JP2015059206A - Modified cellulose, resin composition for masterbatch containing the modified cellulose, resin molding material and molding - Google Patents
Modified cellulose, resin composition for masterbatch containing the modified cellulose, resin molding material and molding Download PDFInfo
- Publication number
- JP2015059206A JP2015059206A JP2013195778A JP2013195778A JP2015059206A JP 2015059206 A JP2015059206 A JP 2015059206A JP 2013195778 A JP2013195778 A JP 2013195778A JP 2013195778 A JP2013195778 A JP 2013195778A JP 2015059206 A JP2015059206 A JP 2015059206A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- modified cellulose
- cellulose
- monoisocyanate
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 100
- 239000001913 cellulose Substances 0.000 title claims abstract description 99
- 229920005989 resin Polymers 0.000 title claims abstract description 87
- 239000011347 resin Substances 0.000 title claims abstract description 87
- 239000012778 molding material Substances 0.000 title claims abstract description 31
- 239000011342 resin composition Substances 0.000 title claims abstract description 27
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 26
- 238000000465 moulding Methods 0.000 title abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 48
- 238000006467 substitution reaction Methods 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- -1 aliphatic alcohols Chemical class 0.000 claims description 20
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 239000008186 active pharmaceutical agent Substances 0.000 claims 3
- 235000010980 cellulose Nutrition 0.000 description 86
- 238000003756 stirring Methods 0.000 description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 238000002347 injection Methods 0.000 description 16
- 239000007924 injection Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002002 slurry Substances 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229920001903 high density polyethylene Polymers 0.000 description 9
- 239000004700 high-density polyethylene Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 229920001131 Pulp (paper) Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
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- 229920001155 polypropylene Polymers 0.000 description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
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- 239000011324 bead Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000012779 reinforcing material Substances 0.000 description 5
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 210000001724 microfibril Anatomy 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
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- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- FIPPFBHCBUDBRR-UHFFFAOYSA-N henicosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCO FIPPFBHCBUDBRR-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- XGFDHKJUZCCPKQ-UHFFFAOYSA-N nonadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCO XGFDHKJUZCCPKQ-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
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- 239000011122 softwood Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- JXNPEDYJTDQORS-HZJYTTRNSA-N (9Z,12Z)-octadecadien-1-ol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCO JXNPEDYJTDQORS-HZJYTTRNSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FMVOPJLFZGSYOS-UHFFFAOYSA-N 2-[2-(2-ethoxypropoxy)propoxy]propan-1-ol Chemical compound CCOC(C)COC(C)COC(C)CO FMVOPJLFZGSYOS-UHFFFAOYSA-N 0.000 description 1
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Polysaccharides And Polysaccharide Derivatives (AREA)
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Abstract
Description
本発明は、成形材料用途に好適な変性セルロースならびに該変性セルロースを含むマスターバッチ用樹脂組成物、樹脂成形材料、および成形体に関し、詳しくは樹脂補強材料として用いた際の、成形体の強度を飛躍的に向上し得るウレタン骨格を導入した変性セルロースに関する。 The present invention relates to a modified cellulose suitable for use as a molding material, a resin composition for a masterbatch containing the modified cellulose, a resin molding material, and a molded body, and more specifically, the strength of the molded body when used as a resin reinforcing material. The present invention relates to a modified cellulose having a urethane skeleton that can be remarkably improved.
従来、樹脂に用いられる補強材料として、炭素繊維やガラス繊維等が広く一般的に使用されている。しかしながら、炭素繊維は高価であり、平滑性、リサイクル性が悪いとの課題がある。また、ガラス繊維は比較的安価であるが、比重が大きく、廃棄時にリサイクルし難いとの課題がある。 Conventionally, carbon fibers, glass fibers, and the like have been widely used as reinforcing materials used for resins. However, there is a problem that carbon fibers are expensive and have poor smoothness and recyclability. Moreover, although glass fiber is comparatively cheap, there is a problem that specific gravity is large and it is difficult to recycle at the time of disposal.
一方、植物繊維から得られるミクロフィブリル化セルロースは軽量、高強度、高弾性、低熱膨張といった優れた特性を持ち、更にサーマルリサイクルが可能といった様々な利点を持つことから樹脂成形体の補強剤として注目されている。 On the other hand, microfibrillated cellulose obtained from plant fibers has excellent properties such as light weight, high strength, high elasticity, and low thermal expansion, and also has various advantages such as thermal recycling, so it is attracting attention as a reinforcing agent for resin moldings. Has been.
しかしながらミクロフィブリル化セルロースは、親水性が高い為、疎水性の高い樹脂中で均一に分散させる事は難しく、ミクロフィブリル化セルロースと樹脂の親和性も低い。この為、ミクロフィブリル化セルロースによる十分な補強効果が得られない。 However, since the microfibrillated cellulose has high hydrophilicity, it is difficult to uniformly disperse it in a highly hydrophobic resin, and the affinity between the microfibrillated cellulose and the resin is low. For this reason, sufficient reinforcing effect by microfibrillated cellulose cannot be obtained.
このような課題に対して、ミクロフィブリル化セルロースの樹脂中での分散性を改善する目的で、相溶化剤を用いる、変性剤等によって疎水化する等の試みがなされている。 In order to improve the dispersibility of the microfibrillated cellulose in the resin, attempts have been made to solve such problems, such as using a compatibilizer or hydrophobizing with a modifier or the like.
例えば特許文献１等に記載されているように、セルロース系のミクロフィブリル化植物繊維とポリプロピレン等のポリオレフィンからなる複合材料において、マレイン酸変性ポリプロピレンを相溶化剤、又は界面補強剤として使用することが広く知られている。 For example, as described in Patent Document 1 and the like, maleic acid-modified polypropylene may be used as a compatibilizing agent or an interfacial reinforcing agent in a composite material composed of cellulose-based microfibrillated plant fibers and polyolefin such as polypropylene. Widely known.
一方、特許文献２には、セルロースミクロフィブリル表面に存在するヒドロキシル官能基に反応可能な、少なくとも１つの有機化合物（シリル化剤、イソシアネート、酸化アルキレン、グリシジル化合物など）によりエーテル化され、その置換度が少なくとも０．０５である変性セルロースミクロフィブリルを粘度変性剤や強化充填剤として用いることが記載されており、実施例には、強化充填剤としての使用に関し、一例としてシリル化剤により変性されたセルロースミクロフィブリルを架橋（加硫）エラストマーに適用した場合の機械的強度の向上が示されている。 On the other hand, Patent Document 2 discloses etherification with at least one organic compound (silylating agent, isocyanate, alkylene oxide, glycidyl compound, etc.) capable of reacting with a hydroxyl functional group existing on the surface of cellulose microfibril, and the degree of substitution thereof. It is described that a modified cellulose microfibril having an A of at least 0.05 is used as a viscosity modifier or a reinforcing filler, and in the Examples, the use as a reinforcing filler was modified by a silylating agent as an example. It shows improved mechanical strength when cellulose microfibrils are applied to cross-linked (vulcanized) elastomers.
上記いずれの方法を用いても、補強材料を用いない場合に比べて成形体の機械的強度は向上する。しかしながら、使用用途によっては、これら前記した従来の方法では補強効果が十分とは言えず、更なる強度向上が求められている。 Whichever method is used, the mechanical strength of the molded body is improved as compared with the case where no reinforcing material is used. However, depending on the intended use, the above-described conventional methods cannot be said to have a sufficient reinforcing effect, and further improvement in strength is required.
本発明は、樹脂に対する分散性や機械的強度に優れた変性セルロースならびに該変性セルロースを含むマスターバッチ用樹脂組成物、樹脂成形材料、および成形体を提供することを目的とする。 An object of this invention is to provide the modified cellulose excellent in the dispersibility with respect to resin and mechanical strength, the resin composition for masterbatches containing this modified cellulose, a resin molding material, and a molded object.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、セルロース繊維表面の水酸基に、特定のイソシアネート化合物を反応してウレタン構造を持たせることで、樹脂の補強材料として用いた場合に機械的強度が顕著に優れる成形体が得られることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have used a urethane structure by reacting a specific isocyanate compound with a hydroxyl group on the surface of a cellulose fiber, and used it as a reinforcing material for a resin. In some cases, the present inventors have found that a molded article having significantly excellent mechanical strength can be obtained, and completed the present invention.
すなわち、本発明は、
（１）モノイソシアネート（Ａ）をセルロース繊維（Ｂ）に反応して得られる変性セルロースであって、前記モノイソシアネート（Ａ）が、芳香族ジイソシアネート（ａ）と一価アルコール（ｂ）との反応物であり、前記モノイソシアネート（Ａ）による前記セルロース繊維（Ｂ）水酸基のウレタン置換度（ＤＳ）が０．０３〜０．５０であることを特徴とする変性セルロース、
（２）モノイソシアネート（Ａ）をセルロース繊維（Ｂ）に反応して得られる変性セルロースであって、前記モノイソシアネート（Ａ）が、下記一般式（１）で示されるウレタン構造を有し、前記モノイソシアネート（Ａ）による前記セルロース繊維（Ｂ）水酸基のウレタン置換度（ＤＳ）が０．０３〜０．５０であることを特徴とする変性セルロース、
Ｏ＝Ｃ＝Ｎ−Ｘ−ＮＨＣ（＝Ｏ）Ｏ−Ｙ （１）
（ただし、Ｘは炭素数６〜２０の芳香族基、Ｙは一価アルコールの残基を表わす。）
（３）一価アルコール（ｂ）が、直鎖または分岐の脂肪族アルコール、芳香族アルコール、ポリエーテルモノアルコールからなる群から選ばれる少なくとも１種以上のアルコールであることを特徴とする、前記（１）に記載の変性セルロース、
（４）一価アルコール（ｂ）が、炭素数３以上１８以下の分岐脂肪族アルコールである、前記（３）に記載の変性セルロース、
（５）セルロース繊維（Ｂ）水酸基の置換度（ＤＳ）が０．１０〜０．５０であることを特徴とする前記（１）または（２）に記載の変性セルロース、
（６）前記（１）〜（５）のいずれか一項に記載の変性セルロースと樹脂とからなる、変性セルロース／樹脂＝１〜５０／５０〜９９の質量比を有するマスターバッチ用樹脂組成物、
（７）前記（６）に記載のマスターバッチ用樹脂組成物を含有してなる樹脂成形材料 、
（８）前記（７）に記載の樹脂成形材料からなる成形体 、
である。
That is, the present invention
(1) Modified cellulose obtained by reacting monoisocyanate (A) with cellulose fiber (B), wherein the monoisocyanate (A) reacts with aromatic diisocyanate (a) and monohydric alcohol (b). A modified cellulose, wherein the cellulose fiber (B) has a hydroxyl group urethane substitution degree (DS) of 0.03 to 0.50 with the monoisocyanate (A),
(2) Modified cellulose obtained by reacting monoisocyanate (A) with cellulose fiber (B), wherein the monoisocyanate (A) has a urethane structure represented by the following general formula (1), Modified cellulose, wherein the cellulose fiber (B) has a urethane substitution degree (DS) of 0.03 to 0.50 with the monoisocyanate (A),
O = C = N-X-NHC (= O) O-Y (1)
(However, X represents an aromatic group having 6 to 20 carbon atoms, and Y represents a monohydric alcohol residue.)
(3) The monohydric alcohol (b) is at least one alcohol selected from the group consisting of linear or branched aliphatic alcohols, aromatic alcohols, and polyether monoalcohols, 1) modified cellulose according to
(4) The modified cellulose according to (3), wherein the monohydric alcohol (b) is a branched aliphatic alcohol having 3 to 18 carbon atoms,
(5) Cellulose fiber (B) Modified cellulose according to (1) or (2) above, wherein the hydroxyl group substitution degree (DS) is 0.10 to 0.50,
(6) Resin composition for masterbatch having a mass ratio of modified cellulose / resin = 1-50 / 50-99, comprising the modified cellulose according to any one of (1) to (5) and a resin. ,
(7) A resin molding material comprising the masterbatch resin composition according to (6),
(8) A molded body made of the resin molding material according to (7),
It is.
本発明の変性セルロースを樹脂の補強材料として用いた場合、樹脂に対する分散性が良好で、従来よりも機械的強度が顕著に優れた成形体を得ることができる。 When the modified cellulose of the present invention is used as a reinforcing material for a resin, it is possible to obtain a molded article having good dispersibility with respect to the resin and remarkably superior mechanical strength as compared with the prior art.
本発明の変性セルロースは、モノイソシアネート（Ａ）をセルロース繊維（Ｂ）に反応して得られる変性セルロースであって、前記モノイソシアネート（Ａ）が、芳香族ジイソシアネート（ａ）と、一価アルコール（ｂ）との反応物であり、前記モノイソシアネート（Ａ）による前記セルロース繊維（Ｂ）水酸基のウレタン置換度（ＤＳ）が０．０３〜０．５０である。ここでＤＳとは、「Ｄｅｇｒｅｅ ｏｆ Ｓｕｂｓｔｉｔｕｔｉｏｎ」の略である。以下、単に「ＤＳ」と記載することがある。 The modified cellulose of the present invention is a modified cellulose obtained by reacting a monoisocyanate (A) with cellulose fibers (B), and the monoisocyanate (A) comprises an aromatic diisocyanate (a) and a monohydric alcohol ( It is a reaction product with b), and the urethane substitution degree (DS) of the hydroxyl group of the cellulose fiber (B) by the monoisocyanate (A) is 0.03 to 0.50. Here, DS is an abbreviation for “Degree of Substation”. Hereinafter, it may be simply referred to as “DS”.
また、本発明の変性セルロースは、モノイソシアネート（Ａ）をセルロース繊維（Ｂ）に反応して得られる変性セルロースであって、前記モノイソシアネート（Ａ）は、下記一般式（１）で示されるウレタン構造を有し、前記モノイソシアネート（Ａ）による前記セルロース繊維（Ｂ）水酸基のウレタン置換度（ＤＳ）が０．０３〜０．５０である。
Ｏ＝Ｃ＝Ｎ−Ｘ−ＮＨＣ（＝Ｏ）Ｏ−Ｙ （１）
（ただし、Ｘは炭素数６〜２０の芳香族基、Ｙは一価アルコールの残基を表わす。）
The modified cellulose of the present invention is a modified cellulose obtained by reacting monoisocyanate (A) with cellulose fiber (B), and the monoisocyanate (A) is a urethane represented by the following general formula (1). The urethane substitution degree (DS) of the hydroxyl group of the cellulose fiber (B) with the monoisocyanate (A) is 0.03 to 0.50.
O = C = N-X-NHC (= O) O-Y (1)
(However, X represents an aromatic group having 6 to 20 carbon atoms, and Y represents a monohydric alcohol residue.)
本発明の変性セルロースに用いるモノイソシアネート（Ａ）は、芳香族ジイソシアネート（ａ）と、一価アルコール（ｂ）とが、１：１のモル比で反応して得ることができる。本発明で規定されるモノイソシアネート（Ａ）に代えて、２価以上のポリイソシアネートを用いた場合は、セルロース繊維（Ｂ）の繊維間架橋やポリイソシアネート同士の二量化、三量化反応が起こり、反応が制御できない。 The monoisocyanate (A) used in the modified cellulose of the present invention can be obtained by reacting the aromatic diisocyanate (a) and the monohydric alcohol (b) at a molar ratio of 1: 1. In place of the monoisocyanate (A) defined in the present invention, when a polyisocyanate having a valence of 2 or more is used, cross-linking between the fibers of the cellulose fiber (B) or dimerization between the polyisocyanates, a trimerization reaction occurs, The reaction cannot be controlled.
また、モノイソシアネートが本発明で規定されるモノイソシアネート（Ａ）以外の場合、機械強度が本発明のモノイソシアネートを用いる場合に比べ劣るものになっている。その原因は明らかではないが、変性セルロースがセルロースとの結合部分以外にウレタン骨格を有することにより、樹脂と変性セルロースの界面でとりわけ顕著な強度を発現するものと考えている。 Moreover, when monoisocyanate is other than the monoisocyanate (A) prescribed | regulated by this invention, mechanical strength is inferior compared with the case where the monoisocyanate of this invention is used. The reason for this is not clear, but it is believed that the modified cellulose has a urethane skeleton in addition to the cellulose-bonding portion, and thereby exhibits particularly remarkable strength at the interface between the resin and the modified cellulose.
芳香族ジイソシアネート（ａ）の例としては、トルエンジイソシアネート、フェニレンジイソシアネート、４， ４’−ジフェニルメタンジイソシアネート、１，５−ナフタレンジイソアネート、キシレンジイソシアネート、トリジンジイソシアネートなどの芳香族ジイソシアネートが挙げられる。これらの中でも、トルエンジイソシアネート、４， ４’−ジフェニルメタンジイソシアネートが工業的に入手しやすく、セルロースの有する水酸基との反応性が高いので所望の置換度の変性セルロースを比較的容易に得ることができ、好ましい。最も好ましくは、トルエンジイソシアネートである。 Examples of the aromatic diisocyanate (a) include aromatic diisocyanates such as toluene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, xylene diisocyanate, and tolidine diisocyanate. Among these, toluene diisocyanate and 4,4′-diphenylmethane diisocyanate are easily available industrially, and because the reactivity with the hydroxyl group of cellulose is high, modified cellulose having a desired substitution degree can be obtained relatively easily. preferable. Most preferred is toluene diisocyanate.
また、一価アルコール（ｂ）の例としては、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、ｔｅｒｔ−ブタノール、ペンタノール、イソペンタノール、ヘキサノール、シクロヘキサノール、へプタノール、オクタノール、２−エチルヘキサノール、ノナノール、デカノール、ウンデシルアルコール、ラウリルアルコール、トリデシルアルコール、ミリスチルアルコール、ペンタデシルアルコール、セタノール、２−ヘキシルデカノール、ヘプタデカノール、ステアリルアルコール、イソステアリルアルコール、ノナデシルアルコール、エイコサノール、イソエイコサノール、２−オクチルドデカノール、ヘンエイコサノール、ベヘニルアルコールなどの飽和脂肪族アルコール；ヒドロキシジシクロペンタジエン、オレイルアルコール、リノレイルアルコール、アリルアルコールなどの不飽和脂肪族アルコール；ベンジルアルコール、サリチルアルコール、アシニルアルコール、α−クミルアルコール、２−フェノキシエタノールなどの芳香族アルコール；エチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノプロピルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノプロピルエーテル、トリプロピレングリコールモノエチルエーテルなど、下記構造式で定義されるポリエーテルモノアルコールが挙げられる。
ＨＯ−（Ｒ１−Ｏ）ｎ−Ｒ２
ただし、ｎは１〜３の整数であり、Ｒ１は炭素数の２〜４の炭化水素、Ｒ２は炭素数１〜４の炭化水素を表す。
一価アルコール（ｂ）は１種単独で用いてもよく、これらから選ばれた２種以上を用いてもよい。一価アルコールの中でも、樹脂への変性セルロースの相溶性や成形体の機械的強度の観点から、分岐アルキル基を有する分岐脂肪族アルコール、芳香族アルコールが好ましく、分岐脂肪族アルコールがより好ましい。更に好ましくは、分岐脂肪族アルコールのうち、炭素数３以上１８以下の分岐脂肪族アルコールであり、中でも好ましいのは、２−エチルヘキサノール、イソステアリルアルコールである。
Examples of the monohydric alcohol (b) include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, cyclohexanol, heptanol, octanol and 2-ethyl. Hexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, 2-hexyldecanol, heptadecanol, stearyl alcohol, isostearyl alcohol, nonadecyl alcohol, eicosanol, isoeicosa Saturated fatty alcohols such as diol, 2-octyldodecanol, heneicosanol, and behenyl alcohol; Unsaturated aliphatic alcohols such as pentadiene, oleyl alcohol, linoleyl alcohol, and allyl alcohol; aromatic alcohols such as benzyl alcohol, salicyl alcohol, asinyl alcohol, α-cumyl alcohol, and 2-phenoxyethanol; ethylene glycol monomethyl ether, diethylene glycol Examples thereof include polyether monoalcohols defined by the following structural formulas such as monobutyl ether, triethylene glycol monopropyl ether, propylene glycol monomethyl ether, dipropylene glycol monopropyl ether, and tripropylene glycol monoethyl ether.
HO— (R 1 —O) n —R 2
However, n is an integer of 1 to 3, R 1 represents a hydrocarbon having 2 to 4 carbon atoms, and R 2 represents a hydrocarbon having 1 to 4 carbon atoms.
A monohydric alcohol (b) may be used individually by 1 type, and may use 2 or more types chosen from these. Among monohydric alcohols, branched aliphatic alcohols and aromatic alcohols having a branched alkyl group are preferred, and branched aliphatic alcohols are more preferred from the viewpoints of the compatibility of the modified cellulose with the resin and the mechanical strength of the molded article. More preferred are branched aliphatic alcohols having 3 to 18 carbon atoms, and 2-ethylhexanol and isostearyl alcohol are particularly preferred.
本発明のモノイソシアネート（Ａ）は、公知のウレタン合成方法で得ることができ、例えば、前記ジイソシアネート（ａ）と当モル量の一価アルコール（ｂ）を混合し、反応させて得る。この際、常温でイソシアネート基との反応が起きない有機溶媒を用いても良く、触媒を添加しても良い。反応後のＮＭＲから、前記一般式（１）で表わされる化合物であることを確認できる。 The monoisocyanate (A) of the present invention can be obtained by a known urethane synthesis method. For example, the diisocyanate (a) and an equimolar amount of a monohydric alcohol (b) are mixed and reacted. At this time, an organic solvent that does not react with an isocyanate group at room temperature may be used, or a catalyst may be added. It can confirm that it is a compound represented by the said General formula (1) from NMR after reaction.
本発明の変性セルロースに用いることができるセルロース繊維（Ｂ）は、特に限定されないが、セルロース繊維（Ｂ）の原料として用いることのできるものとしては、木材、竹、麻、ジュート、ケナフ、綿、ビートなどに含まれる植物由来の繊維、前記植物由来の繊維から得られるパルプ、マーセル化を施したセルロース繊維、レーヨンやセロファン、リヨセル等の再生セルロース繊維、酸無水物変性セルロースなどを含むものも挙げられる。
好ましいセルロース繊維原料としては木材が挙げられ、例えば、マツ、スギ、ヒノキ、ユーカリ、アカシアなどが挙げられ、好ましくは、これらを原料として得られるパルプや紙、あるいは古紙を解繊したものをセルロース繊維（Ｂ）として用いる。セルロース繊維（Ｂ）は、１種単独で用いてもよく、これらから選ばれた２種以上を用いてもよい。
Cellulose fibers (B) that can be used in the modified cellulose of the present invention are not particularly limited, but examples of materials that can be used as raw materials for cellulose fibers (B) include wood, bamboo, hemp, jute, kenaf, cotton, Plant-derived fibers contained in beets and the like, pulps obtained from the above-mentioned plant-derived fibers, cellulose fibers subjected to mercerization, regenerated cellulose fibers such as rayon, cellophane, and lyocell, those containing acid anhydride-modified cellulose, etc. It is done.
Preferred cellulose fiber raw materials include wood, for example, pine, cedar, cypress, eucalyptus, acacia and the like. Preferably, pulp fiber or paper obtained using these as raw materials, or fibrillated waste paper obtained from cellulose fibers Used as (B). A cellulose fiber (B) may be used individually by 1 type, and may use 2 or more types chosen from these.
前記パルプとしては、植物原料を化学的、若しくは機械的に、又は両者を併用してパルプ化することで得られるケミカルパルプ（クラフトパルプ（ＫＰ）、亜硫酸パルプ（ＳＰ））、セミケミカルパルプ（ＳＣＰ）、ケミグランドパルプ（ＣＧＰ）、ケミメカニカルパルプ（ＣＭＰ）、砕木パルプ（ＧＰ）、リファイナーメカニカルパルプ（ＲＭＰ）、サーモメカニカルパルプ（ＴＭＰ）、ケミサーモメカニカルパルプ（ＣＴＭＰ）等が挙げられる。 The pulp includes chemical pulp (kraft pulp (KP), sulfite pulp (SP)), semi-chemical pulp (SCP) obtained by pulping plant raw materials chemically or mechanically, or a combination of both. ), Chemi-Grand Pulp (CGP), Chemi-Mechanical Pulp (CMP), Groundwood Pulp (GP), Refiner Mechanical Pulp (RMP), Thermo-Mechanical Pulp (TMP), Chemi-thermo-Mechanical Pulp (CTMP) and the like.
またセルロース繊維（Ｂ）は、モノイソシアネート（Ａ）との反応性や置換度、樹脂に対する相溶性などに大きな影響を与えず、所望の機械的強度を有する成形体を得るのに差支えない範囲であれば、水酸基のエステル化やカルボキシル基、エーテル基などの官能基により一部水酸基が置換されたものを用いても構わない。また、モノイソシアネート（Ａ）との反応に用いる前に、モノイソシアネート（Ａ）との反応を阻害しないよう、予めセルロース繊維（Ｂ）に含まれる水をトルエンやＮ−メチルピロリドンなどの溶媒で置換しておく必要がある。 In addition, the cellulose fiber (B) does not greatly affect the reactivity with the monoisocyanate (A), the degree of substitution, the compatibility with the resin, and the like, and in a range that does not interfere with obtaining a molded article having a desired mechanical strength. As long as it exists, the hydroxyl group may be partially esterified by a functional group such as esterification of a hydroxyl group or a carboxyl group or an ether group. Prior to use in the reaction with the monoisocyanate (A), the water contained in the cellulose fiber (B) is previously replaced with a solvent such as toluene or N-methylpyrrolidone so as not to inhibit the reaction with the monoisocyanate (A). It is necessary to keep it.
モノイソシアネート（Ａ）とセルロース繊維（Ｂ）との反応方法は、特に限定されず、例えば次の方法で行うことができ、得られた変性セルロースは、通常、濾過、洗浄して溶媒や未反応物などを除去して次のマスターバッチ用樹脂の製造に使用する。
（Ｉ）モノイソシアネート（Ａ）が合成された溶液中に、予め溶媒置換されたセルロース繊維（Ｂ）を添加し、反応させる。
（ＩＩ）予め溶媒置換されたセルロース繊維（Ｂ）を分散させた分散液中に、モノイソシアネート（Ａ）を逐次あるいは一括で添加し、反応させる。
（ＩＩＩ）予め溶媒置換されたセルロース繊維（Ｂ）を分散させた分散液中に、モノイソシアネート（Ａ）の原料である一価アルコール（ｂ）を添加後、または添加と同時にジイソシアネート（ａ）を添加して、モノイソシアネート（Ａ）の合成とセルロース繊維（Ｂ）への反応を一括して行う。この場合、反応はモノイソシアネート（Ａ）の合成が優先して進行する。
The reaction method of monoisocyanate (A) and cellulose fiber (B) is not particularly limited, and can be performed, for example, by the following method. The obtained modified cellulose is usually filtered and washed to obtain a solvent or unreacted. The product is removed and used for the production of the next masterbatch resin.
(I) The cellulose fiber (B) previously substituted with a solvent is added to the solution in which the monoisocyanate (A) has been synthesized and reacted.
(II) Monoisocyanate (A) is added sequentially or collectively in a dispersion in which cellulose fibers (B) previously substituted with a solvent are dispersed, and reacted.
(III) The diisocyanate (a) is added after or simultaneously with the addition of the monohydric alcohol (b), which is the raw material of the monoisocyanate (A), in the dispersion liquid in which the cellulose fibers (B) previously solvent-substituted are dispersed. It adds and performs the synthesis | combination of monoisocyanate (A), and reaction to a cellulose fiber (B) collectively. In this case, the reaction proceeds with priority on the synthesis of the monoisocyanate (A).
イソシアネート（Ａ）によるセルロース繊維（Ｂ）の水酸基のウレタン置換度（ＤＳ）は、樹脂への相溶性や成形体の機械的強度の観点から、０．０３〜０．５０である必要がある。より好ましくは、０．１０〜０．５０である。ＤＳを０．０３以上に設定することによって、樹脂に対する分散性が十分となり、得られる成形材料の機械強度を向上させることができる。また、ＤＳを０．５０以下に設定することによって、セルロースの結晶性を維持できるため、変性セルロースを混合した成形体は十分な強度が得られるもと考えられる。 The urethane substitution degree (DS) of the hydroxyl group of the cellulose fiber (B) with the isocyanate (A) needs to be 0.03 to 0.50 from the viewpoints of compatibility with the resin and mechanical strength of the molded body. More preferably, it is 0.10 to 0.50. By setting DS to 0.03 or more, the dispersibility with respect to the resin becomes sufficient, and the mechanical strength of the obtained molding material can be improved. Moreover, since the crystallinity of cellulose can be maintained by setting DS to 0.50 or less, it is considered that a molded body mixed with modified cellulose can obtain sufficient strength.
本発明のＤＳは、洗浄により原料として用いた変性化剤や、それらの加水分解物等の副生成物を除去した後、質量増加率により算出したものである。 The DS of the present invention is calculated from the rate of mass increase after removing by-products such as the modifying agents used as raw materials and their hydrolysates by washing.
本発明のマスターバッチ用樹脂組成物は、前記変性セルロースと樹脂とを変性セルロース／樹脂＝１／９９〜５０／５０の質量比で混合、溶融混練することで得られる。変性セルロースの質量比が１より少ないと、変性セルロースを混合したことによる成形体の機械的強度向上が見られない。また、変性セルロースの質量比が５０より多いと、得られたマスターバッチ用樹脂組成物をそのまま樹脂成形材料として用いた場合には成形加工できない、あるいは成形できても脆く所望の機械的強度が得られない。好ましくは、変性セルロース／樹脂＝２．５／９７．５〜４０／６０であり、より好ましくは、変性セルロース／樹脂＝５／９５〜３５／６５である。 The resin composition for a masterbatch of the present invention is obtained by mixing, melt-kneading the modified cellulose and the resin at a mass ratio of modified cellulose / resin = 1/99 to 50/50. When the mass ratio of the modified cellulose is less than 1, no improvement in the mechanical strength of the molded product due to the mixing of the modified cellulose is observed. On the other hand, if the mass ratio of the modified cellulose is more than 50, when the obtained masterbatch resin composition is used as it is as a resin molding material, it cannot be molded or is brittle even if it can be molded to obtain a desired mechanical strength. I can't. Preferably, modified cellulose / resin = 2.5 / 97.5 to 40/60, more preferably modified cellulose / resin = 5/95 to 35/65.
本発明のマスターバッチ用樹脂組成物に用いることのできる樹脂は、特に成形加工可能な樹脂であれば限定されず、通常用いられている熱可塑性樹脂や熱硬化性樹脂が挙げられる。例えば、脂肪族または芳香族ポリエステル樹脂、ポリオレフィン、ポリアミド樹脂、アセタール樹脂、ポリカーボネート、フェノール樹脂、ユリア樹脂、メラミン樹脂、エポキシ樹脂、ポリウレタン樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、スチレン系樹脂、ＡＢＳ樹脂、アクリル樹脂、ポリエーテル、ポリイミド樹脂、フッ素樹脂、ケイ素樹脂などを１種単独または２種以上を組み合わせて使用できる。好ましくは、脂肪族または芳香族ポリエステル樹脂、ポリオレフィン、ポリアミド樹脂、アセタール樹脂、ポリカーボネート、フェノール樹脂、エポキシ樹脂、アクリル樹脂であり、より好ましくは、脂肪族または芳香族ポリエステル、ポリオレフィン、ポリアミド樹脂、アセタール樹脂、ポリカーボネートである。 The resin that can be used for the resin composition for a masterbatch of the present invention is not particularly limited as long as it is a resin that can be molded, and examples thereof include commonly used thermoplastic resins and thermosetting resins. For example, aliphatic or aromatic polyester resin, polyolefin, polyamide resin, acetal resin, polycarbonate, phenol resin, urea resin, melamine resin, epoxy resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, styrenic resin, ABS resin, Acrylic resin, polyether, polyimide resin, fluororesin, silicon resin and the like can be used singly or in combination of two or more. Preferably, aliphatic or aromatic polyester resin, polyolefin, polyamide resin, acetal resin, polycarbonate, phenol resin, epoxy resin, acrylic resin, more preferably aliphatic or aromatic polyester, polyolefin, polyamide resin, acetal resin Polycarbonate.
変性セルロースと樹脂との溶融混練は、加工性や樹脂および変性セルロースの分散や劣化を考慮すると、温度が１００〜２４０℃であることが好ましい。 In the melt-kneading of the modified cellulose and the resin, the temperature is preferably 100 to 240 ° C. in consideration of processability and dispersion and deterioration of the resin and the modified cellulose.
変性セルロースは、樹脂との溶融混練後のマスターバッチ用樹脂組成物中で十分にミクロフィブリル化されていることが好ましく、また、溶融混練前に必ずしもミクロフィブリル化されたものである必要はない。ミクロフィブリル化の方法としては、特に限定されないが、予めミクロフィブリル化しておく場合は、セルロース繊維（Ｂ）の懸濁液、又はスラリーをリファイナー、高圧ホモジナイザー、グラインダー、一軸又は多軸混練機、ビーズミル等の機械処理を行った後に変性反応を行う方法、あるいはセルロース繊維（Ｂ）の変性反応を行った後に、得られた変性セルロースの懸濁液、又はスラリーをリファイナー、高圧ホモジナイザー、グラインダー、一軸又は多軸混練機、ビーズミル等の機械処理を行う方法が好ましい。また、溶融混練時にミクロフィブリル化する場合は、変性セルロースと樹脂とを一軸又は多軸混練機等で処理する方法が好ましい。 The modified cellulose is preferably sufficiently microfibrillated in the masterbatch resin composition after melt-kneading with the resin, and is not necessarily microfibrillated before melt-kneading. The microfibrillation method is not particularly limited, but when microfibrillation is performed in advance, the suspension or slurry of the cellulose fiber (B) is refined, a high-pressure homogenizer, a grinder, a uniaxial or multiaxial kneader, a bead mill. A method of performing a modification reaction after performing mechanical processing such as the above, or after performing a modification reaction of the cellulose fiber (B), a suspension or slurry of the modified cellulose obtained is refined, a high-pressure homogenizer, a grinder, uniaxial or A method of performing mechanical processing such as a multi-axis kneader or a bead mill is preferred. Moreover, when microfibrillation is performed at the time of melt kneading, a method of treating the modified cellulose and the resin with a uniaxial or multiaxial kneader or the like is preferable.
ミクロフィブリル化された変性セルロースの繊維径は、平均値が通常４〜８００ｎｍ、好ましくは４〜５００ｎｍ、特に好ましくは２０〜５００ｎｍである。なお、ミクロフィブリル化された変性セルロースの繊維径の平均値（平均繊維径）は、電子顕微鏡の視野内の変性ミクロフィブリル化された変性セルロースの少なくとも５０本以上について測定した時の平均値である。 The fiber diameter of the microfibrillated modified cellulose is usually 4 to 800 nm, preferably 4 to 500 nm, particularly preferably 20 to 500 nm, as an average value. In addition, the average value (average fiber diameter) of the fiber diameter of the microfibrillated modified cellulose is an average value when measuring at least 50 or more of the modified microfibrillated modified cellulose within the field of view of the electron microscope. .
得られた前記マスターバッチ用樹脂組成物は、そのまま樹脂成形材料として、成形体の加工に用いることもできるが、通常は、変性セルロース含有量の高いマスターバッチ用樹脂組成物を更に前記した樹脂で任意の比率に希釈、溶融混練して、樹脂成形材料とする。希釈用樹脂は通常、マスターバッチ用樹脂組成物で用いたものと同じ樹脂を使用するが異なっても良い。樹脂成形材料の樹脂成分と変性セルロースの質量比は、前記したマスターバッチ用樹脂組成物と同様に、成形体の機械的強度を考慮すれば、樹脂成分／変性セルロース＝９９／１〜６０／４０であることが好ましい。 The obtained masterbatch resin composition can be used as it is as a resin molding material for the processing of a molded body. Usually, however, a resin composition for a masterbatch having a high modified cellulose content is further added to the resin described above. It is diluted to an arbitrary ratio, melt kneaded, and used as a resin molding material. The dilution resin usually uses the same resin as that used in the masterbatch resin composition, but may be different. The mass ratio of the resin component of the resin molding material to the modified cellulose is the same as in the masterbatch resin composition described above, taking into account the mechanical strength of the molded product, resin component / modified cellulose = 99/1 to 60/40. It is preferable that
本発明で得られるマスターバッチ用樹脂組成物や樹脂成形材料は、種々の形状に成形して用いることが出来る。形状としては、例えば、シート状、フィルム状、ペレット状、フレーク状、粉末状等が挙げられる。これらの形状を有する成形材料は、例えばプレス成形、射出成形、押出成形、ブロー成形、延伸成形、発泡成形、トランスファー成形、積層成形、注型成形等を用いて得られる。 The masterbatch resin composition and resin molding material obtained in the present invention can be molded into various shapes and used. Examples of the shape include a sheet shape, a film shape, a pellet shape, a flake shape, and a powder shape. The molding material having these shapes can be obtained using, for example, press molding, injection molding, extrusion molding, blow molding, stretch molding, foam molding, transfer molding, laminate molding, cast molding, and the like.
上述した本発明で得られる樹脂成形材料には、必要に応じて、滑材、ワックス類、着色剤、安定剤、フィラー、その他の各種の添加剤を配合してもよい。 The resin molding material obtained by the present invention described above may contain a lubricant, waxes, colorants, stabilizers, fillers, and other various additives as necessary.
更に前記の成形材料から、プレス成形、射出成形、押出成形、ブロー成形、延伸成形、発泡成形、トランスファー成形、積層成形、注型成形等の所望の成形法、所望の成形条件によって樹脂成形体を製造することが出来る。樹脂成形体としては、例えば、自動車、電車、船舶、飛行機等の輸送機器の内装材、外装材、構造材等；パソコン、テレビ、電話、時計等の電化製品等の筺体、構造材、内部部品等；携帯電話等の移動通信機器等の筺体、構造材、内部部品等；携帯音楽再生機器、映像再生機器、印刷機器、複写機器、スポーツ用品等の筺体、構造材、内部部品等；建築材；文具等の事務機器等、容器、コンテナー等が挙げられる。 Further, from the above molding materials, a resin molded body can be produced by a desired molding method and desired molding conditions such as press molding, injection molding, extrusion molding, blow molding, stretch molding, foam molding, transfer molding, laminate molding, and cast molding. Can be manufactured. Examples of resin moldings include interior materials, exterior materials, structural materials, etc. for transportation equipment such as automobiles, trains, ships, airplanes, etc .; housings, structural materials, internal parts, etc. for electrical appliances such as personal computers, televisions, telephones, watches, etc. Etc .; Mobile communication equipment such as mobile phones, structural materials, internal parts, etc .; Portable music playback equipment, video playback equipment, printing equipment, copying equipment, sports equipment, etc., structural materials, internal parts, etc .; ; Office equipment such as stationery, containers, containers and the like.
以下、本発明の実施例について説明する。なお、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below. The present invention is not limited to these examples.
これらの実施例の一部で用いられた物性値測定法は、以下のとおりである。
引張強度（破断）、引張弾性率（ヤング率）の測定
ポリエチレン樹脂、ポリプロピレン樹脂を用いた成形体はＪＩＳＫ−７１６２を参考に１ＢＡ形のダンベル型試験片を作成し、オリエンテック（株）製引張試験機「テンシロンＲＴＭ−５０」を用いて５ｍｍ／ｍｉｎの引張速度で測定した。
ポリアミド樹脂、ポリアセタール樹脂を用いた成形体はＪＩＳＫ−７１６２を参考に１ＢＡ形のダンベル型試験片を作成し、オリエンテック（株）製万能引張圧縮試験機「テンシロンＵＴＭ−１０」を用いて５ｍｍ／ｍｉｎの引張速度で測定した。
モノイソシアネート（Ａ）とセルロース繊維（Ｂ）との反応の確認
モノイソシアネート（Ａ）とセルロース繊維（Ｂ）との反応は、Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製フーリエ変換赤外分光分析装置「Ｓｐｅｃｔｒｕｍ ｏｎｅ」を用いて確認した。具体的には１６５０〜１７５０ｃｍ−１に生じるウレタン基カルボニル炭素と酸素の伸縮振動に由来するピーク強度が増強することから、定性的に確認した。
変性セルロースのウレタン置換度（ＤＳ）の算出
変性セルロースのウレタン置換度（ＤＳ）は、以下の式を利用してセルロース繊維（Ｂ）の水酸基をウレタン置換し変性セルロースとした際の質量変化から算出した。
Ｗc ：セルロース繊維（Ｂ）の乾燥質量
Ｍｄｉ ：反応に使用したジイソシアネートの分子量
Ｍａ ：反応に使用した一価アルコールの分子量
Ｍｇ ：セルロースを構成するグルコースユニットの分子量
（４）固形分の算出
有機溶媒含有変性セルロース（ウレタン変性ＮＢＫＰ）の固形分の測定には赤外線水分計（（株）ケット科学研究所製：「ＦＤ−６２０」）を用いた。
The physical property measurement methods used in some of these examples are as follows.
Measurement of tensile strength (rupture) and tensile modulus (Young's modulus) For molded products using polyethylene resin and polypropylene resin, make 1BA-type dumbbell-shaped specimens with reference to JISK-7162, and make a tensile manufactured by Orientec Co., Ltd. Measurement was performed at a tensile speed of 5 mm / min using a tester “Tensilon RTM-50”.
The molded body using polyamide resin and polyacetal resin was prepared by making a 1BA dumbbell-shaped test piece with reference to JISK-7162, and using a universal tensile compression tester “Tensilon UTM-10” manufactured by Orientec Co., Ltd., 5 mm / It was measured at a tensile rate of min.
Confirmation of the reaction between the monoisocyanate (A) and the cellulose fiber (B) The reaction between the monoisocyanate (A) and the cellulose fiber (B) was performed using a Fourier transform infrared spectrometer “Spectrum one” manufactured by Perkin Elmer. confirmed. Specifically, since the peak intensity derived from the stretching vibration of urethane group carbonyl carbon and oxygen generated at 1650 to 1750 cm −1 is enhanced, it was confirmed qualitatively.
Calculation of the degree of urethane substitution (DS) of the modified cellulose The degree of urethane substitution (DS) of the modified cellulose is calculated from the change in mass when the hydroxyl group of the cellulose fiber (B) is urethane-substituted to obtain a modified cellulose using the following formula. did.
［（Ａ）モノイソシアネートの合成例］
（合成例１）
容積１０００ｍｌのセパラブルフラスコへＮ−メチルピロリドン（以下、ＮＭＰと略すことがある。）を２７３．７ｇ、トルエンジイソシアネート (２，４−トルエンジイソシアネート 約８０質量％、２，６−トルエンジイソシアネート 約２０質量％ の混合物）５２．２６ｇ（０．３ｍｏｌ）、２−エチルヘキサノールを３９．０６ｇ（０．３ｍｏｌ）投入し、５分間撹拌して系内を均一とした。撹拌後、ジラウリル酸ジブチル錫を０．１０ｇ加えて室温で３０分間撹拌してモノイソシアネート含有量２５質量％のＮ−メチルピロリドン溶液（Ａ−１）を得た。ＮＭＲ測定により、トルエンジイソシアネートと２−エチルヘキサノールとの反応により得られるモノイソシアネートが仕込み量に対し９８％生成していることを確認した。
[(A) Synthesis example of monoisocyanate]
(Synthesis Example 1)
273.7 g of N-methylpyrrolidone (hereinafter sometimes abbreviated as NMP) in a separable flask having a volume of 1000 ml, toluene diisocyanate (2,4-toluene diisocyanate about 80 mass%, 2,6-toluene diisocyanate about 20 mass) % Mixture) 52.26 g (0.3 mol) and 2-ethylhexanol 39.06 g (0.3 mol) were added and stirred for 5 minutes to make the system uniform. After stirring, 0.10 g of dibutyltin dilaurate was added and stirred at room temperature for 30 minutes to obtain an N-methylpyrrolidone solution (A-1) having a monoisocyanate content of 25% by mass. NMR measurement confirmed that 98% of the monoisocyanate obtained by the reaction of toluene diisocyanate and 2-ethylhexanol was produced with respect to the charged amount.
（合成例２）〜（合成例９）
表１に記載のジイソシアネート（ａ）、一価アルコール（ｂ）に代え、Ｎ−メチルピロリドンの仕込み量を調整したほかは合成例１と同様に操作を行い、各モノイソシアネート含有量２５質量％のＮ−メチルピロリドン溶液（Ａ−２）〜（Ａ−９）を得た。
(Synthesis Example 2) to (Synthesis Example 9)
In place of the diisocyanate (a) and monohydric alcohol (b) listed in Table 1, the same procedure as in Synthesis Example 1 was carried out except that the amount of N-methylpyrrolidone was adjusted, and each monoisocyanate content was 25% by mass. N-methylpyrrolidone solutions (A-2) to (A-9) were obtained.
［溶媒置換セルロース繊維（Ｂ）の調製］
［調製例１］
含水の針葉樹漂白パルプ（以下、ＮＢＫＰと略することがある。）１００ｇ（固形分３５．０ｇ）にＮ−メチルピロリドン（以下、ＮＭＰと略することがある。）を１４００ｇ加え、撹拌機でよく攪拌した後、ブフナー漏斗で吸引濾過を行った。この操作を３回繰り返し、ＮＭＰで膨潤させたＮＢＫＰ１００ｇを得た。
[Preparation of solvent-substituted cellulose fiber (B)]
[Preparation Example 1]
1400 g of N-methylpyrrolidone (hereinafter sometimes abbreviated as NMP) is added to 100 g (hereinafter may be abbreviated as NBKP) of hydrous softwood bleached pulp (hereinafter sometimes abbreviated as NBKP) and agitator may be used. After stirring, suction filtration was performed with a Buchner funnel. This operation was repeated three times to obtain 100 g of NBKP swollen with NMP.
［変性セルロースの製造］
［実施例１］
攪拌機、温度計、還流冷却器及び窒素ガス導入管を備えた容積１０００ｍｌのセパラブルフラスコへ、窒素雰囲気下、モノイソシアネートとして合成例１で得られた（Ａ−１）３６５．２８ｇ（モノイソシアネートとして０．３ｍｏｌ）を仕込み、調製例１で得られたＮＢＫＰ膨潤セルロース繊維４６．２９ｇ（固形分１６．２０ｇ）を投入した。撹拌しながら９０℃へ昇温し、３時間反応させた後に７０℃まで冷却し、２７．６４ｇのエタノールを投入した上で冷却し反応を終了させた。反応物をＮＭＰ、アセトン、エタノールで順次洗浄し、エタノールを含有した固形分２０質量％の変性セルロース（Ｃ−１）を得た。
[Production of modified cellulose]
[Example 1]
(A-1) 365.28 g (as monoisocyanate) obtained in Synthesis Example 1 as monoisocyanate under a nitrogen atmosphere into a separable flask having a volume of 1000 ml equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube 0.3 mol) was charged, and 46.29 g of NBKP-swelled cellulose fiber obtained in Preparation Example 1 (solid content: 16.20 g) was added. While stirring, the temperature was raised to 90 ° C. and reacted for 3 hours, then cooled to 70 ° C., and 27.64 g of ethanol was added thereto, followed by cooling to complete the reaction. The reaction product was washed sequentially with NMP, acetone, and ethanol to obtain a modified cellulose (C-1) containing ethanol and having a solid content of 20% by mass.
［実施例２］
反応時間を５時間としたほかは、実施例１と同様にエタノールを含有した固形分２０質量％の変性セルロース（Ｃ−２）を得た。
[Example 2]
A modified cellulose (C-2) having a solid content of 20% by mass containing ethanol was obtained in the same manner as in Example 1 except that the reaction time was 5 hours.
［実施例３］
モノイソシアネートとして（Ａ−１）６０．８８ｇ（モノイソシアネートとして０．０５ｍｏｌ）を使用し、ＮＭＰを３０４．４０ｇ加えた以外は、実施例２と同様にエタノールを含有した固形分２０質量％の変性セルロース（Ｃ−３）を得た。
[Example 3]
Modification of 20% by mass of solids containing ethanol in the same manner as in Example 2 except that 60.88 g of (A-1) (0.05 mol as monoisocyanate) was used as monoisocyanate and 304.40 g of NMP was added. Cellulose (C-3) was obtained.
［実施例４］〜［実施例１０］、［比較例１］
表２に記載のモノイソシアネートに代え、モノイソシアネートの仕込み量を調整したほかは実施例２と同様に操作を行い、エタノールを含有した固形分２０質量％の各種変性セルロース（Ｃ−４）〜（Ｃ−１１）を得た。
[Example 4] to [Example 10], [Comparative Example 1]
Instead of the monoisocyanates listed in Table 2, the same procedure as in Example 2 was performed except that the amount of monoisocyanate was adjusted, and various modified celluloses (C-4) to (20% by mass) containing ethanol were added. C-11) was obtained.
［比較例２］
モノイソシアネートとしてオクタデシルイソシアネートを１４．７８ｇ（０．０５ｍｏｌ）使用し、ＮＭＰを２７７．７１ｇ加えた以外は実施例２と同様の方法により、エタノールを含有した固形分２０質量％の変性セルロース（Ｃ−１２）を得た。
[Comparative Example 2]
Modified cellulose (C--) having a solid content of 20% by mass containing ethanol by the same method as in Example 2 except that 14.78 g (0.05 mol) of octadecyl isocyanate was used as the monoisocyanate and 277.71 g of NMP was added. 12) was obtained.
［比較例３］
含水の針葉樹漂白パルプ（以下、ＮＢＫＰと略することがある。）１００ｇ（固形分３５．０ｇ）にエタノールを１４００ｇ加え、撹拌機でよく攪拌した後、ブフナー漏斗で吸引濾過を行った。この操作を３回繰り返し、エタノールで膨潤させたＮＢＫＰ１００ｇを得た。
[Comparative Example 3]
1400 g of ethanol was added to 100 g of water-containing softwood bleached pulp (hereinafter sometimes abbreviated as NBKP) (solid content: 35.0 g), and after stirring well with a stirrer, suction filtration was performed with a Buchner funnel. This operation was repeated three times to obtain 100 g of NBKP swollen with ethanol.
Ｃ−１３：未変性セルロース
［実施例１１］
実施例１で得た変性セルロース（Ｃ−１）を固形分が２８．６ｇとなるように秤量し、
エタノールを加えて３質量％のスラリーとした上で容量２０００ｍｌのビーカーへ仕込んだ。スラリーを撹拌しながら、高密度ポリエチレン樹脂（ＨＤＰＥ、住友精化（株）製：商品名「フロービーズＨＥ３０４０」）７１．４ｇとイソプロピルアルコール１６６．６ｇとを投入した。２０分間撹拌を続けた後に吸引ろ過し、ろ物をフードプロセッサーで粉砕した。その後粉砕物を容量１０００ｍｌのセパラブルフラスコへ仕込み、撹拌しながら減圧乾燥して、変性セルロース繊維と樹脂の混合物（マスターバッチ用樹脂組成物）を得た。得られたマスターバッチ用樹脂組成物を小型二軸混練機（東洋精機（株）製、商品名ラボプラストミル）に投入し、１００ｒｐｍ、１４０℃で１０分間溶融混練して樹脂成形材料を得た。得られた樹脂成形材料を手動射出成形機（井元製作所（株）製；型式１８Ｄ１）に投入し、射出温度１７０℃、金型温度２５℃で射出成形し、厚さ２ｍｍのダンベル型試験片（成形体）を得た。
[Example 11]
The modified cellulose (C-1) obtained in Example 1 was weighed so that the solid content was 28.6 g,
Ethanol was added to make a slurry of 3% by mass and charged into a beaker having a capacity of 2000 ml. While stirring the slurry, 71.4 g of high-density polyethylene resin (HDPE, manufactured by Sumitomo Seika Co., Ltd .: trade name “Flow Beads HE3040”) and 166.6 g of isopropyl alcohol were added. After stirring for 20 minutes, suction filtration was performed, and the filtrate was pulverized with a food processor. Thereafter, the pulverized product was charged into a separable flask having a volume of 1000 ml and dried under reduced pressure while stirring to obtain a mixture of modified cellulose fibers and resin (resin composition for masterbatch). The obtained masterbatch resin composition was put into a small biaxial kneader (trade name Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) and melt-kneaded at 100 rpm and 140 ° C. for 10 minutes to obtain a resin molding material. . The obtained resin molding material was put into a manual injection molding machine (manufactured by Imoto Seisakusho; Model 18D1), injection molded at an injection temperature of 170 ° C. and a mold temperature of 25 ° C., and a dumbbell-shaped test piece having a thickness of 2 mm ( Molded body) was obtained.
［実施例１２］〜［実施例２０］
表３に記載の変性セルロースに代え、高密度ポリエチレン樹脂との配合比を表３の通りに調整したほかは実施例１１と同様の操作を行い、［実施例１２］〜［実施例２０］の各成形体を得た。
[Example 12] to [Example 20]
It replaced with the modified cellulose of Table 3, and performed the same operation as Example 11 except having adjusted the compounding ratio with a high-density polyethylene resin as Table 3, and [Example 12]-[Example 20] Each molded body was obtained.
［比較例４］
変性セルロースとしてＣ−１１を固形分２２．６ｇ、高密度ポリエチレン樹脂を７７．４ｇ使用した以外は実施例１１と同様の方法によりダンベル型試験片（成形体）を得た。
[Comparative Example 4]
A dumbbell-shaped test piece (molded article) was obtained in the same manner as in Example 11 except that C-11 was used as a modified cellulose in a solid content of 22.6 g and a high-density polyethylene resin was used in 77.4 g.
［比較例５］
未変性のエタノール含有ＮＢＫＰ（Ｃ−１３）を固形分が２０．０ｇとなるように秤量し、エタノールを加えて３質量％のスラリーとした上で容量２０００ｍｌのビーカーへ仕込んだ。スラリーを撹拌しながら、高密度ポリエチレン樹脂（ＨＤＰＥ、住友精化（株）製：商品名「フロービーズＨＥ３０４０」）８０．０ｇとイソプロピルアルコール１８６．７ｇとを投入した。２０分間撹拌を続けた後に吸引ろ過し、ろ物をフードプロセッサーで粉砕した後に容量１０００ｍｌのセパラブルへ仕込み、撹拌しながら減圧乾燥して変性セルロース繊維と樹脂の混合物（マスターバッチ用樹脂組成物）を得た。得られたマスターバッチ用樹脂組成物を小型二軸混練機（東洋精機（株）製、商品名ラボプラストミル）に投入し、１００ｒｐｍ、１４０℃で１０分間溶融混練して樹脂成形材料を得た。得られた樹脂成形材料を手動射出成形機（井元製作所（株）製；型式１８Ｄ１）に投入し、射出温度１７０℃、金型温度２５℃で射出成形し、厚さ２ｍｍのダンベル型試験片（成形体）を得た。
[Comparative Example 5]
Undenatured ethanol-containing NBKP (C-13) was weighed so that the solid content was 20.0 g, and ethanol was added to form a 3% by mass slurry, which was then charged into a 2000 ml capacity beaker. While stirring the slurry, 80.0 g of high-density polyethylene resin (HDPE, manufactured by Sumitomo Seika Co., Ltd .: trade name “Flow Beads HE3040”) and 186.7 g of isopropyl alcohol were added. After stirring for 20 minutes, suction filtration is carried out, the filtrate is pulverized with a food processor, charged into a separable of 1000 ml capacity, and dried under reduced pressure with stirring to obtain a mixture of modified cellulose fibers and resin (resin composition for masterbatch). Obtained. The obtained masterbatch resin composition was put into a small biaxial kneader (trade name Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) and melt-kneaded at 100 rpm and 140 ° C. for 10 minutes to obtain a resin molding material. . The obtained resin molding material was put into a manual injection molding machine (manufactured by Imoto Seisakusho; Model 18D1), injection molded at an injection temperature of 170 ° C. and a mold temperature of 25 ° C., and a dumbbell-shaped test piece having a thickness of 2 mm ( Molded body) was obtained.
［比較例６］
未変性のエタノール含有ＮＢＫＰ（Ｃ−１３）を固形分が１０．０ｇ、高密度ポリエチレン樹脂を９０．０ｇ使用した以外は比較例５と同様の方法によりダンベル型試験片（成形体）を得た。
[Comparative Example 6]
A dumbbell-shaped test piece (molded article) was obtained in the same manner as in Comparative Example 5 except that 10.0 g of solid ethanol-containing NBKP (C-13) and 90.0 g of high-density polyethylene resin were used. .
［比較例７］
変性セルロースとしてＣ−１２を固形分３６．１ｇ、高密度ポリエチレン樹脂を６３．９ｇ使用した以外は実施例１１と同様の方法によりダンベル型試験片（成形体）を得た。
[Comparative Example 7]
A dumbbell-shaped test piece (molded body) was obtained in the same manner as in Example 11 except that 36.1 g of solid content of C-12 and 63.9 g of high-density polyethylene resin were used as the modified cellulose.
［参考例１］
高密度ポリエチレン樹脂を手動射出成形機（井元製作所（株）製；型式１８Ｄ１）に投入し、射出温度１７０℃、金型温度２５℃で射出成形し、厚さ２ｍｍのダンベル型試験片（成形体）を得た。
[Reference Example 1]
A high-density polyethylene resin is put into a manual injection molding machine (manufactured by Imoto Seisakusho; Model 18D1), injection-molded at an injection temperature of 170 ° C. and a mold temperature of 25 ° C., and a 2 mm-thick dumbbell test piece (molded body) )
［成形体の物性評価］
実施例１１〜２０、比較例４〜７、参考例１で得られた成形体の物性（ダンベル型試験片の引張強度、弾性率）を表３に示す。
[Evaluation of physical properties of molded products]
Table 3 shows the physical properties (tensile strength and elastic modulus of dumbbell-shaped test pieces) of the molded bodies obtained in Examples 11 to 20, Comparative Examples 4 to 7, and Reference Example 1.
［実施例２１］
実施例２で得た変性セルロース（Ｃ−２）を固形分が１．７ｇとなるように秤量し、エタノールを加えて３質量％のスラリーとした上で容量２０００ｍｌのビーカーへ仕込んだ。スラリーを撹拌しながら、アセタール樹脂（商品名「ユピタールＦ３０−０１Ｆ」、三菱エンジニアリングプラスチックス（株）製）９８．３ｇとイソプロピルアルコール２２９．４ｇとを投入した。２０分間撹拌を続けた後に吸引ろ過し、ろ物をフードプロセッサーで粉砕した後に容量１０００ｍｌのセパラブルフラスコへ仕込み、撹拌しながら減圧乾燥して変性セルロース繊維と樹脂の混合物（マスターバッチ用樹脂組成物）を得た。得られたマスターバッチ用樹脂組成物を小型二軸混練機（東洋精機（株）製、商品名ラボプラストミル）に投入し、７５ｒｐｍ、１８０℃で５分間溶融混練して樹脂成形材料を得た。得られた樹脂成形材料を手動射出成形機（井元製作所（株）製；型式１８Ｄ１）に投入し、射出温度１９０℃、金型温度１２０℃で射出成形し、厚さ２ｍｍのダンベル型試験片（成形体）を得た。
[Example 21]
The modified cellulose (C-2) obtained in Example 2 was weighed so as to have a solid content of 1.7 g, added with ethanol to form a 3% by mass slurry, and charged into a 2000 ml capacity beaker. While stirring the slurry, 98.3 g of acetal resin (trade name “Iupital F30-01F”, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and 229.4 g of isopropyl alcohol were added. After stirring for 20 minutes, suction filtration was performed, and the filtrate was pulverized with a food processor and then charged into a 1000 ml separable flask, dried under reduced pressure with stirring, and a mixture of modified cellulose fibers and resin (resin composition for masterbatch ) The obtained resin composition for masterbatch was put into a small biaxial kneader (trade name Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.) and melt-kneaded at 75 rpm and 180 ° C. for 5 minutes to obtain a resin molding material. . The obtained resin molding material was put into a manual injection molding machine (manufactured by Imoto Seisakusho Co., Ltd .; Model 18D1), injection molded at an injection temperature of 190 ° C. and a mold temperature of 120 ° C., and a 2 mm thick dumbbell specimen ( Molded body) was obtained.
［実施例２２、２３］
表４のように変性セルロースの種類と、樹脂／変性セルロースの組成比を変えた以外は、実施例２１と同様の方法でダンベル型試験片（成形体）を得た。
[Examples 22 and 23]
A dumbbell-shaped test piece (molded body) was obtained in the same manner as in Example 21 except that the type of modified cellulose and the resin / modified cellulose composition ratio were changed as shown in Table 4.
［参考例２］
実施例２１で用いたアセタール樹脂を手動射出成形機（井元製作所（株）製；型式１８Ｄ１）に投入し、射出温度１９０℃、金型温度１２０℃で射出成形し、厚さ２ｍｍのダンベル型試験片（成形体）を得た。
[Reference Example 2]
The acetal resin used in Example 21 was put into a manual injection molding machine (manufactured by Imoto Seisakusho; Model 18D1), injection molded at an injection temperature of 190 ° C. and a mold temperature of 120 ° C., and a dumbbell mold test having a thickness of 2 mm A piece (molded body) was obtained.
［成形体の物性評価］
実施例２１〜２３、参考例２で得られた成形体の物性（ダンベル型試験片の引張強度、弾性率）を表４に示す。
[Evaluation of physical properties of molded products]
Table 4 shows the physical properties (tensile strength and elastic modulus of dumbbell-shaped test pieces) of the molded bodies obtained in Examples 21 to 23 and Reference Example 2.
［実施例２４］
実施例２で得た変性セルロース（Ｃ−２）を固形分が８．３ｇとなるように秤量し、エタノールを加えて３質量％のスラリーとした上で容量２０００ｍｌのビーカーへ仕込んだ。スラリーを撹拌しながら、ポリアミド樹脂（商品名「ベストジント２１５９ｎａｔｕｒａｌ」、ダイセル・エボニック株式会社製）９１．４ｇとイソプロピルアルコール２２９．４ｇとを投入した。２０分間撹拌を続けた後に吸引ろ過し、ろ物をフードプロセッサーで粉砕した後に容量１０００ｍｌのセパラブルフラスコへ仕込み、撹拌しながら減圧乾燥して変性セルロース繊維と樹脂の混合物（マスターバッチ用樹脂組成物）を得た。得られたマスターバッチ用樹脂組成物を小型二軸混練機（東洋精機（株）製、商品名ラボプラストミル）に投入し、１００ｒｐｍ、１８０℃で５分間溶融混練して樹脂成形材料を得た。得られた樹脂成形材料を手動射出成形機（井元製作所（株）製；型式１８Ｄ１）に投入し、射出温度２１０℃、金型温度１２０℃で射出成形し、厚さ２ｍｍのダンベル型試験片（成形体）を得た。
[Example 24]
The modified cellulose (C-2) obtained in Example 2 was weighed so as to have a solid content of 8.3 g, added with ethanol to form a 3% by mass slurry, and charged into a 2000 ml capacity beaker. While stirring the slurry, 91.4 g of a polyamide resin (trade name “Best Ginto 2159 natural”, manufactured by Daicel Evonik Co., Ltd.) and 229.4 g of isopropyl alcohol were added. After stirring for 20 minutes, suction filtration was performed, and the filtrate was pulverized with a food processor and then charged into a 1000 ml separable flask, dried under reduced pressure with stirring, and a mixture of modified cellulose fibers and resin (resin composition for masterbatch ) The obtained resin composition for masterbatch was put into a small biaxial kneader (trade name Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.), and melt-kneaded at 100 rpm and 180 ° C. for 5 minutes to obtain a resin molding material. . The obtained resin molding material was put into a manual injection molding machine (manufactured by Imoto Seisakusho Co., Ltd .; Model 18D1), injection molded at an injection temperature of 210 ° C. and a mold temperature of 120 ° C., and a dumbbell test piece having a thickness of 2 mm ( Molded body) was obtained.
［参考例３］
ポリアミド樹脂（商品名「ベストジント２１５９ｎａｔｕｒａｌ」、ダイセル・エボニック株式会社製）を手動射出成形機（井元製作所（株）製；型式１８Ｄ１）に投入し、射出温度２１０℃、金型温度１２０℃で射出成形し、厚さ２ｍｍのダンベル型試験片（成形体）を得た。
[Reference Example 3]
Polyamide resin (trade name “Best Ginto 2159 natural”, manufactured by Daicel Evonik Co., Ltd.) is put into a manual injection molding machine (manufactured by Imoto Seisakusho Co., Ltd .; Model 18D1) and injected at an injection temperature of 210 ° C. and a mold temperature of 120 ° C. Molding was performed to obtain a dumbbell-shaped test piece (molded body) having a thickness of 2 mm.
［成形体の物性評価］
実施例２４、参考例３で得られた成形体の物性（ダンベル型試験片の引張強度、弾性率）を表５に示す。
[Evaluation of physical properties of molded products]
Table 5 shows the physical properties (tensile strength and elastic modulus of dumbbell test pieces) of the molded bodies obtained in Example 24 and Reference Example 3.
［実施例２５］
実施例７で得た変性セルロース（Ｃ−７）を固形分が２８．２ｇとなるように秤量し、
エタノールを加えて３質量％のスラリーとした上で容量２０００ｍｌのビーカーへ仕込んだ。スラリーを撹拌しながら、マレイン酸変性ポリプロピレン（ＭＰＰ：商品名「トーヨータックＰＭＡ Ｈ１０００Ｐ」、東洋紡株式会社製）８．６ｇとイソプロピルアルコール２０．４ｇとを投入した。２０分間撹拌を続けた後に吸引ろ過し、ろ物をフードプロセッサーで粉砕した後に容量１０００ｍｌのセパラブルフラスコへ仕込み、撹拌しながら減圧乾燥して変性セルロース繊維と樹脂の混合物（マスターバッチ用樹脂組成物）を得た。得られたマスターバッチ用樹脂組成物へポリプロピレン（Ｈ７００、株式会社プライムポリマー製）６３．２ｇを加え、小型二軸混練機（東洋精機（株）製、商品名ラボプラストミル）に投入し、１００ｒｐｍ、１８０℃で１０分間溶融混練して樹脂成形材料を得た。得られた樹脂成形材料を手動射出成形機（井元製作所（株）製；型式１８Ｄ１）に投入し、射出温度２００℃、金型温度２５℃で射出成形し、厚さ２ｍｍのダンベル型試験片（成形体）を得た。
[Example 25]
The modified cellulose (C-7) obtained in Example 7 was weighed so that the solid content was 28.2 g,
Ethanol was added to make a slurry of 3% by mass and charged into a beaker having a capacity of 2000 ml. While stirring the slurry, 8.6 g of maleic acid-modified polypropylene (MPP: trade name “Toyotack PMA H1000P”, manufactured by Toyobo Co., Ltd.) and 20.4 g of isopropyl alcohol were added. After stirring for 20 minutes, suction filtration was performed, and the filtrate was pulverized with a food processor and then charged into a 1000 ml separable flask, dried under reduced pressure with stirring, and a mixture of modified cellulose fibers and resin (resin composition for masterbatch ) Add 63.2 g of polypropylene (H700, manufactured by Prime Polymer Co., Ltd.) to the obtained resin composition for masterbatch, and put into a small twin-screw kneader (product name: Labo Plast Mill, manufactured by Toyo Seiki Co., Ltd.), 100 rpm The mixture was melt-kneaded at 180 ° C. for 10 minutes to obtain a resin molding material. The obtained resin molding material was put into a manual injection molding machine (manufactured by Imoto Seisakusho; Model 18D1), injection molded at an injection temperature of 200 ° C. and a mold temperature of 25 ° C., and a 2 mm thick dumbbell test piece ( Molded body) was obtained.
［参考例４］
ポリプロピレン（Ｈ７００、株式会社プライムポリマー製）を手動射出成形機（井元製作所（株）製；型式１８Ｄ１）に投入し、射出温度２００℃、金型温度２５℃で射出成形し、厚さ２ｍｍのダンベル型試験片（成形体）を得た。
[Reference Example 4]
Polypropylene (H700, manufactured by Prime Polymer Co., Ltd.) is put into a manual injection molding machine (Imoto Seisakusho Co., Ltd .; Model 18D1), injection molded at an injection temperature of 200 ° C. and a mold temperature of 25 ° C., and a 2 mm thick dumbbell A mold test piece (molded body) was obtained.
［成形体の物性評価］
実施例２５、参考例４で得られた成形体の物性（ダンベル型試験片の引張強度、弾性率）を表６に示す。
[Evaluation of physical properties of molded products]
Table 6 shows the physical properties (tensile strength and elastic modulus of dumbbell-shaped test pieces) of the molded bodies obtained in Example 25 and Reference Example 4.
MPP：トーヨータックＰＭＡ Ｈ１０００Ｐ（東洋紡株式会社製）
MPP: Toyo Tack PMA H1000P (Toyobo Co., Ltd.)
表３〜表６より、本発明の変性セルロースを用いた実施例１１〜１９、実施例２１〜２５は、それぞれ対応する樹脂のみからなる参考例１〜４や、未変性のセルロース繊維を添加した比較例５、本発明で規定されるモノイソシアネート（Ａ）以外のモノイソシアネートを用いた比較例４、比較例７に比べ、得られる樹脂成形材料から作成した樹脂成形体の引張強度と弾性率が向上していることが分かる。
また、実施例１１〜１２と実施例１３、比較例５との比較から、あるいは、実施例１６〜１８と比較例５との比較から、ＤＳ＝０．１以上の変性セルロースはＤＳ＝０．１未満の変性セルロースに比べ、得られる樹脂成形材料から作成した樹脂成形体の引張強度と弾性率がとりわけ飛躍的に向上していることが分かる。
さらに、実施例２０および未変性のセルロース繊維を添加した比較例６より、セルロース濃度が半量であっても、本発明の変性セルロースを用いた樹脂成形材料から作成した成形体は、未変性のセルロース繊維を用いた場合より高い弾性率を示していることが分かる。
加えて、実施例１１及び実施例１７と、実施例１４〜１６および実施例１８〜１９との比較から、本発明の変性セルロースに用いるモノイソシアネート（Ａ）の原料である一価アルコール（ｂ）としては、特に、炭素数３以上１８以下の分岐脂肪族アルコールの使用において優れた弾性率を示していることが分かる。
From Tables 3 to 6, Examples 11 to 19 and Examples 21 to 25 using the modified cellulose of the present invention were added with Reference Examples 1 to 4 each consisting only of the corresponding resin and unmodified cellulose fibers. Compared to Comparative Example 5 and Comparative Example 4 and Comparative Example 7 using monoisocyanates other than the monoisocyanate (A) defined in the present invention, the tensile strength and elastic modulus of the resin molded body prepared from the resin molding material obtained are It can be seen that it has improved.
Further, from the comparison between Examples 11 to 12 and Example 13 and Comparative Example 5 or from the comparison between Examples 16 to 18 and Comparative Example 5, the modified cellulose having DS = 0.1 or more has DS = 0. It can be seen that the tensile strength and elastic modulus of the resin molding produced from the resin molding material obtained are significantly improved as compared with the modified cellulose of less than 1.
Furthermore, from Example 20 and Comparative Example 6 to which unmodified cellulose fibers were added, even though the cellulose concentration was half, the molded body made from the resin molding material using the modified cellulose of the present invention was unmodified cellulose. It can be seen that the elastic modulus is higher than that when fibers are used.
In addition, from the comparison of Example 11 and Example 17 with Examples 14 to 16 and Examples 18 to 19, the monohydric alcohol (b) that is the raw material of the monoisocyanate (A) used in the modified cellulose of the present invention In particular, it can be seen that the use of a branched aliphatic alcohol having 3 to 18 carbon atoms exhibits an excellent elastic modulus.
Claims (8)
Ｏ＝Ｃ＝Ｎ−Ｘ−ＮＨＣ（＝Ｏ）Ｏ−Ｙ （１）
（ただし、Ｘは炭素数６〜２０の芳香族基、Ｙは一価アルコールの残基を表わす。） A modified cellulose obtained by reacting a monoisocyanate (A) with a cellulose fiber (B), wherein the monoisocyanate (A) has a urethane structure represented by the following general formula (1), and the monoisocyanate (A) A modified cellulose, wherein the cellulose fiber (B) has a urethane substitution degree (DS) of the hydroxyl group (A) of 0.03 to 0.50.
O = C = N-X-NHC (= O) O-Y (1)
(However, X represents an aromatic group having 6 to 20 carbon atoms, and Y represents a monohydric alcohol residue.)
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