナーによって変則ＣＳＦ（平織り８０メッシュ、パルプ採取量を０．３ｇとした以外はＪＩＳ Ｐ８１２１に準ずる）が２５０ｍｌ、長さ平均繊維長が０．６８ｍｍになるまで叩解した。
得られたパルプ分散液を０．３％に希釈し、そのパルプ分散液を抄紙することによって、含水率９０％、絶乾質量３ｇのパルプシート（厚み２００μｍ）を得た。このパルプシートを前記リン酸化試薬４３．３ｇ（乾燥パルプ１００部に対してリン元素量として１１１．３部）に浸漬させ、１７０℃の送風乾燥機（ヤマト科学株式会社 ＤＫＭ４００）を用いて２時間半加熱処理して、セルロースにリン酸基を導入した。
次いで、リン酸基を導入したシートに５００ｍｌのイオン交換水を加え、攪拌洗浄した後、脱水した。脱水後のシートを３００ｍｌのイオン交換水で希釈し、攪拌しながら、１Ｎの水酸化ナトリウム水溶液５ｍｌを少しずつ添加し、ｐＨが１２〜１３のパルプスラリーを得た。その後、このパルプスラリーを脱水し、５００ｍｌのイオン交換水を加えて洗浄を行った。この脱水と洗浄をさらに２回繰り返した。
洗浄脱水後に得られたシートにイオン交換水を添加した後、攪拌して、０．５％のリン酸基導入パルプ分散液（パルプ濃度０．５％）を得た。
そのリン酸基導入パルプ分散液を、高速回転型解繊機（エム・テクニック社製「クレアミックス」）を用いて、２１，５００回転、６０分間微細化処理（解繊処理）を施して、微細繊維含有分散液を得た。得られた微細繊維含有分散液を製造例１と同様に遠心分離して、上澄み液（Ｅ−１０）を得た。
(Production Example 10)
10.14 g of sodium dihydrogen phosphate dihydrate and 1.79 g of disodium hydrogen phosphate are dissolved in 19.27 g of water to obtain an aqueous solution of a phosphoric acid compound (hereinafter referred to as “phosphorylation reagent”). It was. The pH of this phosphorylating reagent was 4.73 at 25 ° C.
Double water after adding water to conifer bleached kraft pulp (NBKP, manufactured by Oji Paper Co., Ltd., moisture 50%, Canadian standard freeness (CSF) 550 ml measured according to JIS P8121) to a concentration of 4% The disc refiner was beaten until the irregular CSF (plain mesh 80 mesh, according to JIS P8121 except that the amount of pulp collected was 0.3 g) was 250 ml, and the length average fiber length was 0.68 mm.
The obtained pulp dispersion was diluted to 0.3%, and paper production of the pulp dispersion was performed to obtain a pulp sheet (thickness 200 μm) having a moisture content of 90% and an absolutely dry mass of 3 g. This pulp sheet was immersed in 43.3 g of the phosphorylating reagent (111.3 parts as the amount of phosphorus element with respect to 100 parts of dried pulp), and 2 hours using a 170 ° C. blower dryer (Yamato Scientific Co., Ltd. DKM400) A half heat treatment was performed to introduce phosphate groups into the cellulose.
Next, 500 ml of ion-exchanged water was added to the sheet into which the phosphate group had been introduced, and after stirring and washing, dehydration was performed. The dehydrated sheet was diluted with 300 ml of ion exchange water, and 5 ml of 1N sodium hydroxide aqueous solution was added little by little while stirring to obtain a pulp slurry having a pH of 12 to 13. Then, this pulp slurry was dehydrated and washed by adding 500 ml of ion exchange water. This dehydration and washing was repeated two more times.
Ion exchange water was added to the sheet obtained after washing and dehydration, followed by stirring to obtain a 0.5% phosphate group-introduced pulp dispersion (pulp concentration: 0.5%).
The phosphoric acid group-introduced pulp dispersion is subjected to fine processing (defibration processing) for 21,500 rotations for 60 minutes using a high-speed rotation type defibrating machine ("CLEAMIX" manufactured by M Technique Co., Ltd.). A fiber-containing dispersion was obtained. The obtained fine fiber-containing dispersion was centrifuged in the same manner as in Production Example 1 to obtain a supernatant (E-10).
＜微細セルロース繊維の重合度及び平均繊維幅＞
各製造例にて得た上澄み液に含まれる微細セルロース繊維の重合度を上記段落００１１に記載の方法で測定した。また、微細セルロース繊維の平均繊維幅を上記段落００１０に記載の方法で測定した。また、微細セルロース繊維の平均繊維長を上記段落００１２に記載の方法で測定した。また、微細セルロース繊維のアスペクト比を上記段落００１３に記載の方法で測定した。それらの測定結果を表１に示す。
<Polymerization degree and average fiber width of fine cellulose fiber>
The degree of polymerization of fine cellulose fibers contained in the supernatant obtained in each production example was measured by the method described in paragraph 0011 above. Further, the average fiber width of the fine cellulose fibers was measured by the method described in paragraph 0010 above. Further, the average fiber length of the fine cellulose fibers was measured by the method described in paragraph 0012 above. Further, the aspect ratio of the fine cellulose fiber was measured by the method described in paragraph 0013 above. The measurement results are shown in Table 1.
（実施例１）
製造例１で得た上澄み液（Ｅ−１）を濃度０．１％に調整し、これと２５％に濃度を調整した、酸変性スチレン−ブタジエン（ＳＢＲ）共重合体ラテックス（商品名：「ピラテックス Ｊ９０４９」、日本エイアンドエル社製、固形分４９％、Ｔｇ：−４０℃、粒子径２２０ｎｍ）とを表２に示した配合割合で混合して、混合液３００ｇを得た。その混合液を、テフロン（登録商標）トレー上にキャストした後、室温にて一週間乾燥して複合材料の試験シートを得た。
Example 1
The supernatant liquid (E-1) obtained in Production Example 1 was adjusted to a concentration of 0.1%, and this was adjusted to a concentration of 25%, acid-modified styrene-butadiene (SBR) copolymer latex (trade name: “ “Pilatex J9049”, manufactured by Nippon A & L Co., Ltd., solid content 49%, Tg: −40 ° C., particle size 220 nm) were mixed at the mixing ratio shown in Table 2 to obtain 300 g of a mixed solution. The mixed solution was cast on a Teflon (registered trademark) tray and then dried at room temperature for one week to obtain a composite material test sheet.
（実施例２）
実施例１において、上澄み液（Ｅ−１）の代わりに、製造例２で得た上澄み液（Ｅ−２）を使用した以外は実施例１と同様にして複合材料の試験シートを得た。
(Example 2)
In Example 1, instead of the supernatant liquid (E-1), a composite material test sheet was obtained in the same manner as in Example 1 except that the supernatant liquid (E-2) obtained in Production Example 2 was used.
（実施例３）
実施例１において、上澄み液（Ｅ−１）の代わりに、製造例３で得た上澄み液（Ｅ−３）を使用した以外は実施例１と同様にして複合材料の試験シートを得た。
(Example 3)
In Example 1, instead of the supernatant liquid (E-1), a composite material test sheet was obtained in the same manner as in Example 1 except that the supernatant liquid (E-3) obtained in Production Example 3 was used.
（実施例４）
実施例１において、上澄み液（Ｅ−１）の代わりに、製造例４で得た上澄み液（Ｅ−４）を使用した以外は実施例１と同様にして複合材料の試験シートを得た。
Example 4
In Example 1, instead of the supernatant liquid (E-1), a composite material test sheet was obtained in the same manner as in Example 1 except that the supernatant liquid (E-4) obtained in Production Example 4 was used.
（実施例５）
実施例１において、上澄み液（Ｅ−１）の代わりに、製造例５で得た上澄み液（Ｅ−５）を使用した以外は実施例１と同様にして複合材料の試験シートを得た。
(Example 5)
In Example 1, instead of the supernatant liquid (E-1), a composite material test sheet was obtained in the same manner as in Example 1 except that the supernatant liquid (E-5) obtained in Production Example 5 was used.
（実施例６）
実施例１において、上澄み液（Ｅ−１）の代わりに、製造例６で得た上澄み液（Ｅ−６）を使用した以外は実施例１と同様にして複合材料の試験シートを得た。
(Example 6)
In Example 1, instead of the supernatant liquid (E-1), a composite material test sheet was obtained in the same manner as in Example 1 except that the supernatant liquid (E-6) obtained in Production Example 6 was used.
（比較例１）
実施例１において、上澄み液（Ｅ−１）を混合せず、酸変性スチレン−ブタジエンのみで実施例１と同様にして試験シートを得た。
(Comparative Example 1)
In Example 1, a test sheet was obtained in the same manner as in Example 1 using only acid-modified styrene-butadiene, without mixing the supernatant (E-1).
（比較例２）
実施例１において、上澄み液（Ｅ−１）の代わりに、製造例７で得た上澄み液（Ｅ−７）を使用した以外は実施例１と同様にして複合材料の試験シートを得た。
(Comparative Example 2)
In Example 1, instead of the supernatant liquid (E-1), a composite material test sheet was obtained in the same manner as in Example 1 except that the supernatant liquid (E-7) obtained in Production Example 7 was used.
（比較例３）
実施例１において、上澄み液（Ｅ−１）の代わりに、製造例８で得た上澄み液（Ｅ−８）を使用した以外は実施例１と同様にして複合材料の試験シートを得た。
(Comparative Example 3)
In Example 1, instead of the supernatant liquid (E-1), a composite material test sheet was obtained in the same manner as in Example 1 except that the supernatant liquid (E-8) obtained in Production Example 8 was used.
（比較例４）
実施例１において、上澄み液（Ｅ−１）の代わりに、製造例９で得た上澄み液（Ｅ−９）を使用した以外は実施例１と同様にして複合材料の試験シートを得た。
(Comparative Example 4)
In Example 1, instead of the supernatant liquid (E-1), a composite material test sheet was obtained in the same manner as in Example 1 except that the supernatant liquid (E-9) obtained in Production Example 9 was used.
（比較例５）
実施例１において、上澄み液（Ｅ−１）の代わりに、製造例１０で得た上澄み液（Ｅ−１０）を使用した以外は実施例１と同様にして複合材料の試験シートを得た。
(Comparative Example 5)
In Example 1, instead of the supernatant liquid (E-1), a composite material test sheet was obtained in the same manner as in Example 1 except that the supernatant liquid (E-10) obtained in Production Example 10 was used.
＜評価＞
各実施例及び各比較例の複合材料の試験シートについて、引張弾性率及び引張破断強度を以下の方法により測定した。測定結果を表２，３に示す。
試験シートを調湿後（２３℃、湿度５０％、４時間）、厚みを測定し、次いで、定速伸張形引張試験機を用いて、ＪＩＳ Ｐ８１１３に基づき引張弾性率及び引張破断強度を測定した。その際、引張速度５ｍｍ／分、荷重２５０Ｎ、シート試験片幅５．０±０．１ｍｍ、スパン長３０±０．１ｍｍとした。
各実施例及び各比較例の複合材料の試験シートについて、分散性を以下の方法により評価した。評価結果を表２、３に示す。
試験シートからカッターを用いて試料を切り出し、イオンコーターを用いて銀を蒸着し、走査型電子顕微鏡（ＳＥＭ）用試料とした。ＳＥＭ観察を倍率１０００〜１００００倍で行い、幅１μｍ以上のセルロース繊維の凝集物が観察されなかったものを○、幅１μｍから１０μｍの凝集物が観察されたものを△、幅１０μｍ以上の凝集物が観察されたものを×とした。
<Evaluation>
About the test sheet of the composite material of each Example and each comparative example, the tensile elastic modulus and the tensile breaking strength were measured by the following methods. The measurement results are shown in Tables 2 and 3.
After conditioning the humidity of the test sheet (23 ° C., 50% humidity, 4 hours), the thickness was measured, and then the tensile modulus and tensile breaking strength were measured based on JIS P8113 using a constant speed extension type tensile tester. . At that time, the tensile speed was 5 mm / min, the load was 250 N, the sheet specimen width was 5.0 ± 0.1 mm, and the span length was 30 ± 0.1 mm.
About the test sheet of the composite material of each Example and each comparative example, the dispersibility was evaluated by the following method. The evaluation results are shown in Tables 2 and 3.
A sample was cut out from the test sheet using a cutter, and silver was deposited using an ion coater to obtain a sample for a scanning electron microscope (SEM). SEM observation was performed at a magnification of 1000 to 10000 times. A case where an aggregate of cellulose fibers having a width of 1 μm or more was not observed ○, a case where an aggregate of 1 μm to 10 μm in width was observed, and an aggregate having a width of 10 μm or more X was observed.
ＥＧ活性とＣＢＨＩ活性との比率が０．０６以上のセルロース分解酵素を用いて酵素処理して得た微細セルロース繊維を含む実施例１〜４の複合材料では、マトリクス材料中の微細セルロース繊維の分散性に優れ、引張弾性率及び引張破断強度に優れていた。
実施例５，６の複合材料も、マトリクス材料中の微細セルロース繊維の分散性に優れ、引張弾性率及び引張破断強度に優れていた。
微細セルロース繊維を含まない比較例１では、引張破断強度が低かった。
ＥＧ活性とＣＢＨＩ活性との比率が０．０６未満のセルロース分解酵素を用いて酵素処理して得た微細セルロース繊維を含む比較例２，３の複合材料は、微細セルロース繊維の重合度が大きく、マトリクス材料中での分散性が低かった。そのため、引張破断強度が低かった。
機械解繊によって得た微細セルロース繊維を含む比較例４の複合材料、リン酸処理・解繊処理によって得た微細セルロース繊維を含む比較例５の複合材料は、微細セルロース繊維の重合度が大きく、マトリクス材料中での分散性が低かった。そのため、引張破断強度が低かった。
In the composite materials of Examples 1 to 4 including fine cellulose fibers obtained by enzymatic treatment using a cellulolytic enzyme having a ratio of EG activity to CBHI activity of 0.06 or more, dispersion of fine cellulose fibers in the matrix material Excellent tensile properties and tensile strength at break.
The composite materials of Examples 5 and 6 were also excellent in the dispersibility of the fine cellulose fibers in the matrix material and excellent in the tensile modulus and tensile strength at break.
In Comparative Example 1 not containing fine cellulose fibers, the tensile strength at break was low.
The composite material of Comparative Examples 2 and 3 containing fine cellulose fibers obtained by enzymatic treatment using a cellulolytic enzyme having a ratio of EG activity to CBHI activity of less than 0.06 has a high degree of polymerization of the fine cellulose fibers, Dispersibility in the matrix material was low. Therefore, the tensile strength at break was low.
The composite material of Comparative Example 4 containing fine cellulose fibers obtained by mechanical defibration and the composite material of Comparative Example 5 containing fine cellulose fibers obtained by phosphating / defibrating treatment have a high degree of polymerization of the fine cellulose fibers, Dispersibility in the matrix material was low. Therefore, the tensile strength at break was low.
Claims (3)
前記微細セルロース繊維は、アスペクト比が２３以上３００以下、重合度が１００〜５００の繊維である、複合材料。 Containing fine cellulose fibers and a matrix material including at least one of plastic and rubber,
The fine cellulose fiber is a composite material having an aspect ratio of 23 to 300 and a degree of polymerization of 100 to 500.
前記酵素処理セルロースを、アスペクト比が２３以上３００以下、重合度が１００〜５００になるように解繊して微細セルロース繊維を得る解繊処理工程、
前記微細セルロース繊維と、プラスチック及びゴムの少なくとも一方を含むマトリクス材料とを混合する混合工程、
を有する複合材料の製造方法。 An enzyme treatment step of obtaining an enzyme-treated cellulose by subjecting a cellulose raw material to an enzyme treatment with a cellulose-degrading enzyme having a ratio of endoglucanase activity to cellobiohydrolase activity of 0.06 or more;
A defibrating process for obtaining fine cellulose fibers by defibrating the enzyme-treated cellulose so that the aspect ratio is 23 to 300 and the degree of polymerization is 100 to 500;
A mixing step of mixing the fine cellulose fibers and a matrix material containing at least one of plastic and rubber;
The manufacturing method of the composite material which has this.
混合工程の後に、前記混合液を脱液して複合材料を得る脱液工程を有する、請求項２に記載の複合材料の製造方法。 In the mixing step, slurry-like fine cellulose fibers and an emulsion matrix material are mixed to prepare a mixed solution,
The manufacturing method of the composite material of Claim 2 which has the liquid removal process which liquid-discharges the said liquid mixture and obtains a composite material after a mixing process.
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