JP2013018851A - Cellulose fiber, cellulose fiber-containing polymer, resin composition, and molding - Google Patents
Cellulose fiber, cellulose fiber-containing polymer, resin composition, and molding Download PDFInfo
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- JP2013018851A JP2013018851A JP2011152597A JP2011152597A JP2013018851A JP 2013018851 A JP2013018851 A JP 2013018851A JP 2011152597 A JP2011152597 A JP 2011152597A JP 2011152597 A JP2011152597 A JP 2011152597A JP 2013018851 A JP2013018851 A JP 2013018851A
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- Prior art keywords
- cellulose fiber
- group
- resin
- formula
- resin composition
- Prior art date
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- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 165
- 229920000642 polymer Polymers 0.000 title claims abstract description 76
- 239000011342 resin composition Substances 0.000 title claims abstract description 53
- 238000000465 moulding Methods 0.000 title abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 49
- 125000000524 functional group Chemical group 0.000 claims description 31
- 239000003822 epoxy resin Substances 0.000 claims description 30
- 229920000647 polyepoxide Polymers 0.000 claims description 30
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 24
- 239000005011 phenolic resin Substances 0.000 claims description 22
- 238000002834 transmittance Methods 0.000 claims description 22
- 238000005452 bending Methods 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 229920001187 thermosetting polymer Polymers 0.000 claims description 15
- -1 azo compound Chemical class 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 72
- 238000000034 method Methods 0.000 description 46
- 229920002678 cellulose Polymers 0.000 description 42
- 239000001913 cellulose Substances 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000006185 dispersion Substances 0.000 description 20
- 239000000835 fiber Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000010408 film Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000000945 filler Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229920002201 Oxidized cellulose Polymers 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229940107304 oxidized cellulose Drugs 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 229920005610 lignin Polymers 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000001226 reprecipitation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 210000001724 microfibril Anatomy 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- 0 CCC1*CCCC1 Chemical compound CCC1*CCCC1 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000012788 optical film Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- ATBDZSAENDYQDW-UHFFFAOYSA-N 3-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=C)=C1 ATBDZSAENDYQDW-UHFFFAOYSA-N 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000408490 Sovia Species 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 239000004637 bakelite Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical group C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 2
- JMCVCHBBHPFWBF-UHFFFAOYSA-N n,n-diethyl-2-methylprop-2-enamide Chemical compound CCN(CC)C(=O)C(C)=C JMCVCHBBHPFWBF-UHFFFAOYSA-N 0.000 description 2
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- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
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- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical group O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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Abstract
Description
本発明は、セルロース繊維、セルロース繊維含有重合体、樹脂組成物及び成形体に関するものである。 The present invention relates to a cellulose fiber, a cellulose fiber-containing polymer, a resin composition, and a molded body.
樹脂の熱線膨張係数の低減、または弾性率、曲げ強度等の機械的強度を上げるために球状フィラーや繊維状フィラーを充填材として配合することが広く行われている。近年では、シリカ微粒子等の球状の微粒子状充填剤や棒状のウィスカー状充填剤等のナノサイズの充填剤を用いる研究が盛んになっている。 In order to reduce the thermal linear expansion coefficient of the resin or increase the mechanical strength such as the elastic modulus and bending strength, it is widely practiced to blend a spherical filler or a fibrous filler as a filler. In recent years, research using nano-sized fillers such as spherical fine particle fillers such as silica fine particles and rod-like whisker-like fillers has become active.
このようなナノサイズの充填剤を用いる一手段として、セルロースを利用したプラスチック代替品が多く報告されている。例えば、セルロースを高圧ホモジナイザーと呼ばれる装置で極めて高い圧力でフィブリル状物質を高度に微細化して得られたセルロースミクロフィブリルを充填材として用いる方法が挙げられる。その他セルロースをミクロフィブリル化して充填材として用いるために、セルロースをダウンサイジングする方法として、マイクロフリュイダイザー法、グラインダー法、凍結乾燥法、強せん断力混練法およびボールミル粉砕法が挙げられる。これらの方法により得られたセルロースのミクロフィブリルを充填材に用いると、比較的強度の高い成形体が得られるという報告がされている。（例えば特許文献１参照）。 As one means of using such nano-sized fillers, many plastic substitutes using cellulose have been reported. For example, there is a method in which cellulose microfibril obtained by highly miniaturizing a fibrillar substance at a very high pressure with an apparatus called a high-pressure homogenizer is used as a filler. Other methods for downsizing cellulose in order to microfibrillate cellulose and use it as a filler include a microfluidizer method, a grinder method, a freeze-drying method, a high shear force kneading method, and a ball mill grinding method. It has been reported that when a cellulose microfibril obtained by these methods is used as a filler, a molded article having a relatively high strength can be obtained. (For example, refer to Patent Document 1).
セルロースをミクロフィブリル化する方法として、セルロースのＣ６位のメチロールをＮ−オキシル化合物を使用して酸化処理し、アルデヒド基やカルボキシル基を導入することで、セルロースミクロフィブリルを水中に分散させる技術が開示されている（例えば、特許文献２参照）。これにより、平均繊維径が１５ｎｍ以上であるセルロースミクロフィブリルから平均繊維径が数ｎｍ程度のセルロースシングルナノファイバーまでを比較的容易に解繊することができることが報告されている。 As a method of microfibrillating cellulose, a technique for dispersing cellulose microfibrils in water by oxidizing methylol at the C6 position of cellulose using an N-oxyl compound and introducing aldehyde groups or carboxyl groups is disclosed. (For example, refer to Patent Document 2). Thus, it has been reported that cellulose microfibrils having an average fiber diameter of 15 nm or more to cellulose single nanofibers having an average fiber diameter of several nanometers can be defibrated relatively easily.
しかし、前記技術により得られたセルロースシングルナノファイバーは、フェノール樹脂やエポキシ樹脂と配合すると凝集体を形成し、ナノスケールで均一に分散させることが困難である。それゆえ、フェノール樹脂やエポキシ樹脂等に配合した場合に、得られる成形体の透明性が低い、機械的強度が不十分であるなどの問題があった。 However, the cellulose single nanofibers obtained by the above technology form an aggregate when blended with a phenol resin or an epoxy resin, and it is difficult to uniformly disperse the nanoscale. Therefore, when blended with a phenol resin, an epoxy resin, or the like, there are problems such as low transparency of the obtained molded article and insufficient mechanical strength.
本発明の目的は、透明性に優れ、かつ機械的強度にも優れる成形体を提供し得るセルロース繊維、セルロース繊維含有重合体および樹脂組成物を提供することにある。
また、本発明の別の目的は、透明性に優れ、かつ機械的強度にも優れる成形体を提供することにある。
An object of the present invention is to provide a cellulose fiber, a cellulose fiber-containing polymer, and a resin composition that can provide a molded article having excellent transparency and excellent mechanical strength.
Another object of the present invention is to provide a molded article having excellent transparency and excellent mechanical strength.
このような目的は、下記（１）〜（１２）の本発明により達成される。
（１） 下記式（１）で示される繰り返し単位を含むことを特徴とするセルロース繊維。
（２）前記式（１）で示される繰り返し単位の含有量が、セルロース繊維の重量に対して０．２ｍｍｏｌ／ｇ以上、２．２ｍｍｏｌ／ｇ以下である上記（１）に記載のセルロース繊維。
（３）前記ラジカル重合可能な官能基が、アゾ基及びペルオキシ基の少なくともいずれか一方を含む有機基である上記（１）または（２）に記載のセルロース繊維。
（４）前記セルロース繊維が、下記式（２）の繰り返し単位を含む化合物に下記式（３）で表わされるアゾ化合物を反応させることで得られる上記（１）〜（３）のいずれか１つに記載のセルロース繊維。
（５）前記セルロース繊維が、下記式（２）の繰り返し単位を含む化合物に下記式（４）で表わされる過酸化物を反応させることで得られる前記（１）〜（３）のいずれか１つに記載のセルロース繊維。
またＸ５が水素原子である場合、Ｘ４はカルボキシル基と反応性のある官能基を少なくとも１つ含む有機基または１以上の炭素原子を含む有機基である。）
（６）前記カルボキシル基と反応性のある官能基が、アミノ基、エポキシ基、水酸基、チオール基、およびイソシアネート基の中から選ばれる１つ以上の官能基である上記（４）または（５）に記載のセルロース繊維。
（７）上記（１）〜（６）のいずれか１つに記載のセルロース繊維と、ラジカル重合性モノマーとを重合してなるセルロース繊維含有重合体。
（８）前記セルロース繊維含有重合体と、樹脂とを含む樹脂組成物。
（９）前記樹脂が、熱硬化性樹脂である上記（８）に記載の樹脂組成物。
（１０）前記熱硬化性樹脂がフェノール樹脂である上記（９）に記載の樹脂組成物。
（１１）前記熱硬化性樹脂がエポキシ樹脂である上記（９）に記載の樹脂組成物。
（１２）前記セルロース繊維含有重合体の含有量が、前記樹脂１００重量部に対して５重量部以上、１００重量部以下である上記（８）〜（１１）のいずれか１つに記載の樹脂組成物。
（１３）上記（７）〜（１２）のいずれか１つに記載の樹脂組成物を用いて得られる成形体。
（１４）厚み３０μｍにおける全光線透過率が７０％以上である（１３）に記載の成形体。
（１５）曲げ強度が５０Ｎ以上である（１３）または（１４）に記載の成形体。
Such an object is achieved by the present inventions (1) to (12) below.
(1) A cellulose fiber comprising a repeating unit represented by the following formula (1).
(2) The cellulose fiber as described in said (1) whose content of the repeating unit shown by said Formula (1) is 0.2 mmol / g or more and 2.2 mmol / g or less with respect to the weight of a cellulose fiber.
(3) The cellulose fiber according to (1) or (2), wherein the radical polymerizable functional group is an organic group containing at least one of an azo group and a peroxy group.
(4) Any one of the above (1) to (3), wherein the cellulose fiber is obtained by reacting a compound containing a repeating unit of the following formula (2) with an azo compound represented by the following formula (3). Cellulose fiber as described in 2.
(5) Any one of said (1)-(3) obtained by making the said cellulose fiber react the peroxide represented by following formula (4) with the compound containing the repeating unit of following formula (2). Cellulose fiber as described in 1.
When X 5 is a hydrogen atom, X 4 is an organic group containing at least one functional group reactive with a carboxyl group or an organic group containing one or more carbon atoms. )
(6) The above (4) or (5), wherein the functional group reactive with the carboxyl group is one or more functional groups selected from an amino group, an epoxy group, a hydroxyl group, a thiol group, and an isocyanate group. Cellulose fiber as described in 2.
(7) A cellulose fiber-containing polymer obtained by polymerizing the cellulose fiber according to any one of (1) to (6) above and a radical polymerizable monomer.
(8) A resin composition comprising the cellulose fiber-containing polymer and a resin.
(9) The resin composition according to (8), wherein the resin is a thermosetting resin.
(10) The resin composition according to (9), wherein the thermosetting resin is a phenol resin.
(11) The resin composition according to (9), wherein the thermosetting resin is an epoxy resin.
(12) The resin according to any one of (8) to (11), wherein the content of the cellulose fiber-containing polymer is 5 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the resin. Composition.
(13) A molded product obtained using the resin composition according to any one of (7) to (12) above.
(14) The molded product according to (13), wherein the total light transmittance at a thickness of 30 μm is 70% or more.
(15) The molded article according to (13) or (14), which has a bending strength of 50 N or more.
本発明によれば、透明性に優れ、かつ機械的強度にも優れる成形体を提供し得るセルロース繊維、セルロース繊維含有重合体および樹脂組成物を提供することが可能である。また、透明性に優れ、かつ機械的強度にも優れる成形体を提供することも可能である。
前記セルロース繊維と、ラジカル重合性モノマーとを重合してなるセルロース繊維含有重合体は、様々な樹脂との分散性に優れるため、特に透明性に優れ、かつ機械的強度にも優れる成形体を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the cellulose fiber, the cellulose fiber containing polymer, and resin composition which can provide the molded object which is excellent in transparency and excellent in mechanical strength. It is also possible to provide a molded article having excellent transparency and excellent mechanical strength.
The cellulose fiber-containing polymer obtained by polymerizing the cellulose fiber and the radical polymerizable monomer is excellent in dispersibility with various resins, and thus provides a molded product that is particularly excellent in transparency and mechanical strength. can do.
以下、本発明のセルロース繊維、セルロース繊維含有重合体、樹脂組成物及び成形体について詳細に説明する。 Hereinafter, the cellulose fiber, the cellulose fiber-containing polymer, the resin composition, and the molded body of the present invention will be described in detail.
本発明のセルロース繊維は、式（１）で示される繰り返し単位を含むことを特徴とするセルロース繊維である。
本発明のセルロース繊維含有重合体は、前記セルロース繊維と、ラジカル重合性モノマーとを重合してなるセルロース繊維含有重合体である。 The cellulose fiber-containing polymer of the present invention is a cellulose fiber-containing polymer obtained by polymerizing the cellulose fiber and a radical polymerizable monomer.
本発明の樹脂組成物は、前記セルロース繊維含有重合体と、樹脂とを含む樹脂組成物である。 The resin composition of the present invention is a resin composition containing the cellulose fiber-containing polymer and a resin.
本発明の成形体は、樹脂組成物を用いて得られる成形体である。 The molded body of the present invention is a molded body obtained using a resin composition.
［セルロース繊維］
まず、本発明のセルロース繊維について説明する。
[Cellulose fiber]
First, the cellulose fiber of the present invention will be described.
本発明のセルロース繊維は、式（１）で示される繰り返し単位を含むことを特徴とするセルロース繊維である。
式（１）中のＸ１はラジカル重合可能な官能基を含む有機基であれば特に限定されるものではなく、例えばアゾ基やペルオキシ基、ペルオキシエステル基、ペルオキシカーボナート基、トリクロロアセチル基等を含む有機基があげられる。これらの中でも、アゾ基及びペルオキシ基の少なくともいずれか一方を含む有機基であることが好ましい。これにより、特殊な試薬を用いる必要がなく、比較的温和な反応条件で後述のセルロース繊維含有重合体を得ることができる。 X 1 in formula (1) is not particularly limited as long as it is an organic group containing a radical polymerizable functional group. For example, azo group, peroxy group, peroxy ester group, peroxy carbonate group, trichloroacetyl group, etc. An organic group containing Among these, an organic group containing at least one of an azo group and a peroxy group is preferable. Thereby, it is not necessary to use a special reagent, and a cellulose fiber-containing polymer described later can be obtained under relatively mild reaction conditions.
本発明のセルロース繊維の繰り返し単位の数について、ｎは１以上であれば特に限定されないが、ｎは１００以上であることが好ましく、２００以上、１０００００以下であることがより好ましい。前記のセルロース繊維の繰り返し単位の数ｎが範囲内であると、成形体における補強効果が得られやすく、曲げ強度などの機械的強度の向上及び熱線膨張係数の低減化が図れる。 The number of repeating units of the cellulose fiber of the present invention is not particularly limited as long as n is 1 or more, but n is preferably 100 or more, and more preferably 200 or more and 100,000 or less. When the number n of the repeating units of the cellulose fiber is within the range, a reinforcing effect in the molded body can be easily obtained, and mechanical strength such as bending strength can be improved and a thermal expansion coefficient can be reduced.
前記セルロース繊維の平均繊維径は、特に限定されないが、４ｎｍ以上、１０００ｎｍ以下であることが好ましく、８ｎｍ以上、２００ｎｍ以下であることがより好ましい。前記の平均繊維径の範囲内だと、セルロース繊維特有の優れた特性が現れやすくなり、樹脂組成物を用いて得られる成形体における透明性および曲げ強度などの機械的強度の向上につながる。 The average fiber diameter of the cellulose fibers is not particularly limited, but is preferably 4 nm or more and 1000 nm or less, and more preferably 8 nm or more and 200 nm or less. When the average fiber diameter is within the above range, excellent characteristics peculiar to cellulose fibers tend to appear, leading to improvement in mechanical strength such as transparency and bending strength in a molded product obtained using the resin composition.
また本発明のセルロース繊維の長さについては特に限定されないが、繊維の平均長さが０．０５μｍ以上であることが好ましく、０．１μｍ以上、５０μｍ以下であることがより好ましい。前記の繊維の平均長さが範囲内だと、成形体における補強効果が得られやすく、曲げ強度などの機械的強度の向上及び熱線膨張係数の低減化が図れる。 Moreover, although it does not specifically limit about the length of the cellulose fiber of this invention, It is preferable that the average length of a fiber is 0.05 micrometer or more, and it is more preferable that it is 0.1 micrometer or more and 50 micrometers or less. When the average length of the fibers is within the range, a reinforcing effect in the molded body can be easily obtained, and mechanical strength such as bending strength can be improved and the thermal expansion coefficient can be reduced.
前記セルロース繊維は、式（１）で示される繰り返し単位が少なくとも１つを含むものであればよいが、式（１）で示される繰り返し単位の含有量が、セルロース繊維の重量に対して０．２ｍｍｏｌ／ｇ以上、２．２ｍｍｏｌ／ｇ以下であることが好ましく、０．５ｍｍｏｌ／ｇ以上、２．０ｍｍｏｌ／ｇ以下がより好ましい。前記繰り返し単位の含有量が前記下限値以上であると、樹脂と混合したときの分散性がより優れ、前記上限値以下であると、特に透明性に優れたものとなる。 The cellulose fiber may be any one as long as the repeating unit represented by the formula (1) includes at least one, but the content of the repeating unit represented by the formula (1) is 0. 0 relative to the weight of the cellulose fiber. It is preferably 2 mmol / g or more and 2.2 mmol / g or less, and more preferably 0.5 mmol / g or more and 2.0 mmol / g or less. When the content of the repeating unit is not less than the lower limit, the dispersibility when mixed with the resin is more excellent, and when it is not more than the upper limit, the transparency is particularly excellent.
本発明の式（１）で示される繰り返し単位を含むことを特徴とするセルロース繊維の合成方法は特に限定されないが、例えば式（２）の繰り返し単位を含む化合物に式（３）で表わされるアゾ化合物または式（４）で表わされる過酸化物を反応させることで得ることができる。 The method for synthesizing the cellulose fiber characterized by containing the repeating unit represented by the formula (1) of the present invention is not particularly limited. For example, the compound containing the repeating unit of the formula (2) is added to the azo compound represented by the formula (3). It can be obtained by reacting a compound or a peroxide represented by the formula (4).
式（２）の繰り返し単位を含む化合物に式（３）で表されるアゾ化合物を反応させる方法は特に限定されないが、例えば式（２）の繰り返し単位を含む化合物におけるＲが水酸基である場合、水酸基は塩化チオニル、塩化オキサリル、三臭化リンなどのハロゲン化剤を用いた公知の方法によりハロゲン化することができ、式（３）で示されるアゾ化合物は、Ｘ２及びＸ３の少なくともどちらか一方が、カルボキシル基と反応性のある官能基を含む有機基であることから、式（２）の繰り返し単位を含む化合物と反応し、式（１）で示される繰り返し単位を含むことを特徴とするセルロース繊維が得られる。尚、本発明におけるカルボキシル基は、ハロゲン化されたカルボキシル基も含まれるものとする。
また、Ｒが水酸基の場合でも、強酸などの適切な触媒存在下、前記アゾ化合物と式（２）の繰り返し単位を含む化合物とを反応させるなどの方法を用いてもよい。
The method of reacting the compound containing the repeating unit of formula (2) with the azo compound represented by formula (3) is not particularly limited. For example, when R in the compound containing the repeating unit of formula (2) is a hydroxyl group, The hydroxyl group can be halogenated by a known method using a halogenating agent such as thionyl chloride, oxalyl chloride, phosphorus tribromide, and the azo compound represented by the formula (3) is at least either X 2 or X 3 . Since one of them is an organic group containing a functional group reactive with a carboxyl group, it reacts with a compound containing a repeating unit of the formula (2) and contains a repeating unit represented by the formula (1). A cellulose fiber is obtained. The carboxyl group in the present invention includes a halogenated carboxyl group.
Even when R is a hydroxyl group, a method of reacting the azo compound with a compound containing a repeating unit of the formula (2) in the presence of a suitable catalyst such as a strong acid may be used.
式（２）の繰り返し単位を含む化合物に式（４）で表される過酸化物を反応させる方法は特に限定されないが、例えば式（２）の繰り返し単位を含む化合物におけるＲが水酸基である場合、水酸基は塩化チオニル、塩化オキサリル、三臭化リンなどのハロゲン化剤を用いた公知の方法によりハロゲン化することができ、式（４）で示される過酸化物は、Ｘ４はカルボキシル基と反応性のある官能基を少なくとも１つ含む有機基である場合、Ｘ５は水素原子または１以上の炭素原子を含む有機基であり、またＸ５が水素原子である場合、Ｘ４はカルボキシル基と反応性のある官能基を少なくとも１つ含む有機基または１以上の炭素原子を含む有機基であることから、式（２）の繰り返し単位を含む化合物と反応し、式（１）で示される繰り返し単位を含むことを特徴とするセルロース繊維が得られる。１以上の炭素原子を含む有機基とは、特に限定されないが、直鎖または分枝アルキル基、アルケニル基、アリル基等の炭化水素基、フェニル基、ナフチル基等の芳香族炭化水素基等が含まれる。
また、Ｒが水酸基の場合でも、強酸などの適切な触媒存在下、前記過酸化物と式（２）の繰り返し単位を含む化合物とを反応させるなどの方法を用いてもよい。
The method of reacting the peroxide represented by the formula (4) with the compound containing the repeating unit of the formula (2) is not particularly limited. For example, when R in the compound containing the repeating unit of the formula (2) is a hydroxyl group , hydroxyl thionyl chloride, oxalyl chloride, can be halogenated by a known method using a halogenating agent such as phosphorus tribromide, peroxides represented by the formula (4) is, X 4 is a carboxyl group When it is an organic group containing at least one reactive functional group, X 5 is a hydrogen atom or an organic group containing one or more carbon atoms, and when X 5 is a hydrogen atom, X 4 is a carboxyl group Since it is an organic group containing at least one functional group reactive with or an organic group containing one or more carbon atoms, it reacts with a compound containing a repeating unit of the formula (2) and is represented by the formula (1) repeat Cellulose fibers characterized in that it contains a unit are obtained. Examples of the organic group containing one or more carbon atoms include, but are not limited to, hydrocarbon groups such as linear or branched alkyl groups, alkenyl groups, and allyl groups, and aromatic hydrocarbon groups such as phenyl groups and naphthyl groups. included.
Even when R is a hydroxyl group, a method of reacting the peroxide with a compound containing a repeating unit of the formula (2) in the presence of a suitable catalyst such as a strong acid may be used.
また、カルボキシル基と反応性のある官能基を少なくとも一つ含む有機基として、アミノ基、エポキシ基、水酸基、チオール基、イソシアネート基、オキサゾリン基、カルボジイミド基、アジリジン基等を少なくとも一つ含む有機基が挙げられる。このなかでもカルボキシル基と反応性のある官能基として、アミノ基、エポキシ基、水酸基、チオール基、およびイソシアネート基の中から選ばれる１つ以上の官能基を含む有機基が好ましい。これにより、比較的温和な条件で反応を実施することが可能となる。 In addition, as an organic group containing at least one functional group reactive with a carboxyl group, an organic group containing at least one amino group, epoxy group, hydroxyl group, thiol group, isocyanate group, oxazoline group, carbodiimide group, aziridine group, etc. Is mentioned. Among these, as the functional group reactive with the carboxyl group, an organic group containing one or more functional groups selected from an amino group, an epoxy group, a hydroxyl group, a thiol group, and an isocyanate group is preferable. This makes it possible to carry out the reaction under relatively mild conditions.
本発明の分子中に式（１）および（２）で表される繰り返し単位を含むセルロース繊維に用いる原料のセルロース繊維について説明する。原料のセルロース繊維は、分子中にβグルコースがグリコシド結合により重合した構造が含まれていれば何ら限定されないが、針葉樹や広葉樹から得られる精製パルプ、コットンリンターやコットンリントより得られるセルロース、バロニアやシオグサなどの海草より得られるセルロース、ホヤより得られるセルロース、バクテリアの生産するセルロースなどの天然セルロース、前記天然セルロースを微細化した再生セルロースを使用することが出来る。しかしながら特に力学強度の観点からは高結晶性のものが好ましく、その点で再生セルロースよりも天然セルロースより得られる繊維を用いることが好ましい。
また前記の原料セルロースは、必要に応じて、機械的に解繊処理を施した、機械処理されたセルロース繊維を用いることが好ましい。解繊することで、前記の変性に必要な種々の工程において、反応試剤との接触面積を高め、反応率を向上させることができる。原料のセルロース繊維を解繊する方法としては特に限定されず公知の方法を使用することが出来、例えば媒体撹拌ミル処理装置、振動ミル処理装置、高圧ホモジナイザー処理装置、超高圧ホモジナイザー処置装置などの繊維を解繊する機能を有する装置を用いて繰り返し処理する方法などがある。また、エレクトロスピニング法、スチームジェット法、ＡＰＥＸ（登録商標）技術（Ｐｏｌｙｍｅｒ Ｇｒｏｕｐ．Ｉｎｃ）法などを採用することが出来る。
The raw material cellulose fiber used for the cellulose fiber containing the repeating units represented by the formulas (1) and (2) in the molecule of the present invention will be described. The cellulose fiber of the raw material is not limited at all as long as the structure contains β-glucose polymerized by glycosidic bonds in the molecule, but it is not limited to refined pulp obtained from conifers or hardwoods, cellulose obtained from cotton linter or cotton lint, valonia or Cellulose obtained from seaweed such as Shiogusa, cellulose obtained from sea squirt, natural cellulose such as cellulose produced by bacteria, and regenerated cellulose obtained by refining the natural cellulose can be used. However, in particular, from the viewpoint of mechanical strength, highly crystalline ones are preferable, and in this respect, it is preferable to use fibers obtained from natural cellulose rather than regenerated cellulose.
Moreover, it is preferable to use the cellulose fiber by which the said raw material cellulose was mechanically processed and fibrillated as needed. By defibrating, the contact area with the reaction reagent can be increased and the reaction rate can be improved in various steps necessary for the modification. A method for defibrating the raw material cellulose fiber is not particularly limited, and a known method can be used. For example, fibers such as a medium stirring mill processing device, a vibration mill processing device, a high-pressure homogenizer processing device, and an ultrahigh-pressure homogenizer processing device. There is a method of repeatedly processing using an apparatus having a function of defibrating. In addition, an electrospinning method, a steam jet method, an APEX (registered trademark) technique (Polymer Group. Inc) method, or the like can be employed.
本発明の分子中に式（２）で表される繰り返し単位を含むセルロース繊維の合成方法としては、前記原料のセルロース繊維とＮ−オキシル化合物とを反応させることにより誘導することができるが、好ましくは、天然セルロース、より好ましくは前記機械処理された天然セルロース繊維を用いて、水中においてＮ−オキシル化合物を酸化触媒とし、共酸化剤を作用させることにより該天然セルロースを酸化して得られた酸化処理されたセルロース繊維であることが好ましい。 The method for synthesizing the cellulose fiber containing the repeating unit represented by the formula (2) in the molecule of the present invention can be induced by reacting the raw material cellulose fiber with an N-oxyl compound. Is an oxidation product obtained by oxidizing natural cellulose by using natural cellulose, more preferably the machined natural cellulose fiber, using an N-oxyl compound as an oxidation catalyst in water and a cooxidant. A treated cellulose fiber is preferred.
ここで、セルロース繊維の重量に対するセルロースのカルボキシル基の量及び酸化処理での副生成物であるアルデヒド基（ｍｍｏｌ／ｇ）は、以下の手法により評価する。
乾燥重量を精秤したセルロース試料から０．５〜１重量％スラリーを６０ｍｌ調製し、０．１Ｍの塩酸水溶液によってｐＨを約２．５とした後、０．０５Ｍの水酸化ナトリウム水溶液を滴下して電気伝導度測定を行う。測定はｐＨが約１１になるまで続ける。電気伝導度の変化が緩やかな弱酸の中和段階において消費された水酸化ナトリウム量（Ｖ）から、下記式を用いて官能基量１を決定する。該官能基量１がカルボキシル基の量を示す。
官能基量１（ｍｍｏｌ／ｇ）＝Ｖ（ｍｌ）×０．０５／セルロースの質量（ｇ）
次に、セルロース試料を、酢酸でｐＨを４〜５に調製した２％亜塩素酸ナトリウム水溶液中でさらに４８時間常温で酸化し、上記手法によって再び官能基量２を測定する。この酸化によって追加された官能基量（＝官能基量２−官能基量１）を算出し、アルデヒド基量とする。
Here, the amount of the carboxyl group of cellulose relative to the weight of the cellulose fiber and the aldehyde group (mmol / g) as a by-product in the oxidation treatment are evaluated by the following method.
60 ml of a 0.5 to 1 wt% slurry was prepared from a dry-weighted cellulose sample, and the pH was adjusted to about 2.5 with a 0.1 M aqueous hydrochloric acid solution, and then a 0.05 M aqueous sodium hydroxide solution was added dropwise. To measure the electrical conductivity. The measurement is continued until the pH is about 11. The amount of functional group 1 is determined from the amount (V) of sodium hydroxide consumed in the neutralization step of the weak acid with a slow change in electrical conductivity using the following formula. The functional group amount 1 indicates the amount of carboxyl groups.
Functional group amount 1 (mmol / g) = V (ml) × 0.05 / mass of cellulose (g)
Next, the cellulose sample is further oxidized at room temperature for 48 hours in a 2% aqueous sodium chlorite solution adjusted to pH 4 to 5 with acetic acid, and the functional group amount 2 is measured again by the above method. The amount of functional groups added by this oxidation (= functional group amount 2 -functional group amount 1) is calculated and used as the aldehyde group amount.
［セルロース繊維含有重合体］
次に、本発明のセルロース繊維含有重合体について説明する。
[Cellulose fiber-containing polymer]
Next, the cellulose fiber-containing polymer of the present invention will be described.
本発明のセルロース繊維含有重合体は、前記セルロース繊維と、ラジカル重合性モノマーとを重合してなるセルロース繊維含有重合体である。 The cellulose fiber-containing polymer of the present invention is a cellulose fiber-containing polymer obtained by polymerizing the cellulose fiber and a radical polymerizable monomer.
前記セルロース繊維含有重合体に用いるラジカル重合性モノマーとしては、特に限定されないが、メタクリル酸、アクリル酸、メチルメタクリレート、エチルメタクリレート、グリシジルメタクリレート等のメタクリレート系モノマー、メチルアクリレート、エチルアクリレート、グリシジルアクリレート等のアクリレート系モノマー、スチレン、α−メチルスチレン、ｍ−スチレンスルホン酸等のスチレン系モノマー、エチレン、プロピレン、イソブテン等のα−オレフィン系モノマー、酢酸ビニル、プロピオン酸ビニル、安息香酸ビニル等のビニルエステル系モノマー、ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトン等のビニルケトン系モノマー、Ｎ−ビニルピロリドン、Ｎ−ビニルピロール、４−ビニルピリジン等のビニル置換複素芳香族系モノマー、Ｎ−イソプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド等のアクリルアミド系モノマー、Ｎ−イソプロピルメタクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミド、Ｎ，Ｎ−ジエチルメタクリルアミド等のメタクリルアミド系モノマー、塩化ビニル、塩化ビニリデン、フッ化ビニル等のハロゲン化ビニル系モノマー、アクリロニトリル、メタクリロニトリル、マレイン酸、無水マレイン酸、ブタジエン、イソプレン等のジエン系モノマー、ジアリルフタレートなどのアリル基を２つ有するジアリル系モノマーなどが挙げられるが、特にメチルメタクリレート、スチレンは、本発明で用いるフェノール樹脂及びエポキシ樹脂と親和性が優れるため好ましい。 The radically polymerizable monomer used in the cellulose fiber-containing polymer is not particularly limited, but includes methacrylate monomers such as methacrylic acid, acrylic acid, methyl methacrylate, ethyl methacrylate, and glycidyl methacrylate, methyl acrylate, ethyl acrylate, glycidyl acrylate, and the like. Acrylate monomers, styrene monomers such as styrene, α-methyl styrene, m-styrene sulfonic acid, α-olefin monomers such as ethylene, propylene, and isobutene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, etc. Monomers, vinyl ketone monomers such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, N-vinyl pyrrolidone, N-vinyl pyrrole, 4-vinyl pyridine Vinyl substituted heteroaromatic monomers such as gin, acrylamide monomers such as N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylmethacrylamide, N, N-dimethylmethacrylamide, N , N-diethylmethacrylamide, etc., methacrylamide monomers, vinyl chloride, vinylidene chloride, vinyl halide monomers such as vinyl fluoride, acrylonitrile, methacrylonitrile, maleic acid, maleic anhydride, butadiene, isoprene, etc. Examples include monomers and diallyl monomers having two allyl groups such as diallyl phthalate, but methyl methacrylate and styrene are particularly preferred because of their excellent affinity with the phenol resin and epoxy resin used in the present invention. There.
前記セルロース繊維含有重合体は、ラジカル重合性モノマーにより前記式（１）で表されるセルロース繊維がグラフト重合されたものである。ここで前記セルロース繊維に対するラジカル重合性モノマーの量は、前記セルロース繊維１００％に対する、グラフト重合体部の割合としてグラフト率と定義すると、前記セルロース繊維含有重合体のグラフト率は、５％以上、５００％以下が好ましく、１０％以上、２００％以下がより好ましい。グラフト率が前記範囲内であることにより、透明性及び曲げ強度などの機械的強度が特に優れる。 The cellulose fiber-containing polymer is obtained by graft polymerization of the cellulose fiber represented by the formula (1) with a radical polymerizable monomer. Here, when the amount of the radical polymerizable monomer with respect to the cellulose fiber is defined as a graft ratio as a ratio of the graft polymer part to the cellulose fiber 100%, the graft ratio of the cellulose fiber-containing polymer is 5% or more, 500 % Or less is preferable, and 10% or more and 200% or less are more preferable. When the graft ratio is within the above range, mechanical strength such as transparency and bending strength is particularly excellent.
前記セルロース繊維と前記ラジカル重合性モノマーとの重合方法は、特に限定されないが、これらを溶剤に溶解させた溶液を脱気または不活性ガス雰囲気下で、加熱撹拌しながら重合させる方法や、加熱以外に光や放射線の照射により重合させる方法等も挙げられるが、設備コスト等の観点から、加熱撹拌しながら重合させる方法が好ましい。 The method for polymerizing the cellulose fiber and the radically polymerizable monomer is not particularly limited, but a method in which a solution obtained by dissolving these in a solvent is polymerized while heating and stirring in a degassed or inert gas atmosphere, or other than heating. Examples of the method include polymerizing by irradiation with light or radiation, but from the viewpoint of equipment cost and the like, a method of polymerizing while heating and stirring is preferable.
［樹脂組成物］
次に、本発明における樹脂組成物について説明する。
[Resin composition]
Next, the resin composition in the present invention will be described.
本発明における樹脂組成物は、前記セルロース繊維含有重合体と、樹脂とを含む樹脂組成物である。 The resin composition in the present invention is a resin composition containing the cellulose fiber-containing polymer and a resin.
前記樹脂組成物に用いる樹脂としては、特に限定されないが、ポリメタクリル酸、ポリアクリル酸、ポリメチルメタクリレート、ポリエチルメタクリレート、ポリグリシジルメタクリレート等のポリメタクリレート系樹脂、ポリメチルアクリレート、ポリエチルアクリレート、ポリグリシジルアクリレート等のポリアクリレート系樹脂、ポリスチレン、ポリ（α−メチルスチレン）、ポリ（ｍ−スチレンスルホン酸）等のポリスチレン系樹脂、ポリエチレン、ポリプロピレン、ポリイソブテン等のポリオレフィン系樹脂、ポリ酢酸ビニル、ポリプロピオン酸ビニル、ポリ安息香酸ビニル等のポリビニルエステル系樹脂、ポリビニルメチルケトン、ポリビニルヘキシルケトン、ポリメチルイソプロペニルケトン等のポリビニルケトン系樹脂、ポリ（Ｎ−ビニルピロリドン）、ポリ（Ｎ−ビニルピロール）、ポリ（４−ビニルピリジン）等のポリビニル置換複素芳香族系樹脂、ポリ（Ｎ−イソプロピルアクリルアミド）、ポリ（Ｎ，Ｎ−ジメチルアクリルアミド）、ポリ（Ｎ，Ｎ−ジエチルアクリルアミド）等のポリアクリルアミド系、ポリ（Ｎ−イソプロピルメタクリルアミド）、ポリ（Ｎ，Ｎ−ジメチルメタクリルアミド）、ポリ（Ｎ，Ｎ−ジエチルメタクリルアミド）等のポリメタクリルアミド系樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリフッ化ビニル等のポリハロゲン化ビニル系樹脂、ポリアクリロニトリル、ポリメタクリロニトリル、ポリマレイン酸、ポリブタジエン、ポリイソプレン等のポリジエン系樹脂、ポリジアリルフタレートなどのアリル基を２つ有するポリジアリル系樹脂等の熱可塑性樹脂や、フェノール樹脂、エポキシ樹脂、メラミン樹脂、尿素樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、シアネート樹脂、イソシアネート樹脂、マレイミド樹脂、ウレタン樹脂、熱硬化性ポリイミド、ベンゾオキサジン樹脂等の熱硬化性樹脂が挙げられる。この中でも熱硬化性樹脂が好ましく、特にフェノール樹脂やエポキシ樹脂が好ましい。これにより、特に透明性に優れ、かつ曲げ強度などの機械的強度も向上することができる。 The resin used in the resin composition is not particularly limited, but polymethacrylate resins such as polymethacrylic acid, polyacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polyglycidyl methacrylate, polymethyl acrylate, polyethyl acrylate, poly Polyacrylate resins such as glycidyl acrylate, polystyrene resins such as polystyrene, poly (α-methylstyrene) and poly (m-styrenesulfonic acid), polyolefin resins such as polyethylene, polypropylene and polyisobutene, polyvinyl acetate, polypropion Polyvinyl ester resins such as vinyl acid and polyvinyl benzoate, polyvinyl ketone resins such as polyvinyl methyl ketone, polyvinyl hexyl ketone, and polymethyl isopropenyl ketone; (N-vinylpyrrolidone), poly (N-vinylpyrrole), polyvinyl substituted heteroaromatic resins such as poly (4-vinylpyridine), poly (N-isopropylacrylamide), poly (N, N-dimethylacrylamide), Polyacrylamide such as poly (N, N-diethylacrylamide), polymethacrylamide such as poly (N-isopropylmethacrylamide), poly (N, N-dimethylmethacrylamide), poly (N, N-diethylmethacrylamide) Resins, polyhalogenated vinyl resins such as polyvinyl chloride, polyvinylidene chloride and polyvinyl fluoride, polydiene resins such as polyacrylonitrile, polymethacrylonitrile, polymaleic acid, polybutadiene and polyisoprene, and allyl such as polydiallyl phthalate Poly with two groups Thermoplastic resins such as diallyl resins, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, diallyl phthalate resins, cyanate resins, isocyanate resins, maleimide resins, urethane resins, thermosetting polyimides, benzoxazines Examples thereof include thermosetting resins such as resins. Of these, thermosetting resins are preferable, and phenol resins and epoxy resins are particularly preferable. Thereby, it is excellent in especially transparency, and mechanical strength, such as bending strength, can also be improved.
前記樹脂組成物に用いるフェノール樹脂としては、分子内にフェノール性水酸基を１つ以上有する化合物が含まれ、ノボラック型フェノール、ノボラック型クレゾール、ノボラック型ナフトールなどのノボラック樹脂やビスフェノールＦ、ビスフェノールＡなどのビスフェノール樹脂、パラキシリレン変性フェノール樹脂などのフェノールアラルキル樹脂、ジメチレンエーテル型レゾール、メチロール型フェノール等のレゾール型フェノール樹脂、前記樹脂等をさらにメチロール化させた化合物、フェノール性水酸基を１つ以上含むリグニンやリグニン誘導体、リグニン分解物、さらにリグニンやリグニン誘導体、リグニン分解物を変性したもの、あるいはこれらを石油資源から製造されたフェノール樹脂と混合した物を含むものであるが、ノボラック型フェノール樹脂および／またはレゾール型フェノール樹脂が、成形物における透明性および強度の向上させることができるため好ましい。 The phenol resin used in the resin composition includes a compound having one or more phenolic hydroxyl groups in the molecule, such as novolak resins such as novolak phenol, novolac cresol, and novolak naphthol, and bisphenol F and bisphenol A. Bisphenol resins, phenol aralkyl resins such as paraxylylene-modified phenol resins, dimethylene ether type resols, resol type phenol resins such as methylol type phenols, compounds obtained by further methylolating the resins, lignins containing one or more phenolic hydroxyl groups, Including lignin derivatives, lignin degradation products, lignin and lignin derivatives, modified lignin degradation products, or those mixed with phenol resins produced from petroleum resources, Novolak type phenol resin and / or a resol type phenol resin is preferable because it can improve the transparency and strength in the molded product.
前記樹脂組成物に用いるエポキシ樹脂としては、分子内にエポキシ基を１つ以上有する化合物が含まれ、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂などのビスフェノール型のエポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂などのノボラック型のエポキシ樹脂、フェニレン骨格、ビフェニレン骨格を有するフェノールアラルキル型のエポキシ樹脂、ビフェニル骨格を有するビフェニル型のエポキシ樹脂、ジシクロペンタジエン骨格を有するエポキシ樹脂、トリグリシジルイソシアヌレート骨格を有するエポキシ樹脂、カルド骨格を有するエポキシ樹脂、ポリシロキサン構造を有するエポキシ樹脂、脂環式多官能のエポキシ樹脂、水添ビフェニル骨格を有する脂環式のエポキシ樹脂、水添ビスフェノールＡ骨格を有する脂環式のエポキシ樹脂などが挙げられ、これらを単独または２種類以上を混合した物を含むものであるが、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、および／または、ビフェニル型エポキシ樹脂が、樹脂組成物を用いて得られる成形体における透明性および強度を向上させることができるため好ましい。 The epoxy resin used in the resin composition includes a compound having one or more epoxy groups in the molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin. Bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin and other novolak type epoxy resin, phenylene skeleton, phenol aralkyl type epoxy resin having biphenylene skeleton, biphenyl type epoxy resin having biphenyl skeleton , Epoxy resin having dicyclopentadiene skeleton, epoxy resin having triglycidyl isocyanurate skeleton, epoxy resin having cardo skeleton, epoxy having polysiloxane structure Examples include alicyclic, alicyclic polyfunctional epoxy resins, alicyclic epoxy resins having a hydrogenated biphenyl skeleton, and alicyclic epoxy resins having a hydrogenated bisphenol A skeleton. Although it contains a mixture, the bisphenol-type epoxy resin, novolac-type epoxy resin, phenol-aralkyl-type epoxy resin, and / or biphenyl-type epoxy resin have improved transparency and strength in the molded product obtained using the resin composition. It is preferable because it can be improved.
前記樹脂組成物には、必要に応じて、従来の熱硬化性樹脂に使用される各種添加剤、例えば硬化剤、若しくは硬化触媒、ステアリン酸亜鉛、若しくはステアリン酸カルシウムなどの離型剤、前記セルロース繊維とフェノール樹脂との界面強化のために、カップリング剤、特性を損なわない範囲で、酸化防止剤、紫外線吸収剤、染顔料、他の無機フィラー等の充填剤等を配合することもできる。これらを配合することで、樹脂組成物を用いて得られる成形体の耐腐食性等が改善される。 In the resin composition, if necessary, various additives used in conventional thermosetting resins, for example, a curing agent or a release catalyst such as a curing catalyst, zinc stearate, or calcium stearate, the cellulose fiber In order to strengthen the interface between the phenolic resin and the phenol resin, a filler, such as an antioxidant, an ultraviolet absorber, a dye / pigment, and other inorganic fillers, may be blended within a range that does not impair the coupling agent and characteristics. By blending these, the corrosion resistance and the like of the molded product obtained using the resin composition are improved.
前記樹脂組成物におけるセルロース繊維含有重合体の含有量は、前記樹脂１００重量部に対して５重量部以上、１００重量部以下であるであることが好ましく、１０重量部以上、９０重量部以下がより好ましい。前記セルロース繊維含有重合体の含有量が前記下限値以上であると、樹脂と混合したときの分散性がより優れ、前記上限値以下であると、樹脂組成物を用いて得られる成形体における透明性及び曲げ強度などの機械的強度が特に良好となり、熱線膨張係数の低減化も図れる。 The content of the cellulose fiber-containing polymer in the resin composition is preferably 5 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the resin, and is 10 parts by weight or more and 90 parts by weight or less. More preferred. If the content of the cellulose fiber-containing polymer is equal to or higher than the lower limit, the dispersibility when mixed with a resin is more excellent, and if it is equal to or lower than the upper limit, the molded article obtained using the resin composition is transparent. The mechanical strength such as the property and the bending strength is particularly good, and the thermal expansion coefficient can be reduced.
前記樹脂組成物を得る方法としては、任意の方法により得ることができる。本発明のセルロース繊維含有重合体は、Ｎ,Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン、Ｎ,Ｎ−ジメチルアセトアミド、ジメチルスルホキシドなどの有機溶剤中に分散することができ、この状態で該セルロース繊維含有重合体と前記熱硬化性樹脂とを混合させて、熱硬化性樹脂にセルロース繊維含有重合体が均一に分散した透明性の高い樹脂組成物を得ることが可能となる。セルロース繊維含有重合体を有機溶剤中に分散させる際は、必要に応じてホモジナイザーなどの分散装置を用いてセルロース繊維含有重合体の解繊処理を施すことが好ましく、熱硬化性樹脂にセルロース繊維含有重合体を均一に分散させる際においても、必要に応じてホモジナイザーなどの分散装置を用いてセルロース繊維含有重合体の解繊処理することがより好ましい。前記のセルロース繊維含有重合体と熱硬化性樹脂とを混合させて樹脂組成物を得る方法は一例であり、例えば、熱硬化性樹脂と本発明のセルロース繊維含有重合体を溶媒を用いないで、二軸混練機やロール、ニーダーなどで混合・分散するなど、必要に応じて適切な方法を採用することは何ら差し支えない。 The resin composition can be obtained by any method. The cellulose fiber-containing polymer of the present invention can be dispersed in an organic solvent such as N, N-dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, and in this state, By mixing the cellulose fiber-containing polymer and the thermosetting resin, it is possible to obtain a highly transparent resin composition in which the cellulose fiber-containing polymer is uniformly dispersed in the thermosetting resin. When dispersing the cellulose fiber-containing polymer in an organic solvent, it is preferable to perform a fibrillation treatment of the cellulose fiber-containing polymer using a dispersing device such as a homogenizer, if necessary, and the thermosetting resin contains cellulose fibers. Even when the polymer is uniformly dispersed, it is more preferable that the cellulose fiber-containing polymer is defibrated using a dispersing device such as a homogenizer as necessary. The method of mixing the cellulose fiber-containing polymer and the thermosetting resin to obtain a resin composition is an example, for example, without using a solvent for the thermosetting resin and the cellulose fiber-containing polymer of the present invention. An appropriate method may be employed as needed, such as mixing and dispersing with a twin-screw kneader, roll, kneader, or the like.
［成形体］
次に、本発明における成形体について説明する。
[Molded body]
Next, the molded body in the present invention will be described.
本発明における成形体とは、前記樹脂組成物を用いて得られる成形体である。 The molded product in the present invention is a molded product obtained using the resin composition.
成形体とは、太陽電池用基板、有機ＥＬ用基板、電子ペーパー用基板、液晶表示素子用プラスチック基板、光学シート、光学フィルムなどの光学特性が重要な特性である成形体、またはダッシュボードやインスツルメントパネルなどの自動車用内装部品などの機械的強度が重要な特性である成形体等が挙げられる。 The molded body is a molded body whose optical characteristics are important characteristics, such as a solar cell substrate, an organic EL substrate, an electronic paper substrate, a liquid crystal display plastic substrate, an optical sheet, an optical film, or a dashboard or inboard. Examples thereof include molded products having an important characteristic of mechanical strength, such as automotive interior parts such as instrument panels.
前記成形体の製造方法としては、従来からの溶融注型による成形方法を用いることができ、前記用途の成形体の場合、トランスファー成形、コンプレッション成形、インジェクション成形などの成形方法を用いることが好ましい。 As a method for producing the molded body, a conventional molding method by melt casting can be used. In the case of a molded body for the above-mentioned use, it is preferable to use a molding method such as transfer molding, compression molding, or injection molding.
また、本発明で得られる成形体は、太陽電池用基板、有機ＥＬ用基板、電子ペーパー用基板、液晶表示素子用プラスチック基板、光学シート、光学フィルムなどの光学特性が重要な特性である成形体、として用いる場合、厚み３０μｍにおける全光線透過率が７０％以上であることが好ましく、特に好ましくは８０％以上である。 In addition, the molded product obtained in the present invention is a molded product in which optical characteristics are important characteristics such as a solar cell substrate, an organic EL substrate, an electronic paper substrate, a liquid crystal display plastic substrate, an optical sheet, and an optical film. , The total light transmittance at a thickness of 30 μm is preferably 70% or more, and particularly preferably 80% or more.
また、本発明で得られる成形体は、ダッシュボードやインスツルメントパネルなどの自動車用内装部品などの機械的強度が重要な特性である成形体として用いる場合、ＪＩＳ Ｋ ７１７１の評価方法に従い、厚み１ｍｍ、幅１０ｍｍの試験片を用いた場合の曲げ強度が５０Ｎ以上であることが好ましく、特に７０Ｎ以上であることが好ましい。 Further, when the molded product obtained in the present invention is used as a molded product in which mechanical strength is an important characteristic of automobile interior parts such as dashboards and instrument panels, the thickness is determined according to the evaluation method of JIS K 7171. The bending strength when a test piece having a width of 1 mm and a width of 10 mm is used is preferably 50 N or more, and particularly preferably 70 N or more.
本発明を実施例に基づいて説明するが、構造の解析および特性評価方法は、以下の通りとした。 The present invention will be described based on examples. The structure analysis and characteristic evaluation methods were as follows.
（ａ）ＦＴ−ＩＲ
フーリエ変換赤外分光光度計ＩＲＰｒｅｓｔｉｇｅ−２１（株式会社島津製作所製）でＦＴ−ＩＲスペクトルを測定した。
(A) FT-IR
The FT-IR spectrum was measured with a Fourier transform infrared spectrophotometer IRPrestige-21 (manufactured by Shimadzu Corporation).
（ｂ）ＮＭＲ
ＦＴ−ＮＭＲ装置ＥＣＡ−４００（日本電子株式会社製）で固体ＮＭＲ法による１３Ｃ−ＮＭＲを測定した。
(B) NMR
13 C-NMR by a solid-state NMR method was measured with an FT-NMR apparatus ECA-400 (manufactured by JEOL Ltd.).
（ｃ）全光線透過率
ヘイズメーターＮＤＨ−２０００（日本電色社製）で全光線透過率を測定した。
(C) Total light transmittance Total light transmittance was measured with a haze meter NDH-2000 (manufactured by Nippon Denshoku).
（ｄ）曲げ強度
ＪＩＳ Ｋ ７１７１に準拠し、伸展間距離３６ｍｍ、クロスヘッド速度１ｍｍ/分、２３℃、相対湿度６０％下で株式会社オリエンテック社製ＵＣＴ−３０Ｔ型テンシロンで測定した。
(D) Bending strength Based on JIS K 7171, it was measured with a UCT-30T type Tensilon manufactured by Orientec Co., Ltd. under an extension distance of 36 mm, a crosshead speed of 1 mm / min, 23 ° C., and a relative humidity of 60%.
（作製例１）
乾燥重量で２重量部相当分の未乾燥のパルプ（主に１０００ｎｍを超える繊維径の繊維から成る）、０．０２５重量部のＴＥＭＰＯ（２，２，６，６‐テトラメチル−１−ピペリジン−Ｎ−オキシル）および０．２５重量部の臭化ナトリウムを水１５０重量部に分散させた後、１３重量％次亜塩素酸ナトリウム水溶液を、１ｇのパルプに対して次亜塩素酸ナトリウムの量が２．５ｍｍｏｌとなるように次亜塩素酸ナトリウムを加えて反応を開始した。反応中は自動滴定装置を用い、０．５Ｍの水酸化ナトリウム水溶液を滴下してｐＨを１０．５に保った。ｐＨに変化が見られなくなった時点で反応終了と見なし、０．５Ｍの塩酸水溶液でｐＨ７に中和し反応物をろ過した後、十分な量の水による水洗、ろ過を６回繰り返し、固形分量２重量％の水を含浸させた酸化処理されたセルロース繊維を得た。
(Production Example 1)
2 parts by weight of undried pulp (mainly consisting of fibers with a fiber diameter of more than 1000 nm), 0.025 parts by weight of TEMPO (2,2,6,6-tetramethyl-1-piperidine- N-oxyl) and 0.25 parts by weight of sodium bromide are dispersed in 150 parts by weight of water, and then a 13% by weight aqueous sodium hypochlorite solution is added to the amount of sodium hypochlorite per gram of pulp. The reaction was initiated by adding sodium hypochlorite to 2.5 mmol. During the reaction, an automatic titrator was used, and a 0.5 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 10.5. When no change in pH is observed, the reaction is considered to be complete. After neutralizing to pH 7 with 0.5 M aqueous hydrochloric acid and filtering the reaction product, washing with a sufficient amount of water and filtration are repeated 6 times to obtain a solid content. An oxidized cellulose fiber impregnated with 2% by weight of water was obtained.
次に、酸化処理されたセルロース繊維に水を加え０．２重量％混合液とした。
この混合液を高圧ホモジナイザー（ノロ・ソビア社製、１５−８ＴＡ）型）を用いて圧力２０ＭＰａで１０回処理し、酸化処理されたセルロース繊維の水分散液を得た。
また、乾燥させて得られた膜状のセルロースの広角Ｘ線回折像から、セルロースＩ型結晶構造を有するセルロースから成ることが示され、また同じ膜状セルロースのＡＴＲスペクトルのパターンからカルボニル基の存在が確認され、上述した方法により評価したセルロース中のアルデヒド基の量およびカルボキシル基の量はそれぞれ０．３１ｍｍｏｌ／ｇ、および１．６７ｍｍｏｌ／ｇであった。
Next, water was added to the oxidized cellulose fiber to obtain a 0.2 wt% mixed solution.
This mixed solution was treated 10 times at a pressure of 20 MPa using a high-pressure homogenizer (manufactured by Noro Sovia, 15-8TA) to obtain an aqueous dispersion of oxidized cellulose fibers.
In addition, the wide-angle X-ray diffraction image of the membrane-like cellulose obtained by drying showed that it was composed of cellulose having a cellulose I-type crystal structure, and the presence of carbonyl groups from the ATR spectrum pattern of the same membrane-like cellulose. The amount of aldehyde groups and the amount of carboxyl groups in the cellulose evaluated by the method described above were 0.31 mmol / g and 1.67 mmol / g, respectively.
さらに、前記セルロース繊維の水分散液を、１Ｍの塩酸を用いてｐＨ１に調整し２４時間攪拌することで、酸化処理されたセルロース繊維の凝集物を得た。次に該凝集物をアセトンで洗浄し、Ｎ−メチル−２−ピロリドン（ＮＭＰ）で洗浄した。酸化処理されたセルロース繊維の凝集物にＮＭＰを加え前記酸化処理されたセルロース濃度０．２重量％とし、超音波ホモジナイザー（ヒールッシャー社製、ＵＰ４００Ｓ）を用いて３０分間処理し、酸化処理されたセルロース繊維のＮＭＰ分散液を得た。
酸化処理されたセルロース繊維のＮＭＰ分散液を３つ口セパラブルフラスコに移し、窒素気流化において氷水浴中で１０℃以下に冷却しながら、塩化チオニルを前記ＮＭＰ分散液中の酸化処理されたセルロース繊維のＣ６位のメチロール由来の炭素数と当モル滴下した。さらに３つ口セパラブルフラスコをオイルバスに移し、窒素気流化７０℃で４時間反応させた後、後処理を行い、式（２）の繰り返し単位を含む化合物（ただし、この場合式（２）のＲが塩素原子と考えられる）を得た後、超音波ホモジナイザーを使用して０．２重量％のＮＭＰ溶液を作製した。
Further, the aqueous dispersion of cellulose fibers was adjusted to pH 1 using 1M hydrochloric acid and stirred for 24 hours to obtain an oxidized cellulose fiber aggregate. The aggregate was then washed with acetone and washed with N-methyl-2-pyrrolidone (NMP). NMP is added to the aggregate of the oxidized cellulose fibers to make the oxidized cellulose concentration 0.2% by weight, treated with an ultrasonic homogenizer (Heelscher, UP400S) for 30 minutes, and oxidized cellulose. An NMP dispersion of fibers was obtained.
Transfer the oxidized NMP dispersion of cellulose fiber to a three-necked separable flask and cool thionyl chloride to the oxidized cellulose in the NMP dispersion while cooling to 10 ° C or lower in an ice-water bath in a nitrogen stream. The number of carbon atoms derived from methylol at the C6 position of the fiber was equimolarly dropped. Further, the three-necked separable flask was transferred to an oil bath, reacted at 70 ° C. with nitrogen flow for 4 hours, and then subjected to post-treatment, and a compound containing a repeating unit of the formula (2) (in this case, the formula (2) Then, a 0.2 wt% NMP solution was prepared using an ultrasonic homogenizer.
また、セルロース繊維を酸化処理する過程で、ＴＥＭＰＯや臭化ナトリウム等の仕込み量を変えることで、表１に示す前記セルロース繊維のＮＭＰ溶液を調製した。 Moreover, the cellulose fiber NMP solution shown in Table 1 was prepared by changing the amount of TEMPO or sodium bromide charged in the process of oxidizing the cellulose fiber.
（作製例２）
原料のセルロース繊維「セリッシュ（ダイセル化学工業製）ＫＹ１００Ｇ（セルロース分濃度１０重量％）」に水を加え、０．２重量％の混合液とした。この混合液を高圧ホモジナイザー（ノロ・ソビア社製、１５−８ＴＡ）型）を用いて圧力２０Ｍｐａで１０回処理し、機械処理されたセルロース繊維の水分散液を得た。このセルロース繊維を原料４とした。
(Production Example 2)
Water was added to the raw material cellulose fiber “Serish (manufactured by Daicel Chemical Industries) KY100G (cellulose concentration 10% by weight)” to obtain a 0.2% by weight mixed solution. This mixed solution was treated 10 times at a pressure of 20 Mpa using a high-pressure homogenizer (manufactured by Noro Sovia, 15-8TA type) to obtain a mechanically treated aqueous dispersion of cellulose fibers. This cellulose fiber was used as the raw material 4.
（実施例１）
乾燥管をつけた３つ口セパラブルフラスコに作製例１で得られた原料１のセルロース繊維のＮＭＰ溶液と水酸化ナトリウムを入れた後、前記式（４）の化合物として、ｔ−ブチルヒドロペルオキシド溶液（デカン溶液、シグマ アルドリッチ製）（前記式（２）の繰り返し単位を含む化合物におけるＣ６位のメチロール由来の炭素数と当モル以上）をＮＭＰに５質量％となるように加えた混合液を撹拌しながら窒素雰囲気下で滴下し、その後、室温で１０時間撹拌した。反応終了後、減圧ろ過して不溶分を除去し、ろ液を大過剰のヘキサンに再沈殿させ、析出物をろ過した後、該析出物をＮＭＰにホモジナイザーを使用して溶解・分散させ、大過剰の水に３回再沈殿させることで粗生成物の精製を行い、本発明の分子中に式（１）で表される繰り返し単位を含むペルオキシ基含有セルロース繊維を得た。得られたセルロース繊維をＦＴ−ＩＲにより測定した結果、セルロースに由来するスペクトル、ｔ−ブチルヒドロペルオキシドのペルオキシ基に由来するスペクトルがそれぞれ観察された。また、セルロース繊維を固体ＮＭＲ法による１３Ｃ−ＮＭＲ測定を行った結果、Ｃ６位の原料メチロール由来の炭素と結合を形成したｔ−ブチルヒドロペルオキシドが観測された。
前記セルロース繊維１００重量部にＮＭＰを加え該セルロース濃度０．２重量％の混合液とし、ラジカル重合性モノマーとして、スチレン（東京化成工業製）を２００重量部加え、室温で３０分間窒素をバブリングした後、８０℃で８時間撹拌しながら重合させた。反応終了後、不溶分を除去し、ろ液を大過剰のメタノールに再沈殿させ、析出物をろ過した後、該析出物をＮＭＰにホモジナイザーを使用して溶解・分散させ、大過剰の水に３回再沈殿させることで粗生成物の精製を行い、本発明のセルロース繊維含有重合体を得た。得られたセルロース繊維含有重合体をＦＴ−ＩＲにより測定した結果、セルロースに由来するスペクトル、ポリスチレンの芳香環に由来するスペクトルがそれぞれ観察された。また、セルロース繊維を固体ＮＭＲ法による１３Ｃ−ＮＭＲ測定を行った結果、Ｃ６位の原料メチロール由来の炭素と結合を形成したポリスチレンが観測された。さらに、重合体部のグラフト率は、９８％であった。
次に、前記セルロース繊維含有重合体にＮＭＰを加え該重合体濃度０．２質量％の混合液とし、超音波ホモジナイザーを用いて３０分間処理し、セルロース繊維含有重合体のＮＭＰ分散液を得た。
その後、前記分散液中のセルロース繊維含有重合体５０重量部に対してノボラック型フェノール樹脂Ａ１０８７（住友ベークライト製）を１００重量部配合、撹拌し、セルロース繊維含有重合体が均一に分散した混合物を得た。得られた前記混合物を離型処理したシャーレに注ぎ、温度１４０℃の熱板上で８時間脱溶媒処理をして、樹脂組成物を得た。
得られた樹脂組成物を表面が平滑なステンレス板に挟み、プレス機により９０℃で成形し、３０μｍのフィルムを得た。光線透過率を測定したところ、全光線透過率は８２％であった。
前記と同様の手法により得られた樹脂組成物を粉砕し、樹脂組成物中のノボラック型フェノール樹脂１０重量部に対して、ヘキサメチレンテトラミン（三菱ガス化学製）１.５重量部を配合し、ミキサーで３分間混合した後、２本ロールにより１００℃で溶融混練して、成形材料に用いる樹脂組成物を得た。得られた成形材料に用いる樹脂組成物を圧縮成形で１２５℃で２時間、１５０℃で２時間硬化させ、厚み１ｍｍ、幅１０ｍｍのテストピースを得た。曲げ強度を測定した結果、７９Ｎであった。
Example 1
After putting the NMP solution of cellulose fiber of the raw material 1 obtained in Production Example 1 and sodium hydroxide into a three-necked separable flask with a drying tube, t-butyl hydroperoxide is used as the compound of the formula (4). A solution obtained by adding a solution (decane solution, manufactured by Sigma-Aldrich) (equal to or more than the number of carbon atoms derived from methylol at the C6 position in the compound containing the repeating unit of the formula (2) to 5% by mass in NMP. The mixture was added dropwise with stirring under a nitrogen atmosphere, and then stirred at room temperature for 10 hours. After completion of the reaction, filtration is performed under reduced pressure to remove insoluble matter, the filtrate is reprecipitated in a large excess of hexane, the precipitate is filtered, and the precipitate is dissolved and dispersed in NMP using a homogenizer. The crude product was purified by reprecipitation three times in excess water to obtain a peroxy group-containing cellulose fiber containing a repeating unit represented by the formula (1) in the molecule of the present invention. As a result of measuring the obtained cellulose fiber by FT-IR, a spectrum derived from cellulose and a spectrum derived from a peroxy group of t-butyl hydroperoxide were observed. Further, as a result of 13 C-NMR measurement of the cellulose fiber by a solid NMR method, t-butyl hydroperoxide forming a bond with carbon derived from the methylol at the C6 position was observed.
NMP was added to 100 parts by weight of the cellulose fiber to form a mixed solution having a cellulose concentration of 0.2% by weight, 200 parts by weight of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a radical polymerizable monomer, and nitrogen was bubbled at room temperature for 30 minutes. Thereafter, polymerization was carried out with stirring at 80 ° C. for 8 hours. After completion of the reaction, the insoluble matter is removed, the filtrate is reprecipitated in a large excess of methanol, and the precipitate is filtered, and then the precipitate is dissolved and dispersed in NMP using a homogenizer, and added to a large excess of water. The crude product was purified by reprecipitation three times to obtain the cellulose fiber-containing polymer of the present invention. As a result of measuring the obtained cellulose fiber-containing polymer by FT-IR, a spectrum derived from cellulose and a spectrum derived from an aromatic ring of polystyrene were observed. In addition, as a result of performing 13 C-NMR measurement on the cellulose fiber by a solid-state NMR method, polystyrene forming a bond with carbon derived from the raw material methylol at the C6 position was observed. Furthermore, the graft ratio of the polymer part was 98%.
Next, NMP was added to the cellulose fiber-containing polymer to obtain a mixed solution having a polymer concentration of 0.2% by mass, and the mixture was treated with an ultrasonic homogenizer for 30 minutes to obtain an NMP dispersion of the cellulose fiber-containing polymer. .
Thereafter, 100 parts by weight of novolac-type phenol resin A1087 (manufactured by Sumitomo Bakelite) is blended with 50 parts by weight of the cellulose fiber-containing polymer in the dispersion and stirred to obtain a mixture in which the cellulose fiber-containing polymer is uniformly dispersed. It was. The obtained mixture was poured into a petri dish that had been subjected to mold release treatment, and the solvent was removed on a hot plate at a temperature of 140 ° C. for 8 hours to obtain a resin composition.
The obtained resin composition was sandwiched between stainless steel plates having a smooth surface and molded at 90 ° C. by a press machine to obtain a 30 μm film. When the light transmittance was measured, the total light transmittance was 82%.
The resin composition obtained by the same method as described above is pulverized, and 1.5 parts by weight of hexamethylenetetramine (manufactured by Mitsubishi Gas Chemical) is blended with 10 parts by weight of the novolac type phenol resin in the resin composition. After mixing for 3 minutes with a mixer, the mixture was melt kneaded at 100 ° C. with two rolls to obtain a resin composition for use as a molding material. The resin composition used for the obtained molding material was cured by compression molding at 125 ° C. for 2 hours and 150 ° C. for 2 hours to obtain a test piece having a thickness of 1 mm and a width of 10 mm. The bending strength was measured and found to be 79N.
（実施例２）
作製例１のカルボキシル基の量が異なるセルロース繊維のＮＭＰ溶液（原料２）を用いた以外、実施例１と同様の操作を実施し、セルロース繊維含有重合体を得た。得られたセルロース繊維含有重合体をＦＴ−ＩＲにより測定した結果、セルロースに由来するスペクトル、ポリスチレンの芳香環に由来するスペクトルがそれぞれ観察された。また、セルロース繊維を固体ＮＭＲ法による１３Ｃ−ＮＭＲ測定を行った結果、Ｃ６位の原料メチロール由来の炭素と結合を形成したポリスチレンが観測された。さらに、重合体部のグラフト率は、９５％であった。
次に、カルボキシル基の量が異なるセルロース繊維を用いた以外は、実施例１と同様に
セルロース繊維含有重合体のＮＭＰ分散液を得た後、ノボラック型フェノール樹脂Ａ１０８７を用いる樹脂組成物の作製、３０μｍのフィルムの作製、さらに、厚み１ｍｍ、幅１０ｍｍのテストピースの作製も実施例１と同様の操作で実施した。
前記３０μｍのフィルムの光線透過率を測定したところ、全光線透過率は７１％、厚み１ｍｍ、幅１０ｍｍのテストピースでの曲げ強度は、６０Ｎであった。
(Example 2)
A cellulose fiber-containing polymer was obtained by performing the same operation as in Example 1 except that the NMP solution (raw material 2) of cellulose fibers having a different amount of carboxyl groups in Production Example 1 was used. As a result of measuring the obtained cellulose fiber-containing polymer by FT-IR, a spectrum derived from cellulose and a spectrum derived from an aromatic ring of polystyrene were observed. In addition, as a result of performing 13 C-NMR measurement on the cellulose fiber by a solid-state NMR method, polystyrene forming a bond with carbon derived from the raw material methylol at the C6 position was observed. Furthermore, the graft ratio of the polymer part was 95%.
Next, after obtaining an NMP dispersion of a cellulose fiber-containing polymer in the same manner as in Example 1 except that cellulose fibers having different amounts of carboxyl groups were used, preparation of a resin composition using a novolac type phenol resin A1087, Production of a 30 μm film and production of a test piece having a thickness of 1 mm and a width of 10 mm were carried out in the same manner as in Example 1.
When the light transmittance of the 30 μm film was measured, the total light transmittance was 71%, and the bending strength of a test piece having a thickness of 1 mm and a width of 10 mm was 60 N.
（実施例３）
作製例１のカルボキシル基の量が異なるセルロース繊維のＮＭＰ溶液（原料３）を用いた以外、実施例１と同様の操作を実施し、セルロース繊維含有重合体を得た。得られたセルロース繊維含有重合体をＦＴ−ＩＲにより測定した結果、セルロースに由来するスペクトル、ポリスチレンの芳香環に由来するスペクトルがそれぞれ観察された。また、セルロース繊維を固体ＮＭＲ法による１３Ｃ−ＮＭＲ測定を行った結果、Ｃ６位の原料メチロール由来の炭素と結合を形成したポリスチレンが観測された。さらに、重合体部のグラフト率は、９７％であった。
次に、カルボキシル基の量が異なるセルロース繊維を用いた以外は、実施例１と同様に
セルロース繊維含有重合体のＮＭＰ分散液を得た後、ノボラック型フェノール樹脂Ａ１０８７を用いる樹脂組成物の作製、３０μｍのフィルムの作製、さらに、厚み１ｍｍ、幅１０ｍｍのテストピースの作製も実施例１と同様の操作で実施した。
前記３０μｍのフィルムの光線透過率を測定したところ、全光線透過率は７５％、厚み１ｍｍ、幅１０ｍｍのテストピースでの曲げ強度は、６４Ｎであった。
(Example 3)
A cellulose fiber-containing polymer was obtained by carrying out the same operation as in Example 1 except that the NMP solution (raw material 3) of cellulose fibers having a different amount of carboxyl groups in Production Example 1 was used. As a result of measuring the obtained cellulose fiber-containing polymer by FT-IR, a spectrum derived from cellulose and a spectrum derived from an aromatic ring of polystyrene were observed. In addition, as a result of performing 13 C-NMR measurement on the cellulose fiber by a solid-state NMR method, polystyrene forming a bond with carbon derived from the raw material methylol at the C6 position was observed. Furthermore, the graft ratio of the polymer part was 97%.
Next, after obtaining an NMP dispersion of a cellulose fiber-containing polymer in the same manner as in Example 1 except that cellulose fibers having different amounts of carboxyl groups were used, preparation of a resin composition using a novolac type phenol resin A1087, Production of a 30 μm film and production of a test piece having a thickness of 1 mm and a width of 10 mm were carried out in the same manner as in Example 1.
When the light transmittance of the 30 μm film was measured, the total light transmittance was 75%, the bending strength of a test piece having a thickness of 1 mm and a width of 10 mm was 64 N.
（実施例４）
乾燥管をつけた３つ口セパラブルフラスコに作製例１で得られた原料１のセルロース繊維のＮＭＰ溶液と水酸化ナトリウムを入れた後、前記式（３）の化合物として、２，２‘−アゾビス（２−アミジノプロパン）二塩酸塩（和光純薬工業製）（前記式（２）の繰り返し単位を含む化合物におけるＣ６位のメチロール由来の炭素数と当モル以上）をＮＭＰに５質量％となるように加えた混合液を撹拌しながら窒素雰囲気下で滴下し、その後、室温で６時間撹拌した。反応終了後、減圧ろ過して不溶分を除去し、ろ液を大過剰のヘキサンに再沈殿させ、析出物をろ過した後、該析出物をＮＭＰにホモジナイザーを使用して溶解・分散させ、大過剰の水に３回再沈殿させることで粗生成物の精製を行い、本発明の分子中に式（１）で表される繰り返し単位を含むアゾ基含有セルロース繊維を得た。得られたセルロース繊維をＦＴ−ＩＲにより測定した結果、セルロースに由来するスペクトル、２，２‘−アゾビス（２−アミジノプロパン）二塩酸塩のアゾ基に由来するスペクトルがそれぞれ観察された。また、セルロース繊維を固体ＮＭＲ法による１３Ｃ−ＮＭＲ測定を行った結果、Ｃ６位の原料メチロール由来の炭素と結合を形成した２，２‘−アゾビス（２−アミジノプロパン）二塩酸塩が観測された。
前記セルロース繊維１００重量部にＮＭＰを加え該セルロース濃度０．２重量％の混合液とし、ラジカル重合性モノマーとして、スチレンを２００重量部加え、室温で３０分間窒素をバブリングした後、６０℃で１０時間撹拌しながら重合させた。反応終了後、不溶分を除去し、ろ液を大過剰のメタノールに再沈殿させ、析出物をろ過した後、該析出物をＮＭＰにホモジナイザーを使用して溶解・分散させ、大過剰の水に３回再沈殿させることで粗生成物の精製を行い、本発明のセルロース繊維含有重合体を得た。得られたセルロース繊維含有重合体をＦＴ−ＩＲにより測定した結果、セルロースに由来するスペクトル、ポリスチレンの芳香環に由来するスペクトルがそれぞれ観察された。また、セルロース繊維を固体ＮＭＲ法による１３Ｃ−ＮＭＲ測定を行った結果、Ｃ６位の原料メチロール由来の炭素と結合を形成したポリスチレンが観測された。さらに、重合体部のグラフト率は、９９％であった。
次に、異なる重合開始基から重合させた以外は、実施例１と同様にセルロース繊維含有重合体のＮＭＰ分散液を得た後、ノボラック型フェノール樹脂Ａ１０８７を用いる樹脂組成物の作製、３０μｍのフィルムの作製、さらに、厚み１ｍｍ、幅１０ｍｍのテストピースの作製も実施例１と同様の操作で実施した。
前記３０μｍのフィルムの光線透過率を測定したところ、全光線透過率は８１％、厚み１ｍｍ、幅１０ｍｍのテストピースでの曲げ強度は、７５Ｎであった。
Example 4
After putting the NMP solution of cellulose fiber of the raw material 1 obtained in Preparation Example 1 and sodium hydroxide into a three-necked separable flask equipped with a drying tube, 2,2′- as the compound of the above formula (3) Azobis (2-amidinopropane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) (the number of carbons derived from methylol at the C6 position in the compound containing the repeating unit of the above formula (2) and an equivalent mole or more) is 5% by mass in NMP The mixed solution was added dropwise with stirring under a nitrogen atmosphere, and then stirred at room temperature for 6 hours. After completion of the reaction, filtration is performed under reduced pressure to remove insoluble matter, the filtrate is reprecipitated in a large excess of hexane, the precipitate is filtered, and the precipitate is dissolved and dispersed in NMP using a homogenizer. The crude product was purified by reprecipitation three times in excess water to obtain an azo group-containing cellulose fiber containing a repeating unit represented by the formula (1) in the molecule of the present invention. As a result of measuring the obtained cellulose fiber by FT-IR, a spectrum derived from cellulose and a spectrum derived from the azo group of 2,2′-azobis (2-amidinopropane) dihydrochloride were observed. In addition, as a result of 13 C-NMR measurement of the cellulose fiber by solid-state NMR method, 2,2′-azobis (2-amidinopropane) dihydrochloride that forms a bond with carbon derived from the methylol at the C6 position was observed. It was.
NMP is added to 100 parts by weight of the cellulose fiber to obtain a mixed solution having a cellulose concentration of 0.2% by weight, 200 parts by weight of styrene is added as a radical polymerizable monomer, and nitrogen is bubbled at room temperature for 30 minutes. Polymerization was conducted with stirring for a period of time. After completion of the reaction, the insoluble matter is removed, the filtrate is reprecipitated in a large excess of methanol, and the precipitate is filtered, and then the precipitate is dissolved and dispersed in NMP using a homogenizer, and added to a large excess of water. The crude product was purified by reprecipitation three times to obtain the cellulose fiber-containing polymer of the present invention. As a result of measuring the obtained cellulose fiber-containing polymer by FT-IR, a spectrum derived from cellulose and a spectrum derived from an aromatic ring of polystyrene were observed. In addition, as a result of performing 13 C-NMR measurement on the cellulose fiber by a solid-state NMR method, polystyrene forming a bond with carbon derived from the raw material methylol at the C6 position was observed. Furthermore, the graft ratio of the polymer part was 99%.
Next, an NMP dispersion of a cellulose fiber-containing polymer was obtained in the same manner as in Example 1 except that polymerization was performed from a different polymerization initiating group, and then a resin composition was prepared using a novolac-type phenol resin A1087, and a 30 μm film. Further, a test piece having a thickness of 1 mm and a width of 10 mm was prepared in the same manner as in Example 1.
When the light transmittance of the 30 μm film was measured, the total light transmittance was 81%, the bending strength of a test piece having a thickness of 1 mm and a width of 10 mm was 75 N.
（実施例５）
実施例１と同様にセルロース繊維含有重合体のＮＭＰ分散液を得た後、前記分散液中のセルロース繊維含有重合体５０重量部に対してレゾール型フェノール樹脂ＰＲ−９６１Ａ（住友ベークライト製）を１００重量部配合して撹拌し、セルロース繊維含有重合体が均一に分散した混合物を得た。得られた前記混合物を離型処理したシャーレに注ぎ、減圧下において、温度８０℃の熱板上で８時間脱溶媒処理をし、さらに１５０℃で２時間プレス成形し、３０μｍのフィルム、および厚み１ｍｍ、幅１０ｍｍのテストピースを得た。
３０μｍのフィルムの光線透過率を測定したところ、全光線透過率は８０％であった。厚み１ｍｍ、幅１０ｍｍのテストピースの曲げ強度を測定した結果、７８Ｎであった。
(Example 5)
After obtaining an NMP dispersion of the cellulose fiber-containing polymer in the same manner as in Example 1, 100 resol type phenolic resin PR-961A (manufactured by Sumitomo Bakelite) was added to 50 parts by weight of the cellulose fiber-containing polymer in the dispersion. Part by weight was blended and stirred to obtain a mixture in which the cellulose fiber-containing polymer was uniformly dispersed. The obtained mixture was poured into a petri dish subjected to a mold release treatment, desolvated on a hot plate at a temperature of 80 ° C. for 8 hours under reduced pressure, and further press-molded at 150 ° C. for 2 hours to form a 30 μm film and a thickness. A test piece having a width of 1 mm and a width of 10 mm was obtained.
When the light transmittance of a 30 μm film was measured, the total light transmittance was 80%. The bending strength of a test piece having a thickness of 1 mm and a width of 10 mm was measured and found to be 78N.
（実施例６）
実施例１と同様にペルオキシ基含有セルロース繊維を得た後、前記セルロース繊維１００重量部にＮＭＰを加え該セルロース濃度０．２重量％の混合液とし、ラジカル重合性モノマーとして、メチルメタクリレート（東京化成工業製）を２００重量部加え、室温で３０分間窒素をバブリングした後、８０℃で８時間撹拌しながら重合させた。反応終了後、不溶分を除去し、ろ液を大過剰のメタノールに再沈殿させ、析出物をろ過した後、該析出物をＮＭＰにホモジナイザーを使用して溶解・分散させ、大過剰の水に３回再沈殿させることで粗生成物の精製を行い、本発明のセルロース繊維含有重合体を得た。得られたセルロース繊維含有重合体をＦＴ−ＩＲにより測定した結果、セルロースに由来するスペクトル、ポリメチルメタクリレートに由来するスペクトルがそれぞれ観察された。また、セルロース繊維を固体ＮＭＲ法による１３Ｃ−ＮＭＲ測定を行った結果、Ｃ６位の原料メチロール由来の炭素と結合を形成したポリメチルメタクリレートが観測された。さらに、重合体部のグラフト率は、９６％であった。
次に、前記セルロース繊維含有重合体にＮＭＰを加え該重合体濃度０．２質量％の混合液とし、超音波ホモジナイザーを用いて３０分間処理し、セルロース繊維含有重合体のＮＭＰ分散液を得た。
その後、前記分散液中のセルロース繊維含有重合体５０重量部に対してビスフェノールＡ型エポキシ樹脂ＪＥＲ８２８（ジャパンエポキシレジン製）と芳香族アミン系硬化剤ジアミノフェニルメタン（スリーボンド製）の当量配合物を１００重量部配合、撹拌し、セルロース繊維含有重合体が均一に分散した混合物を得た。得られた前記混合物を離型処理したシャーレに注ぎ、減圧下において、温度８０℃の熱板上で８時間脱溶媒処理をし、さらに１５０℃で２時間プレス成形し、３０μｍの樹脂組成物のフィルム、および厚み１ｍｍ、幅１０ｍｍのテストピースを得た。
３０μｍのフィルムの光線透過率を測定したところ、全光線透過率は８４％であった。厚み１ｍｍ、幅１０ｍｍのテストピースの曲げ強度を測定した結果、７３Ｎであった。
(Example 6)
After obtaining a peroxy group-containing cellulose fiber in the same manner as in Example 1, NMP was added to 100 parts by weight of the cellulose fiber to obtain a mixed solution having a cellulose concentration of 0.2% by weight, and methyl methacrylate (Tokyo Kasei Co., Ltd.) was used as a radical polymerizable monomer. 200 parts by weight of Kogyo Co., Ltd. was added, and nitrogen was bubbled at room temperature for 30 minutes, followed by polymerization with stirring at 80 ° C. for 8 hours. After completion of the reaction, the insoluble matter is removed, the filtrate is reprecipitated in a large excess of methanol, and the precipitate is filtered, and then the precipitate is dissolved and dispersed in NMP using a homogenizer, and added to a large excess of water. The crude product was purified by reprecipitation three times to obtain the cellulose fiber-containing polymer of the present invention. As a result of measuring the obtained cellulose fiber-containing polymer by FT-IR, a spectrum derived from cellulose and a spectrum derived from polymethyl methacrylate were observed, respectively. Moreover, as a result of performing the 13 C-NMR measurement by the solid-state NMR method of the cellulose fiber, the polymethylmethacrylate which formed the bond with carbon derived from the C6 raw material methylol was observed. Furthermore, the graft ratio of the polymer part was 96%.
Next, NMP was added to the cellulose fiber-containing polymer to obtain a mixed solution having a polymer concentration of 0.2% by mass, and the mixture was treated with an ultrasonic homogenizer for 30 minutes to obtain an NMP dispersion of the cellulose fiber-containing polymer. .
Thereafter, an equivalent composition of bisphenol A type epoxy resin JER828 (made by Japan Epoxy Resin) and aromatic amine-based curing agent diaminophenylmethane (made by ThreeBond) is added to 100 parts by weight of the cellulose fiber-containing polymer in the dispersion. Part by weight was mixed and stirred to obtain a mixture in which the cellulose fiber-containing polymer was uniformly dispersed. The obtained mixture was poured into a petri dish that had been subjected to mold release treatment, subjected to desolvation treatment on a hot plate at a temperature of 80 ° C. for 8 hours under reduced pressure, and further press-molded at 150 ° C. for 2 hours to obtain a 30 μm resin composition. A film and a test piece having a thickness of 1 mm and a width of 10 mm were obtained.
When the light transmittance of a 30 μm film was measured, the total light transmittance was 84%. It was 73N as a result of measuring the bending strength of the test piece of thickness 1mm and width 10mm.
（実施例７）
実施例１と同様にセルロース繊維含有重合体のＮＭＰ分散液を得た後、前記分散液中のセルロース繊維含有重合体１００重量部に対してノボラック型フェノール樹脂Ａ１０８７を１００重量部配合して撹拌し、セルロース繊維含有重合体が均一に分散した混合物を得た。得られた前記混合物を樹脂組成物の作製、３０μｍのフィルムの作製、さらに、厚み１ｍｍ、幅１０ｍｍのテストピースの作製も実施例１と同様の操作で実施した。
前記３０μｍのフィルムの光線透過率を測定したところ、全光線透過率は７９％、厚み１ｍｍ、幅１０ｍｍのテストピースでの曲げ強度は、７５Ｎであった。
(Example 7)
After obtaining an NMP dispersion of the cellulose fiber-containing polymer in the same manner as in Example 1, 100 parts by weight of the novolac-type phenol resin A1087 was added to 100 parts by weight of the cellulose fiber-containing polymer in the dispersion and stirred. A mixture in which the cellulose fiber-containing polymer was uniformly dispersed was obtained. Production of the resin mixture, production of a 30 μm film, and production of a test piece having a thickness of 1 mm and a width of 10 mm were carried out in the same manner as in Example 1.
When the light transmittance of the 30 μm film was measured, the total light transmittance was 79%, the bending strength of a test piece having a thickness of 1 mm and a width of 10 mm was 75 N.
（比較例）
作製例２で得られた原料４の機械処理されたセルロース繊維の水分散液を１Ｍの塩酸を用いてｐＨ１に調整し２４時間攪拌することで、機械処理されたセルロース繊維の凝集物を得た。該凝集物をアセトンで洗浄し、ＮＭＰで洗浄した。セルロース繊維の凝集物にＮＭＰを加え固形分濃度０．２質量％とし、超音波ホモジナイザーを用いて３０分間処理し、機械処理されたセルロース繊維のＮＭＰ分散液を得た。
次に前記機械処理されたセルロース繊維のＮＭＰ分散液を用いる以外は、実施例１と同様にノボラック型フェノール樹脂Ａ１０８７を用いる樹脂組成物の作製、３０μｍのフィルムの作製、さらに厚み１ｍｍ、幅１０ｍｍのテストピースを作製も実施例１と同様の操作で実施した。前記３０μｍのフィルムの光線透過率を測定したところ、全光線透過率は２９％、厚み１ｍｍ、幅１０ｍｍのテストピースでの曲げ強度は４４Ｎであった。
(Comparative example)
The mechanically treated cellulose fiber aqueous dispersion of the raw material 4 obtained in Production Example 2 was adjusted to pH 1 using 1M hydrochloric acid and stirred for 24 hours to obtain a mechanically treated cellulose fiber aggregate. . The aggregate was washed with acetone and washed with NMP. NMP was added to the aggregate of cellulose fibers to a solid content concentration of 0.2% by mass and treated for 30 minutes using an ultrasonic homogenizer to obtain an NMP dispersion of machined cellulose fibers.
Next, except for using the NMP dispersion of the machined cellulose fiber, a resin composition using a novolac-type phenolic resin A1087, a 30 μm film, a thickness of 1 mm, and a width of 10 mm are obtained in the same manner as in Example 1. A test piece was produced in the same manner as in Example 1. When the light transmittance of the 30 μm film was measured, the total light transmittance was 29%, the bending strength of a test piece having a thickness of 1 mm and a width of 10 mm was 44N.
上記の評価の結果を表２に示した。 The results of the above evaluation are shown in Table 2.
表から明らかなように、実施例１〜７は本研究のセルロース繊維含有重合体を用いた樹脂組成物を用いて得られる成形体であり、高い光線透過率と曲げ強度を示す結果となった。
比較例は、本発明のセルロース繊維含有重合体を用いず、機械処理されたセルロース繊維とノボラック型フェノール樹脂による樹脂組成物を用いて得られる成形体であるが、光線透過率と曲げ強度が本発明のセルロース繊維含有重合体を用いた樹脂組成物と比較して大幅に低い結果であった。
以上のことから、本発明は、透明性に優れ、かつ機械的強度にも優れる成形体を提供し得るセルロース繊維、セルロース繊維含有重合体および樹脂組成物を提供できることが確認された。
As is apparent from the table, Examples 1 to 7 are molded products obtained using the resin composition using the cellulose fiber-containing polymer of this study, and resulted in high light transmittance and bending strength. .
A comparative example is a molded article obtained by using a resin composition comprising a cellulose fiber and a novolac type phenol resin which are machined without using the cellulose fiber-containing polymer of the present invention. The result was significantly lower than that of the resin composition using the cellulose fiber-containing polymer of the invention.
From the above, it was confirmed that the present invention can provide a cellulose fiber, a cellulose fiber-containing polymer, and a resin composition that can provide a molded article excellent in transparency and mechanical strength.
本発明のセルロース繊維、セルロース繊維含有重合体、および樹脂組成物のいずれかを用いて得られる成形体は透明性に優れ、かつ機械的強度にも優れていることから、光学特性が重要な特性である太陽電池用基板、有機ＥＬ用基板、電子ペーパー用基板、液晶表示素子用プラスチック基板、光学シート、光学フィルムなどの光学部品に有用に使用することができ、また、機械的強度が重要な特性であるダッシュボードやインスツルメントパネルなどの自動車部品、絶縁性の高い樹脂であることから、半導体封止材などの半導体材料にも有用に使用することが出来る。
また、機械的強度に優れていることに加え、セルロースの軽量性や生物由来の材料による環境負荷低減効果から、鉄道、航空機、船等の輸送用機器の部品、住宅やオフィスにおけるサッシ、壁板及び床板などの建材、柱あるいは鉄筋コンクリートにおける鉄筋のような構造部材、電子回路、パソコン及び携帯電話等の家電製品の筐体（ハウジング）、文具等の事務用機器、家具、使い捨て容器等の生活用品、スポーツ用品、玩具など家庭内で使用される小物、看板、標識などの野外設置物、防弾盾、防弾チョッキなどの衝撃吸収部材、ヘルメットなどの護身用具、人工骨、医療用品、研磨剤、防音壁、防護壁、振動吸収部材、工具、板ばねなどの機械部品、楽器、梱包材などにも使用することが出来、本発明の有用性は高い。
The molded product obtained by using any of the cellulose fiber, the cellulose fiber-containing polymer, and the resin composition of the present invention is excellent in transparency and mechanical strength. It can be usefully used for optical components such as solar cell substrates, organic EL substrates, electronic paper substrates, plastic substrates for liquid crystal display elements, optical sheets and optical films, and mechanical strength is important. Since it is a characteristic automotive component such as a dashboard or an instrument panel, or a highly insulating resin, it can be usefully used for a semiconductor material such as a semiconductor encapsulant.
In addition to its excellent mechanical strength, the light weight of cellulose and the effect of reducing the environmental impact of biological materials make it possible to use parts for transportation equipment such as railways, aircraft and ships, sashes and wallboards in houses and offices. Building materials such as floorboards, pillars or structural members such as reinforcing bars in reinforced concrete, housings for home appliances such as electronic circuits, personal computers and mobile phones, office equipment such as stationery, household items such as furniture and disposable containers , Sports equipment, toys and other small household items, signboards, signs and other outdoor installations, bulletproof shields, shock absorbers such as bulletproof vests, protective equipment such as helmets, artificial bones, medical supplies, abrasives, soundproof walls It can also be used for machine parts such as protective walls, vibration absorbing members, tools, leaf springs, musical instruments, packing materials, etc., and the utility of the present invention is high.
Claims (15)
またＸ５が水素原子である場合、Ｘ４はカルボキシル基と反応性のある官能基を少なくとも１つ含む有機基または１以上の炭素原子を含む有機基である。） The cellulose fiber according to any one of claims 1 to 3, wherein the cellulose fiber is obtained by reacting a peroxide represented by the following formula (4) with a compound containing a repeating unit of the following formula (2). .
When X 5 is a hydrogen atom, X 4 is an organic group containing at least one functional group reactive with a carboxyl group or an organic group containing one or more carbon atoms. )
The molded article according to claim 13 or 14, which has a bending strength of 50 N or more.
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