JP2011219722A - Resin composition and molded body - Google Patents
Resin composition and molded body Download PDFInfo
- Publication number
- JP2011219722A JP2011219722A JP2010192127A JP2010192127A JP2011219722A JP 2011219722 A JP2011219722 A JP 2011219722A JP 2010192127 A JP2010192127 A JP 2010192127A JP 2010192127 A JP2010192127 A JP 2010192127A JP 2011219722 A JP2011219722 A JP 2011219722A
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- JP
- Japan
- Prior art keywords
- organic solvent
- water
- resin composition
- soluble
- insoluble
- 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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- 239000011342 resin composition Substances 0.000 title claims abstract description 67
- 229920005610 lignin Polymers 0.000 claims abstract description 55
- 239000002195 soluble material Substances 0.000 claims abstract description 42
- 239000002198 insoluble material Substances 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 12
- 125000004434 sulfur atom Chemical group 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 7
- 150000002513 isocyanates Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 19
- 235000013311 vegetables Nutrition 0.000 abstract 2
- 238000001723 curing Methods 0.000 description 31
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- 239000000047 product Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
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- 239000011347 resin Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- -1 potato Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229920001732 Lignosulfonate Polymers 0.000 description 8
- 238000004880 explosion Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000004312 hexamethylene tetramine Substances 0.000 description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
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- 229920002678 cellulose Polymers 0.000 description 5
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
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- 241000588724 Escherichia coli Species 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 244000082204 Phyllostachys viridis Species 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 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 3
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 239000005022 packaging material Substances 0.000 description 1
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- 229920002866 paraformaldehyde Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
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- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Abstract
Description
本発明は、水蒸気処理した植物原料を用いた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 resin composition and a molded body using a steam-treated plant raw material.
従来、化学製品には石油などの化石資源を原料としていたが、近年、カーボンニュートラルの概念導入によりバイオマスブラスチックの需要が高まっている。そこで、包装資材、家電製品の部材、自動車用部材など、身の回りのプラスチック製品を植物由来樹脂（バイオプラスチック）に置き換える動きが活発化している。 Conventionally, fossil resources such as petroleum have been used as raw materials for chemical products, but in recent years, demand for biomass plastics has increased due to the introduction of the concept of carbon neutral. Therefore, there is an active movement to replace plastic products around us, such as packaging materials, household appliance components, and automotive components, with plant-derived resins (bioplastics).
前記植物由来樹脂の具体例としては、ジャガイモやサトウキビやトウモロコシ等の糖質を醗酵させて得られた乳酸をモノマーとし、これを用いて化学重合を行い作製したポリ乳酸：ＰＬＡ（ＰｏｌｙＬａｃｔｉｃ Ａｃｉｄ）や、澱粉を主成分としたエステル化澱粉、微生物が体内に生産するポリエステルである微生物産生樹脂：ＰＨＡ（ＰｏｌｙＨｙｄｏｒｏｘｙ Ａｌｋａｎｏａｔｅ）、醗酵法で得られる１，３−プロパンジオールと石油由来のテレフタル酸とを原料とするＰＴＴ（Ｐｏｌｙ Ｔｒｉｍｅｔｈｙｌｅｎｅ Ｔｅｌｅｐｈｔａｌａｔｅ）等が挙げられる。
また、ＰＢＳ（Ｐｏｌｙ Ｂｕｔｙｌｅｎｅ Ｓｕｃｃｉｎａｔｅ）は、現在は石油由来の原料が用いられているが、今後においては、植物由来樹脂として作製する研究が開発されており、主原料の一つであるコハク酸を植物由来で作製する技術についての開発がなされている。
Specific examples of the plant-derived resin include polylactic acid: PLA (Polylactic Acid) produced by chemical polymerization using lactic acid obtained by fermenting sugars such as potato, sugarcane, and corn as a monomer. , Starch-based esterified starch, microorganism-produced resin that is a polyester produced by microorganisms in the body: PHA (PolyHydroxy Alkanoate), 1,3-propanediol obtained by fermentation, and petroleum-derived terephthalic acid as raw materials And PTT (Poly Trimethylene Telephthalate).
In addition, PBS (Poly Butylene Succinate) is currently used as a raw material derived from petroleum, but in the future, research to produce it as a plant-derived resin has been developed, and succinic acid, one of the main raw materials, has been developed. Developments have been made on technologies that are derived from plants.
これらの植物由来原料を用いた樹脂は、電気／電子関係用部品、ＯＡ関連用部品または自動車部品に加え、便座・台所・風呂場まわり等のサニタリー分野、雑貨、建築資材などの幅広い分野に導入されている。特に、電気／電子関係用部品、ＯＡ関連用部品または自動車部品用途では、安全上の問題から耐熱性、難燃性が要求される。また、サニタリー分野では使われている製品において細菌や黴（かび）が繁殖すると、人体に悪影響を及ぼすことが指摘されており、抗菌性を付与することが好ましい。 Resins using these plant-derived materials are introduced in a wide range of fields such as sanitary fields such as toilet seats, kitchens, and bathrooms, as well as miscellaneous goods and building materials, in addition to electrical / electronic parts, OA-related parts, and automobile parts. Has been. In particular, in electrical / electronic related parts, OA related parts, or automobile parts, heat resistance and flame retardancy are required for safety reasons. In addition, it has been pointed out that when bacteria and molds propagate in products used in the sanitary field, it has been pointed out to have an adverse effect on the human body, and it is preferable to impart antibacterial properties.
上記植物由来樹脂はいずれも熱可塑性である（非特許文献１参照）。これら熱可塑性樹脂を電気／電子関係用部品、ＯＡ関連用部品または自動車部品として用いるには高強度、耐熱性、難燃性が求められる。しかし上記植物由来樹脂はガラス転移温度が低いため、耐熱性、難燃性の面で課題が多くあった。 All the plant-derived resins are thermoplastic (see Non-Patent Document 1). In order to use these thermoplastic resins as electrical / electronic related parts, OA related parts or automobile parts, high strength, heat resistance and flame retardancy are required. However, since the plant-derived resin has a low glass transition temperature, there are many problems in terms of heat resistance and flame retardancy.
また、電気／電子関係用部品、ＯＡ関連用部品または自動車部品を製造する手法として、圧縮成形、押出し成形、射出成形が挙げられる。特に射出成形は生産性に優れた成形手法であり、成形体を大量に製造するのに適している。 Moreover, compression molding, extrusion molding, and injection molding are mentioned as a method of manufacturing the electrical / electronic related parts, the OA related parts, or the automobile parts. In particular, injection molding is a molding method with excellent productivity, and is suitable for manufacturing a large number of molded articles.
植物由来の耐熱性樹脂材料の原料としてリグニンが注目されており、生分解性樹脂材料にリグニンを添加させた複合材料が知られている。特許第４３８４９４９号公報では、セルロースとリグニン及び乳酸系樹脂からなる成形体が開示されている。また、特開２００８−３７０２２号公報では、リグノセルロース系樹脂組成物に生分解性樹脂を混練した樹脂組成物が開示されている。しかしながら、これらの複合材料では熱可塑性樹脂が複合されていることから、耐熱性が未だ十分ではなく、実用上問題を生じることがあった。 Lignin is attracting attention as a raw material for heat-resistant resin materials derived from plants, and composite materials obtained by adding lignin to biodegradable resin materials are known. Japanese Patent No. 4384949 discloses a molded body made of cellulose, lignin and a lactic acid resin. Japanese Patent Application Laid-Open No. 2008-37022 discloses a resin composition in which a biodegradable resin is kneaded with a lignocellulosic resin composition. However, in these composite materials, since the thermoplastic resin is composited, the heat resistance is not yet sufficient, which may cause problems in practice.
本発明は、環境負荷低減化の観点から、植物由来の木質系材料を利用した成形用の樹脂組成物及び成形体を提供することを目的とする。特に植物由来であるリグニンを主原料とし、耐熱性に優れ、なおかつ難燃性、抗菌性を付与した成形体を提供することにある。 An object of this invention is to provide the resin composition for shaping | molding and the molded object which utilized the woody material derived from a plant from a viewpoint of environmental load reduction. In particular, the object is to provide a molded article that uses plant-derived lignin as a main raw material, has excellent heat resistance, and imparts flame retardancy and antibacterial properties.
本発明は以下の通りである。
（１）（Ａ）水不溶物と硬化剤を含み、前記（Ａ）水不溶物の含有量が３０〜９５質量％である、樹脂組成物であって、前記（Ａ）水不溶物が、植物原料を水蒸気処理した水蒸気処理物のうち、水蒸気処理により生成した水溶性可溶物を取り除いた、リグニンを含むセルロース繊維を主成分とするものであることを特徴とする樹脂組成物。
（２）（Ｂ）有機溶剤可溶物と、（Ｃ）有機溶剤不溶物と、硬化剤を含み、前記（Ｂ）有機溶剤可溶物の含有量が５〜８０質量％であり、前記（Ｃ）有機溶剤不溶物の含有量が１０〜９０質量％である、樹脂組成物であって、前記（Ｂ）有機溶剤可溶物が、植物原料を水蒸気処理した水蒸気処理物のうち、水蒸気処理により生成した水溶性可溶物を取り除いた、リグニンを含むセルロース繊維を主成分とする（Ａ）水不溶物から有機溶剤により抽出して得た有機溶剤可溶リグニンを主成分とするものであり、前記（Ｃ）有機溶剤不溶物が、前記（Ａ）水不溶物から前記（Ｂ）有機溶剤可溶物を除いた、有機溶剤に不溶な高分子リグニンを含むセルロース繊維を主成分とするものであることを特徴とする樹脂組成物。
（３）（Ａ）水不溶物と、（Ｂ）有機溶剤可溶物と、硬化剤とを含み、前記（Ａ）水不溶物の含有量が１０〜８０質量％であり、前記（Ｂ）有機溶剤可溶物の含有量が１０〜８０質量％である、樹脂組成物であって、前記（Ａ）水不溶物が、植物原料を水蒸気処理した水蒸気処理物のうち、水蒸気処理により生成した水溶性可溶物を取り除いた、リグニンを含むセルロース繊維を主成分とするものであり、前記（Ｂ）有機溶剤可溶物が、前記（Ａ）水不溶物から有機溶剤により抽出して得た有機溶剤可溶リグニンを主成分とするものであることを特徴とする樹脂組成物。
（４）（Ａ）水不溶物又は（Ｃ）有機溶剤不溶物のセルロース繊維の平均繊維長が０．０１〜１０ｍｍであることを特徴とする（１）〜（３）のいずれかに記載の樹脂組成物。
（５）（Ａ）水不溶物、（Ｂ）有機溶剤可溶物、（Ｃ）有機溶剤不溶物のうちいずれかの硫黄原子含有率が２質量％以下である（１）〜（４）のいずれかに記載の樹脂組成物。
（６）硬化剤がエポキシ樹脂である（１）〜（５）のいずれかに記載の樹脂組成物。
（７）硬化剤がイソシアネートである（１）〜（５）のいずれかに記載の樹脂組成物。
（８）硬化剤がアルデヒド又はホルムアルデヒドを生成する化合物である（１）〜（５）のいずれかに記載の樹脂組成物。
（９）硬化剤がアクリル樹脂である（１）〜（５）のいずれかに記載の樹脂組成物。
（１０）（１）〜（９）のいずれかに記載の樹脂組成物を、圧縮、押出し、または、射出することにより成形してなる成形体。
The present invention is as follows.
(1) (A) A resin composition comprising a water insoluble matter and a curing agent, wherein the content of the (A) water insoluble matter is 30 to 95% by mass, wherein the (A) water insoluble matter is A resin composition comprising, as a main component, cellulose fibers containing lignin, from which water-soluble soluble substances generated by steam treatment are removed from steam-treated products obtained by steam-treating plant raw materials.
(2) (B) an organic solvent soluble material, (C) an organic solvent insoluble material, and a curing agent, wherein the content of the (B) organic solvent soluble material is 5 to 80% by mass, C) A resin composition having a content of organic solvent insolubles of 10 to 90% by mass, wherein the (B) organic solvent soluble material is a steam-treated water-treated product obtained by steam-treating plant raw materials. (A) The main component is an organic solvent-soluble lignin obtained by extracting from a water-insoluble material with an organic solvent, the main component being cellulose fibers containing lignin, from which water-soluble soluble matters produced by The (C) organic solvent insoluble matter is mainly composed of cellulose fibers containing a polymer lignin insoluble in an organic solvent obtained by removing the (B) organic solvent soluble matter from the (A) water insoluble matter. A resin composition characterized by the above.
(3) (A) a water-insoluble material, (B) an organic solvent-soluble material, and a curing agent, wherein the content of the (A) water-insoluble material is 10 to 80% by mass, and (B) It is a resin composition whose content of organic-solvent soluble material is 10-80 mass%, Comprising: The said (A) water insoluble matter produced | generated by the water vapor | steam processing among the water vapor processed materials which carried out the water vapor processing of the plant raw material. The main component is cellulose fiber containing lignin from which water-soluble soluble substances have been removed, and (B) the organic solvent-soluble substance is obtained by extracting the water-insoluble substance (A) with an organic solvent. A resin composition comprising an organic solvent-soluble lignin as a main component.
(4) The average fiber length of cellulose fibers of (A) water-insoluble matter or (C) organic solvent-insoluble matter is 0.01 to 10 mm, according to any one of (1) to (3) Resin composition.
(5) The sulfur atom content of any one of (A) water-insoluble matter, (B) organic solvent-soluble matter, and (C) organic solvent-insoluble matter is 2% by mass or less. The resin composition in any one.
(6) The resin composition according to any one of (1) to (5), wherein the curing agent is an epoxy resin.
(7) The resin composition according to any one of (1) to (5), wherein the curing agent is isocyanate.
(8) The resin composition according to any one of (1) to (5), wherein the curing agent is a compound that generates aldehyde or formaldehyde.
(9) The resin composition according to any one of (1) to (5), wherein the curing agent is an acrylic resin.
(10) A molded article obtained by molding the resin composition according to any one of (1) to (9) by compression, extrusion, or injection.
本発明によれば、植物由来成分を主原料としたことにより、化石資源使用量の削減、及び二酸化炭素の排出量の低減効果が得られ、また、硬化剤を用いて硬化させることにより、高いガラス転移温度を有する樹脂組成物及び成形体を提供できた。
本発明によれば、前記効果に加え難燃性に優れた樹脂組成物（植物由来成形用樹脂）を提供できた。
本発明によれば、前記効果に加え抗菌効果を付与した樹脂組成物（植物由来成形用樹脂）を提供できた。
According to the present invention, the use of plant-derived components as the main raw material provides a reduction in the use of fossil resources and the effect of reducing the amount of carbon dioxide emitted. A resin composition having a glass transition temperature and a molded article could be provided.
According to this invention, in addition to the said effect, the resin composition (plant-derived molding resin) excellent in the flame retardance could be provided.
According to the present invention, a resin composition (plant-derived molding resin) imparted with an antibacterial effect in addition to the above effects can be provided.
本発明によれば、植物原料から有効成分を取り出した後の廃棄物を大幅に低減でき、植物資源を有効に利用し、なおかつ強度に優れた樹脂組成物及び成形体を提供できた。 ADVANTAGE OF THE INVENTION According to this invention, the waste after taking out an active ingredient from a plant raw material can be reduced significantly, the plant resource was used effectively, and the resin composition and the molded object excellent in intensity | strength were able to be provided.
以下、本発明をさらに詳細に説明する。
本発明の樹脂組成物は、（Ａ）水不溶物と硬化剤を含み、前記（Ａ）水不溶物の含有量が３０〜９５質量％である、樹脂組成物であって、前記（Ａ）水不溶物が、植物原料を水蒸気処理した水蒸気処理物のうち、水蒸気処理により生成した水溶性可溶物を取り除いた、リグニンを含むセルロース繊維を主成分とするものであることを特徴とする。
植物は、一般的に、親水性の線状高分子の多糖類（セルロースとヘミセルロース）と疎水性の架橋構造リグニンの相互侵入網目（ＩＰＮ）構造を形成している。前記（Ａ）水不溶物は、植物原料を水蒸気処理した水蒸気処理物のうちセルロース成分、ヘミセルロース成分及び水蒸気処理により生成した分解物等の水溶性可溶物を取り除いた水不溶物であり、ヒドロキシフェニルプロパン単位を基本単位とする架橋構造の高分子であるリグニンを含むセルロース繊維を主成分とするものでもよい。なお、本発明において、主成分とは、通常、８０質量％以上含むことを意味し、さらに９０質量％以上含むことが好ましい。
Hereinafter, the present invention will be described in more detail.
The resin composition of the present invention is a resin composition comprising (A) a water-insoluble material and a curing agent, wherein the content of the (A) water-insoluble material is 30 to 95% by mass, The water-insoluble matter is characterized in that, among the steam-treated products obtained by steam-treating plant raw materials, the water-soluble soluble matter generated by the steam treatment is removed and the cellulose fiber containing lignin is the main component.
Plants generally form an interpenetrating network (IPN) structure of hydrophilic linear polymer polysaccharides (cellulose and hemicellulose) and a hydrophobic cross-linked lignin. The (A) water-insoluble matter is a water-insoluble matter obtained by removing water-soluble soluble substances such as a cellulose component, a hemicellulose component, and a decomposition product generated by the steam treatment from the steam-treated product obtained by steam-treating a plant raw material. The main component may be cellulose fiber containing lignin, which is a polymer having a crosslinked structure having a phenylpropane unit as a basic unit. In addition, in this invention, a main component means containing 80 mass% or more normally, and also containing 90 mass% or more is preferable.
また、本発明の樹脂組成物は、（Ｂ）有機溶剤可溶物、あるいは、（Ｃ）有機溶剤不溶物を配合してもよい。また、本発明の樹脂組成物は、必要に応じ、有機溶剤を配合してもよい。
本発明の樹脂組成物において使用される（Ｂ）有機溶剤可溶物は（Ａ）水不溶物から溶媒抽出により取り出した有機溶剤可溶成分であり、有機溶剤可溶リグニンを主成分とする。また、（Ａ）水不溶物から（Ｂ）有機溶剤可溶物を除いた成分を（Ｃ）有機溶剤不溶物とする。（Ｃ）有機溶剤不溶物は有機溶剤に不溶な高分子リグニンを含むセルロース繊維を主成分とする。図１は、本発明における、水蒸気処理物、水溶性可溶物（水可溶物）、（Ａ）水不溶物、（Ｂ）有機溶剤可溶物、（Ｃ）有機溶剤不溶物の概念を示す図である。
また、（Ｂ）有機溶剤可溶物は、有機溶剤可溶リグニンを主成分とするが、すべてが有機溶剤可溶リグニンであることが好ましい。
以下、本発明において、特に断りが無い限り、リグニンとは、高分子リグニンと有機溶剤可溶リグニンの両方を意味する。
Moreover, the resin composition of this invention may mix | blend (B) organic solvent soluble material, or (C) organic solvent insoluble material. Moreover, the resin composition of this invention may mix | blend an organic solvent as needed.
The organic solvent soluble material (B) used in the resin composition of the present invention is an organic solvent soluble component extracted from the water insoluble material (A) by solvent extraction, and contains organic solvent soluble lignin as a main component. Moreover, the component remove | excluding (B) organic solvent soluble material from (A) water insoluble material is set to (C) organic solvent insoluble material. (C) The organic solvent-insoluble material is mainly composed of cellulose fibers containing a polymer lignin that is insoluble in the organic solvent. FIG. 1 shows the concept of steam-treated product, water-soluble soluble material (water-soluble material), (A) water-insoluble material, (B) organic solvent-soluble material, and (C) organic solvent-insoluble material in the present invention. FIG.
Moreover, although (B) organic solvent soluble material has organic solvent soluble lignin as a main component, it is preferable that all are organic solvent soluble lignin.
Hereinafter, in the present invention, unless otherwise specified, lignin means both polymer lignin and organic solvent-soluble lignin.
植物原料からリグニン又は水蒸気処理物を取得する方法としては、水蒸気爆砕法が好ましい。水蒸気爆砕法は高温高圧の水蒸気による加水分解と、圧力を瞬時に開放することによる物理的破砕効果により、植物を短時間に破砕するものである。この方法は硫酸法、クラフト法など他の分離方法と比較し、硫酸、亜硫酸塩等を用いることなく、水のみを使用するので、クリーンな分離方法である。 As a method for obtaining lignin or a steam-treated product from plant materials, a steam explosion method is preferred. The steam explosion method crushes plants in a short time by hydrolysis with high-temperature and high-pressure steam and a physical crushing effect by instantaneously releasing the pressure. This method is a clean separation method because only water is used without using sulfuric acid, sulfite or the like, compared with other separation methods such as sulfuric acid method and kraft method.
水蒸気爆砕の条件は特に限定しないが、通常、植物原料を水蒸気爆砕装置用の耐圧容器に入れ、３〜４ＭＰａの水蒸気を圧入し、１〜４０分間放置した後、瞬時に圧力を開放することにより爆砕する。また、この条件は原料により大きく変化する The conditions for steam explosion are not particularly limited. Usually, by putting plant raw materials in a pressure vessel for a steam explosion apparatus, injecting 3-4 MPa of steam, leaving it for 1-40 minutes, and then immediately releasing the pressure. Explode. This condition varies greatly depending on the raw material.
この方法では、触媒等を使用せず水を用いて処理することから、リグニン中に硫黄原子をほとんど含まない（Ａ）水不溶物、（Ｂ）有機溶剤可溶物及び（Ｃ）有機溶剤不溶物が得られる。通常、（Ａ）水不溶物、（Ｂ）有機溶剤可溶物及び（Ｃ）有機溶剤不溶物中の硫黄原子の含有率は、２質量％以下が好ましく、１質量％以下であることがより好ましく、０．５質量％以下であることが特に好ましい。 In this method, since the treatment is performed using water without using a catalyst or the like, (A) water-insoluble matter, (B) organic solvent-soluble matter, and (C) organic solvent-insoluble matter containing almost no sulfur atoms in lignin. A thing is obtained. Usually, the content of sulfur atoms in (A) water-insoluble matter, (B) organic solvent-soluble matter and (C) organic solvent-insoluble matter is preferably 2% by mass or less, more preferably 1% by mass or less. Preferably, it is particularly preferably 0.5% by mass or less.
本発明で用いる（Ｂ）有機溶剤可溶物の抽出に用いる有機溶剤は、１種又は２種以上複数の混合のアルコール溶剤、アルコールと水を混合した含水アルコール溶剤、そのほかの有機溶剤、または、水と混合した含水有機溶剤を使用することができる。水にはイオン交換水を使用することが好ましい。水との混合溶剤の含水率は０質量％〜７０質量％が好ましい。また、用いる溶剤を選択することにより、得られる（Ｂ）有機溶剤可溶物の重量平均分子量を制御することが可能である。 (B) The organic solvent used for the extraction of the organic solvent-soluble matter used in the present invention is one or a mixture of two or more kinds of alcohol solvents, a hydrous alcohol solvent in which alcohol and water are mixed, other organic solvents, or A water-containing organic solvent mixed with water can be used. It is preferable to use ion exchange water as water. The water content of the mixed solvent with water is preferably 0% by mass to 70% by mass. Moreover, it is possible to control the weight average molecular weight of the (B) organic solvent soluble material obtained by selecting the solvent to be used.
（Ｂ）有機溶剤可溶物の重量平均分子量は、ポリスチレン換算値において、１００〜７０００が好ましく、さらに２００〜５０００が好ましく、５００〜４０００であることが特に好ましい。（Ｂ）有機溶剤可溶物の重量平均分子量が７０００を超えると有機溶剤への溶解性が低下する。重量平均分子量が１００未満であると有機溶剤可溶リグニンの構造を活かした樹脂組成物を得ることができない。
なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定し、標準ポリスチレン換算した値を使用した。
(B) The weight average molecular weight of the organic solvent soluble material is preferably from 100 to 7000, more preferably from 200 to 5,000, particularly preferably from 500 to 4,000 in terms of polystyrene. (B) If the weight average molecular weight of the organic solvent soluble material exceeds 7000, the solubility in the organic solvent decreases. When the weight average molecular weight is less than 100, it is not possible to obtain a resin composition utilizing the structure of organic solvent-soluble lignin.
The weight average molecular weight was measured by gel permeation chromatography (GPC), and a value converted to standard polystyrene was used.
本発明はリグニンを主原料とし、リグニンが有する複雑な化学構造を活かすことにある。植物からリグニンを取り出す際に、低分子量としてしまうと、複雑なポリフェノール構造を活かすことができず、高い耐熱性が得られない。また、リグニンが有するフェノール性水酸基及びアルコール性水酸基を利用し、硬化剤を用いて３次元架橋構造を形成することにある。これにより、高いガラス転移温度を有する樹脂材料及び成形体を得ることが可能となった。また、硫酸等を用いた処理方法により得たリグニンは水酸基がスルホン酸塩に置換されているため、硬化剤との相溶性が悪く、反応性が低下し、低剛直な骨格が得られにくい。 The present invention consists in using lignin as a main raw material and taking advantage of the complex chemical structure of lignin. When taking out lignin from a plant, if the molecular weight is low, a complicated polyphenol structure cannot be utilized, and high heat resistance cannot be obtained. Another object is to use a phenolic hydroxyl group and an alcoholic hydroxyl group possessed by lignin to form a three-dimensional crosslinked structure using a curing agent. Thereby, it became possible to obtain a resin material and a molded body having a high glass transition temperature. In addition, since the lignin obtained by a treatment method using sulfuric acid or the like has a hydroxyl group substituted with a sulfonate, the compatibility with the curing agent is poor, the reactivity is lowered, and it is difficult to obtain a low-rigid skeleton.
また、フェノール類は燃焼の際、黒鉛を形成し易いため難燃性に優れ、抗菌作用を有することが知られている。本発明は植物から得られたこの複雑な構造をそのまま活かし、樹脂原料とすることで、難燃性、抗菌性を有する樹脂組成物及び成形体を提供するものである。 In addition, phenols are known to have excellent flame retardancy and antibacterial action because they easily form graphite upon combustion. The present invention provides a resin composition and a molded article having flame retardancy and antibacterial properties by utilizing the complicated structure obtained from plants as it is and using it as a resin raw material.
リグニンの原料に特に制限は無い。例えば、スギ、竹、稲わら、麦わら、ひのき、アカシア、ヤナギ、ポプラ、バガス、とうもろこし、サトウキビ、米穀、ユーカリ、エリアンサスなどが挙げられる。 There are no particular restrictions on the raw material of lignin. Examples include cedar, bamboo, rice straw, straw, hinoki, acacia, willow, poplar, bagasse, corn, sugar cane, rice grain, eucalyptus, and Eliansus.
植物原料からリグニンを分離し取り出す方法としては、クラフト法、硫酸法、爆砕法などが挙げられる。現在多量に製造されているリグニンの多くは、紙やバイオエタノールの原料であるパルプ製造時に残渣として得られる。容易に入手可能なリグニンとしては、主に硫酸法により副生するリグニンスルホン酸塩があげられる。硫酸を用いて処理することから、リグニンスルホン酸塩は多くの硫黄原子を含んでいる。 Examples of methods for separating and taking out lignin from plant materials include kraft method, sulfuric acid method, and explosion method. Many of the lignins currently produced in large quantities are obtained as residues when producing pulp, which is a raw material for paper and bioethanol. The lignin which can be easily obtained includes lignin sulfonate which is mainly produced as a by-product by the sulfuric acid method. Since it is treated with sulfuric acid, lignin sulfonate contains many sulfur atoms.
取りだした際、リグニン以外の例えばセルロースやヘミセルロースのような成分が、多少含まれていても良い。また、これらの（Ｂ）有機溶剤可溶物をアセチル化、メチル化、ハロゲン化、ニトロ化、スルホン化、硫化ナトリウムや硫化水素との反応等によって作製されたリグニン誘導体も含む。 When taking out, components other than lignin, such as cellulose and hemicellulose, may be contained to some extent. Also included are lignin derivatives prepared by acetylation, methylation, halogenation, nitration, sulfonation, reaction with sodium sulfide or hydrogen sulfide, etc., from these (B) organic solvent soluble materials.
本発明は（Ｂ）有機溶剤可溶物を得る際に残る（Ｃ）有機溶剤不溶物を有効に利用することにある。さらに、（Ｂ）有機溶剤可溶物と（Ｃ）有機溶剤不溶物を分離する前の（Ａ）水不溶物をそのまま利用することで、製造工程を短縮できることにある。 This invention exists in utilizing effectively the (C) organic solvent insoluble matter which remains when (B) organic solvent soluble material is obtained. Furthermore, the manufacturing process can be shortened by using (A) the water-insoluble matter as it is before separating (B) the organic solvent-soluble matter and (C) the organic solvent-insoluble matter.
本発明は（Ａ）水不溶物と硬化剤を含む樹脂組成物であって、（Ａ）水不溶物が３０〜９５質量％含むことを特徴とする樹脂組成物である。（Ａ）水不溶物を、好ましくは４０〜９５質量％、また、さらに５０〜９０質量％含むことが好ましい。９５質量％を超えると成形体の強度が低下するおそれがある。また、３０質量％未満であると、化石資源使用量の削減効果、難燃性効果、抗菌性効果が得られないおそれがある。 The present invention is (A) a resin composition containing a water-insoluble material and a curing agent, wherein (A) the water-insoluble material contains 30 to 95% by mass. (A) The water-insoluble material is preferably contained in an amount of 40 to 95% by mass, and more preferably 50 to 90% by mass. If it exceeds 95% by mass, the strength of the molded product may decrease. Moreover, there exists a possibility that the reduction effect of a fossil resource usage-amount, a flame retardance effect, and an antimicrobial effect may not be acquired as it is less than 30 mass%.
本発明は（Ｂ）有機溶剤可溶物と（Ｃ）有機溶剤不溶物と硬化剤を含む樹脂組成物であって、（Ｂ）有機溶剤可溶物を５〜８０質量％、前記（Ｃ）有機溶剤不溶物を１０〜９０質量％含むことを特徴とする樹脂組成物である。（Ｂ）有機溶剤可溶物を、好ましくは１０〜８０質量％、また、さらに２０〜７０質量％含むことが好ましい。また、（Ｃ）有機溶剤不溶物を、好ましくは２０〜９０質量％、また、さらに２０〜８０質量％含むことが好ましい。（Ｂ）有機溶剤可溶物が８０質量％を超えると成形体の強度が劣化するおそれがある。また、５質量％未満であると、難燃性効果、抗菌性効果が得られないおそれがある。 The present invention is a resin composition containing (B) an organic solvent soluble material, (C) an organic solvent insoluble material, and a curing agent, wherein (B) the organic solvent soluble material is 5 to 80% by mass, It is a resin composition characterized by containing 10-90 mass% of organic solvent insolubles. (B) The organic solvent soluble material is preferably contained in an amount of 10 to 80% by mass, and further preferably 20 to 70% by mass. Moreover, (C) It is preferable that 20-90 mass% of organic solvent insoluble matter is contained, and also 20-80 mass% is included. (B) If the organic solvent-soluble matter exceeds 80% by mass, the strength of the molded article may be deteriorated. Moreover, there exists a possibility that a flame-retardant effect and an antimicrobial effect may not be acquired as it is less than 5 mass%.
本発明は（Ａ）水不溶物と（Ｂ）有機溶剤可溶物と硬化剤を含む樹脂組成物であって、（Ａ）水不溶物を１０〜８０質量％、前記（Ｂ）有機溶剤可溶物を１０〜８０質量％含むことを特徴とする樹脂組成物である。（Ａ）水不溶物を、好ましくは２０〜８０質量％、また、さらに２０〜７０質量％含むことが好ましい。また、（Ｂ）有機溶剤可溶物を、好ましくは２０〜８０質量％、また、さらに２０〜７０質量％含むことが好ましい。（Ｂ）有機溶剤可溶物が８０質量％を超えると成形体の強度が劣化するおそれがある。また、１０質量％未満であると、難燃性効果、抗菌性効果が得られないおそれがある。 The present invention is a resin composition comprising (A) a water-insoluble material, (B) an organic solvent-soluble material, and a curing agent, wherein (A) the water-insoluble material is 10 to 80% by mass, and the (B) organic solvent is acceptable. It is a resin composition characterized by containing 10-80 mass% of solutes. (A) It is preferable that a water-insoluble matter is contained preferably 20 to 80% by mass, and further 20 to 70% by mass. Moreover, (B) It is preferable that 20-80 mass% of organic solvent soluble material is contained preferably 20-70 mass%. (B) If the organic solvent-soluble matter exceeds 80% by mass, the strength of the molded article may be deteriorated. Moreover, there exists a possibility that a flame-retardant effect and an antimicrobial effect may not be acquired as it is less than 10 mass%.
本発明は（Ａ）水不溶物又は（Ｃ）有機溶剤不溶物を繊維形状とすることで、セルロース繊維強化樹脂組成物が得られ、強度に優れた樹脂組成物が得られる。セルロース繊維の平均繊維長は０．０１〜１０ｍｍが好ましく、さらに０．０５ｍｍ〜５ｍｍが好ましく、０．１〜３ｍｍであることが特に好ましい。樹脂組成物中の繊維の平均繊維長が０．０１ｍｍ未満では機械的強度が低く、１０ｍｍを超えると成形しにくくなる。
なお、セルロース繊維の平均繊維長としては、例えば、試料（水不溶物又は有機溶剤不溶物）の一定量を採取して、カヤーニＦＳ−２００自動繊維長分布測定機（バルメット オートメーション社製）により繊維本数及び数平均繊維長を測定することができる。
In the present invention, (A) a water-insoluble material or (C) an organic solvent-insoluble material is formed into a fiber shape, whereby a cellulose fiber-reinforced resin composition is obtained and a resin composition having excellent strength is obtained. The average fiber length of the cellulose fibers is preferably 0.01 to 10 mm, more preferably 0.05 mm to 5 mm, and particularly preferably 0.1 to 3 mm. If the average fiber length of the fibers in the resin composition is less than 0.01 mm, the mechanical strength is low, and if it exceeds 10 mm, molding becomes difficult.
In addition, as an average fiber length of a cellulose fiber, for example, a fixed amount of a sample (a water insoluble matter or an organic solvent insoluble matter) is collected, and a fiber is measured by a Kajaani FS-200 automatic fiber length distribution measuring machine (made by Valmet Automation). The number and number average fiber length can be measured.
本発明の樹脂組成物の構成の一つとしては、（Ａ）水不溶物、（Ｂ）有機溶剤可溶物又は（Ｃ）有機溶剤不溶物と少なくとも１種の硬化剤とからなるものでもよい。さらに所望の各種添加剤成分、硬化促進剤、粘度調整剤、離型剤、可塑剤（鉱油、シリコンオイル等）、滑剤、安定剤、酸化防止剤、紫外線吸収剤、防黴剤、無機充填材、有機充填材などを配合することもできる。また、紙粉、木粉、セルロース粉末、籾殻粉末、果実殻粉末、キチン粉末、キトサン粉末、タンパク質、澱粉等の粉末を添加しても良い。 One of the constitutions of the resin composition of the present invention may be composed of (A) a water-insoluble substance, (B) an organic solvent-soluble substance, or (C) an organic solvent-insoluble substance and at least one curing agent. . Furthermore, various desired additive components, curing accelerators, viscosity modifiers, mold release agents, plasticizers (mineral oil, silicone oil, etc.), lubricants, stabilizers, antioxidants, ultraviolet absorbers, antifungal agents, inorganic fillers Organic fillers can also be blended. Further, paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like may be added.
（Ｂ）有機溶剤可溶物の抽出に用いられる有機溶剤、又は、本発明の樹脂組成物に含まれる有機溶剤としてはアルコール、トルエン、ベンゼン、Ｎ−メチルピロリドン、メチルエチルケトン、メチルイソブチルケトン、ジエチルエーテル、メチルセロソルブ（エチレングリコールモノメチルエーテル）、シクロヘキサノン、ジメチルホルムアミド、酢酸メチル、酢酸エチル、アセトン、テトラヒドロフランなどがあり、これらは二種類以上、混合して用いることができる。 (B) Organic solvents used for extraction of organic solvent soluble materials, or organic solvents contained in the resin composition of the present invention include alcohol, toluene, benzene, N-methylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, and diethyl ether. , Methyl cellosolve (ethylene glycol monomethyl ether), cyclohexanone, dimethylformamide, methyl acetate, ethyl acetate, acetone, tetrahydrofuran, and the like, and two or more of these can be used in combination.
アルコールには、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｔｅｒｔ−ブタノール、ｎ−ヘキサノール、ベンジルアルコール、シクロヘキサノールなどのモノオール系とエチレングリコール、ジエチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、トリメチロールプロパン、グリセリン、トリエタノールアミンなどのポリオールが挙げられる。また、さらに好ましくは、天然物質から得られるアルコールであることが、環境負荷低減化の観点で好ましい。具体的には、天然物質から得たメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｔｅｒｔ−ブタノール、１，３−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、エチレングリコール、グリセリン、ヒドロキシメチルフルフラールなどが挙げられる。 Alcohols include monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, n-hexanol, benzyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol, 1,4-butanediol, , 6-hexanediol, trimethylolpropane, glycerin, triethanolamine and other polyols. Further, an alcohol obtained from a natural substance is more preferable from the viewpoint of reducing environmental load. Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, ethylene obtained from natural substances Examples include glycol, glycerin, and hydroxymethylfurfural.
本発明で用いる硬化剤としてエポキシ樹脂が挙げられる。エポキシ樹脂にはビスフェノールＡグリシジルエーテル型エポキシ、ビスフェノールＦグリシジルエーテル型エポキシ、ビスフェノールＳグリシジルエーテル型エポキシ、ビスフェノールＡＤグリシジルエーテル型エポキシ、フェノールノボラック型エポキシ、ビフェニル型エポキシ、クレゾールノボラック型エポキシがある。また、さらに天然由来物質から得られたエポキシ樹脂であることが環境負荷低減化の観点で好ましい。具体的には、エポキシ化大豆油、エポキシ化脂肪酸エステル類、エポキシ化アマニ油、ダイマー酸変性エポキシ樹脂などが挙げられる。 An epoxy resin is mentioned as a hardening | curing agent used by this invention. Epoxy resins include bisphenol A glycidyl ether type epoxy, bisphenol F glycidyl ether type epoxy, bisphenol S glycidyl ether type epoxy, bisphenol AD glycidyl ether type epoxy, phenol novolac type epoxy, biphenyl type epoxy, and cresol novolac type epoxy. Further, an epoxy resin obtained from a naturally-derived substance is preferable from the viewpoint of reducing the environmental load. Specific examples include epoxidized soybean oil, epoxidized fatty acid esters, epoxidized linseed oil, and dimer acid-modified epoxy resin.
本発明で用いる硬化剤としてイソシアネートが挙げられる。イソシアネートには、脂肪族系イソシアネート、脂環族系イソシアネートおよび芳香族系イソシアネートの他、それらの変性体が挙げられる。脂肪族系イソシアネートとしては、例えば、ヘキサメチレンジイソシアネート、リジンジイソシアネート、リジントリイソシアネート等が挙げられ、脂環族系イソシアネートとしては、例えば、イソホロンジイソシアネートが挙げられる。芳香族系イソシアネートとしては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、ポリメリックジフェニルメタンジイソシアネート、トリフェニルメタントリイソシアネート、トリス（イソシアネートフェニル）チオホスフェート等が挙げられる。イソシアネート変性体としては、例えば、ウレタンプレポリマー、ヘキサメチレンジイソシアネートビューレット、ヘキサメチレンジイソシアネートトリマー、イソホロンジイソシアネートトリマー等が挙げられる。 An isocyanate is mentioned as a hardening | curing agent used by this invention. Isocyanates include aliphatic isocyanates, alicyclic isocyanates and aromatic isocyanates, as well as modified products thereof. Examples of the aliphatic isocyanate include hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate. Examples of the alicyclic isocyanate include isophorone diisocyanate. Examples of the aromatic isocyanate include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, and the like. Examples of the modified isocyanate include urethane prepolymer, hexamethylene diisocyanate burette, hexamethylene diisocyanate trimer, and isophorone diisocyanate trimer.
本発明で用いる硬化剤としてアルデヒド又はホルムアルデヒドを生成する化合物が挙げられる。アルデヒドとしては、特に限定されず、例えば、ホルムアルデヒド、パラホルムアルデヒド、トリオキサン、アセトアルデヒド、プロピオンアルデヒド、クロラール、フルフラール、グリオキザール、ｎ−ブチルアルデヒド、カプロアルデヒド、アリルアルデヒド、ベンズアルデヒド、クロトンアルデヒド、アクロレイン、フェニルアセトアルデヒド、ｏ−トルアルデヒド、サリチルアルデヒド等が挙げられる。また、ホルムアルデヒドを生成する化合物としてはヘキサメチレンテトラミンが挙げられる。特にヘキサメチレンテトラミンが好ましい。これらを単独または２種類以上組み合わせて使用することもできる。また、硬化性、耐熱性の面からヘキサメチレンテトラミンが好ましい。 Examples of the curing agent used in the present invention include compounds that generate aldehyde or formaldehyde. The aldehyde is not particularly limited. For example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, chloral, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde , O-tolualdehyde, salicylaldehyde and the like. Moreover, hexamethylenetetramine is mentioned as a compound which produces | generates formaldehyde. Hexamethylenetetramine is particularly preferable. These may be used alone or in combination of two or more. Moreover, hexamethylenetetramine is preferable from the viewpoint of curability and heat resistance.
本発明で用いる硬化剤としてアクリル樹脂が挙げられる。アクリル樹脂としてはアクリル酸、メタクリル酸、スチレン、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸ブチル、メタクリル酸ブチル、脂肪酸ビニルエステルから選ばれる一つ以上のモノマーを単独または共重合したものが使用できる。 An acrylic resin is mentioned as a hardening | curing agent used by this invention. As the acrylic resin, one or more monomers selected from acrylic acid, methacrylic acid, styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl ester are used alone or Copolymerized products can be used.
本発明の樹脂組成物は硬化促進剤を含んでも良い。硬化促進剤としては、シクロアミジン化合物、キノン化合物、三級アミン類、有機ホスフィン類、金属塩類、１−シアノエチル−２−フェニルイミダゾール、２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、２−ヘプタデシルイミダゾール等のイミダゾール類などが挙げられる。 The resin composition of the present invention may contain a curing accelerator. Curing accelerators include cycloamidine compounds, quinone compounds, tertiary amines, organic phosphines, metal salts, 1-cyanoethyl-2-phenylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4- Examples include imidazoles such as methylimidazole and 2-heptadecylimidazole.
本発明の成形体の製造方法は特に限定しないが、前記の樹脂組成物を、圧縮、押出し、または、射出することにより成形し成形体を製造する。なお、その形状は特に限定されない。例えば、射出成形機により、本発明の樹脂組成物を、ノズル温度８０〜２００℃、射出圧力１〜３０ＭＰａ、型締圧力１〜３０ＭＰａ、金型温度５０〜２００℃、硬化時間１分〜３０分の条件で射出、成形し、さらに１００〜２５０℃で１〜８時間熱処理し、十分に硬化させる。
また、例えば、８０〜２５０℃に加熱したコンプレッション成形機の金型へ、本発明の樹脂組成物を充填し、１〜３０ＭＰａ、１分〜６０分間加圧し、硬化、成形し、さらに１００〜３００℃で１〜８時間、熱硬化処理し、十分に硬化させる。
Although the manufacturing method of the molded object of this invention is not specifically limited, The said resin composition is shape | molded by compressing, extruding, or injecting, and a molded object is manufactured. The shape is not particularly limited. For example, with an injection molding machine, the resin composition of the present invention is sprayed at a nozzle temperature of 80 to 200 ° C., an injection pressure of 1 to 30 MPa, a mold clamping pressure of 1 to 30 MPa, a mold temperature of 50 to 200 ° C., and a curing time of 1 to 30 minutes. The mixture is injected and molded under the conditions of, and further heat-treated at 100 to 250 ° C. for 1 to 8 hours to be sufficiently cured.
Further, for example, the mold of a compression molding machine heated to 80 to 250 ° C. is filled with the resin composition of the present invention, pressed for 1 to 30 MPa, 1 to 60 minutes, cured and molded, and further 100 to 300 Heat cure at 1 ° C. for 1-8 hours and fully cure.
以下、実施例により本発明を具体的に説明するが、本発明の範囲はこれらの実施例に限定されるものではない。
〔水蒸気処理〕
〔実施例１〕
植物原料として竹を使用した。適当な大きさにカットした竹材を水蒸気爆砕装置の３Ｌの耐圧容器に入れ、３．５ＭＰａの水蒸気を圧入し、４分間保持した。その後バルブを急速に開放することで爆砕処理物（水蒸気処理物）を得た。洗浄液のｐＨが６以上になるまで得られた爆砕処理物（水蒸気処理物）を水により洗浄して水溶性成分を除去した。その後、真空乾燥機で残存水分を除去し、リグニンを含むセルロース繊維を９０質量％含む、（Ａ）水不溶物を得た。
なお、前記セルロース繊維の平均繊維長を、カヤーニＦＳ−２００自動繊維長分布測定機（バルメット オートメーション社製）を用い、測定した結果、１ｍｍであった。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the scope of the present invention is not limited to these Examples.
[Steam treatment]
[Example 1]
Bamboo was used as a plant material. Bamboo material cut to an appropriate size was placed in a 3 L pressure-resistant container of a steam explosion apparatus, 3.5 MPa of steam was injected, and held for 4 minutes. Thereafter, the valve was rapidly opened to obtain an explosion-treated product (steam-treated product). The explosion-treated product (steam-treated product) obtained until the pH of the cleaning liquid reached 6 or more was washed with water to remove water-soluble components. Thereafter, residual moisture was removed with a vacuum dryer, and (A) a water-insoluble material containing 90% by mass of cellulose fibers containing lignin was obtained.
In addition, as a result of measuring the average fiber length of the said cellulose fiber using the Kajaani FS-200 automatic fiber length distribution measuring machine (made by Valmet Automation), it was 1 mm.
〔硫黄原子の含有率測定〕
前記（Ａ）水不溶物中の硫黄原子の含有率は燃焼分解−イオンクロマトグラフ法により定量した。装置は株式会社三菱化学アナリテック製自動試料燃焼装置（ＡＱＦ−１００）及び日本ダイオネクス株式会社製イオンクロマトグラフ（ＩＣＳ−１６００）を用いた。上記（Ａ）水不溶物中の硫黄原子の含有率は０．１質量％であった。
[Measurement of sulfur atom content]
The content of sulfur atoms in the water insoluble matter (A) was determined by combustion decomposition-ion chromatography. As the apparatus, an automatic sample combustion apparatus (AQF-100) manufactured by Mitsubishi Chemical Analytech Co., Ltd. and an ion chromatograph (ICS-1600) manufactured by Nippon Dionex Co., Ltd. were used. The content rate of the sulfur atom in the said (A) water insoluble matter was 0.1 mass%.
〔樹脂組成物の作製〕
前記（Ａ）水不溶物１００ｇに硬化剤としてクレゾールノボラック型エポキシ樹脂２０ｇ（ＹＤＣＮ−７００−１０、東都化成株式会社製、エポキシ当量２１０ｇ／ｅｑ．）、キュアゾール２ＰＺ−ＣＮ１．２ｇ（四国化成工業株式会社製、１−シアノエチル−２−フェニルイミダゾール）を添加し、１８０℃の加熱ロールで３分混練した。得られた半硬化物を粉砕機により平均粒子径２ｍｍの粒子（粉砕物）に粉砕し、（Ａ）水不溶物を８３質量％含む樹脂組成物を得た。
[Preparation of resin composition]
(A) 100 g of water-insoluble material, 20 g of cresol novolac type epoxy resin (YDCN-700-10, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210 g / eq.) As a curing agent, 1.2 g of Curesol 2PZ-CN (Shikoku Chemicals Co., Ltd.) 1-cyanoethyl-2-phenylimidazole) was added and kneaded with a 180 ° C. heating roll for 3 minutes. The obtained semi-cured product was pulverized into particles (pulverized product) having an average particle diameter of 2 mm by a pulverizer to obtain (A) a resin composition containing 83% by mass of a water-insoluble material.
（成形体の作製）
上記樹脂組成物を熱硬化性用射出成形機により成形した。ノズル温度１３０℃、射出圧力１３ＭＰａ、型締圧力１４ＭＰａ、金型温度１８０℃、硬化時間３分で成形体を得た。さらに２００℃で４時間処理し、十分に硬化させた。
(Production of molded body)
The resin composition was molded with a thermosetting injection molding machine. A molded body was obtained at a nozzle temperature of 130 ° C., an injection pressure of 13 MPa, a mold clamping pressure of 14 MPa, a mold temperature of 180 ° C., and a curing time of 3 minutes. Furthermore, it processed at 200 degreeC for 4 hours, and was fully hardened.
（難燃性試験）
難燃性の評価としては、ＵＬ耐炎試験規格（ＵＬ９４）に準じて行った。試験片として上記成形体を乾燥後、破砕して粉末を作製し、厚さ３ｍｍ、長さ１３０ｍｍ、幅１３ｍｍの型に充填し、１８０℃、２時間で加圧加熱成形させたものを使用した。水平燃焼試験にてＨＢレベル以上を難燃性ありとした。評価の結果、ＨＢレベルを満たしていた。
(Flame retardancy test)
The evaluation of flame retardancy was performed according to UL flame resistance test standard (UL94). The molded body was dried as a test piece, and then crushed to produce a powder. The powder was filled in a mold having a thickness of 3 mm, a length of 130 mm, and a width of 13 mm, and was subjected to pressure heating molding at 180 ° C. for 2 hours. . In the horizontal combustion test, the HB level or higher was regarded as flame retardant. As a result of the evaluation, the HB level was satisfied.
（抗菌性試験）
ＪＩＳ Ｚ２８０１に準じて、黄色ぶどう球菌、大腸菌に対する抗菌性を評価した。試験片上に菌液（生菌数２．５〜１０×１０の５乗個／ｍＬ）０．４ｍＬを播き、フィルムをかぶせ３５℃±１℃、２４時間培養した。試験片上の生菌数を測定するため、サンプリングし、サンプルを適宜希釈し、寒天平板培養にて３５℃±１℃、４８時間培養して生菌数を得た。
Ｒ＝［Ｌｏｇ（Ｂ／Ａ）−ｌｏｇ（Ｃ／Ａ）］＝［Ｌｏｇ（Ｂ／Ｃ）］
Ｒ：抗菌活性値
Ａ：無加工試験片における接種直後の生菌数の平均値（個）
Ｂ：無加工試験片における２４時間後の生菌数の平均値（個）
Ｃ：抗菌加工試験片における２４時間後の生菌数の平均値（個）
抗菌活性値２以上を抗菌性ありとした。成形体の抗菌活性値は大腸菌、黄色ブドウ球菌に対して、それぞれ３．０、２．４であった。
よって、得られた成形体は、難燃性、抗菌性ありであった。
(Antimicrobial test)
According to JIS Z2801, antibacterial activity against Staphylococcus aureus and Escherichia coli was evaluated. On the test piece, 0.4 mL of a bacterial solution (viable cells of 2.5 to 10 × 10 5 cells / mL) was inoculated, and the film was covered and cultured at 35 ° C. ± 1 ° C. for 24 hours. In order to measure the number of viable bacteria on the test piece, sampling was performed, the sample was appropriately diluted, and cultured in an agar plate culture at 35 ° C. ± 1 ° C. for 48 hours to obtain the viable cell count.
R = [Log (B / A) -log (C / A)] = [Log (B / C)]
R: antibacterial activity value A: average number of viable bacteria immediately after inoculation in unprocessed test pieces (pieces)
B: Average number of viable cells after 24 hours in unprocessed test piece
C: Average number of viable bacteria after 24 hours in antibacterial processed test piece
An antibacterial activity value of 2 or more was considered to be antibacterial. The antibacterial activity value of the molded product was 3.0 and 2.4 for Escherichia coli and Staphylococcus aureus, respectively.
Therefore, the obtained molded body was flame retardant and antibacterial.
（ガラス転移温度測定）
ＪＩＳ Ｋ７２４４に準じて、粘弾性スペクトロメータ（エスアイアイ・ナノテクノロジー株式会社製、ＥＸＳＴＡＲＤＭＳ６１００）を用いて貯蔵弾性率及び損失正接を測定し（サンプルサイズ：長さ４０ｍｍ、幅５ｍｍ、厚さ１ｍｍ、チャック間２０ｍｍ、２５℃〜３５０℃、昇温速度５℃／分、引張りモード、合成波（２Ｈｚ、１Ｈｚ、０．４Ｈｚ、０．２Ｈｚ、０．１Ｈｚ））、１Ｈｚ時の損失正接のピーク温度をガラス転移温度とした。成形体のガラス転移温度は１６５℃であった。
(Glass transition temperature measurement)
In accordance with JIS K7244, the storage elastic modulus and loss tangent were measured using a viscoelastic spectrometer (EXTARDMS 6100, manufactured by SII Nano Technology Co., Ltd.) (sample size: length 40 mm, width 5 mm, thickness 1 mm, chuck) Between 20 mm, 25 ° C. to 350 ° C., heating rate 5 ° C./min, tension mode, composite wave (2 Hz, 1 Hz, 0.4 Hz, 0.2 Hz, 0.1 Hz), peak temperature of loss tangent at 1 Hz The glass transition temperature was taken. The glass transition temperature of the molded body was 165 ° C.
〔実施例２〕
実施例１で得た（Ａ）水不溶物１０００ｇにアセトン５Ｌを加え、２０分攪拌した後、ろ過により（Ｃ）有機溶剤不溶物として有機溶剤に不溶な高分子リグニンを含むセルロース繊維を９０質量％含む繊維物質を分離した。得られた濾液から抽出溶剤（アセトン）を除去し、（Ｂ）有機溶剤可溶物として有機溶剤可溶リグニンを３００ｇ得た。得られた（Ｂ）有機溶剤可溶物（有機溶剤可溶リグニン）は常温（２５℃）で茶褐色の粉末であった。なお、実施例１と同様にして、前記セルロース繊維の平均繊維長を測定した結果、１ｍｍであった。
[Example 2]
After adding 5 L of acetone to 1000 g of (A) water-insoluble material obtained in Example 1 and stirring for 20 minutes, 90 mass of cellulose fibers containing polymer lignin insoluble in organic solvent as (C) organic solvent-insoluble material by filtration. % Fiber material was isolated. The extraction solvent (acetone) was removed from the obtained filtrate to obtain 300 g of organic solvent-soluble lignin as (B) organic solvent-soluble material. The obtained (B) organic solvent soluble material (organic solvent soluble lignin) was a brown powder at room temperature (25 ° C.). In addition, it was 1 mm as a result of measuring the average fiber length of the said cellulose fiber like Example 1. FIG.
上記で得られた（Ｂ）有機溶剤可溶物（有機溶剤可溶リグニン）の水酸基当量は無水酢酸−ピリジン法により水酸基価、電位差滴定法により酸価を測定し求めた（下記の水酸基当量及びエポキシ当量の単位は、グラム／当量であって以下ｇ／ｅｑ．で表わす。）。
アセトン抽出竹由来（Ｂ）有機溶剤可溶物の水酸基当量は１４０ｇ／ｅｑ．であった。（Ｂ）有機溶剤可溶物のフェノール性水酸基とアルコール性水酸基のモル比（以下Ｐ／Ａ比）を以下の方法で決定した。（Ｂ）有機溶剤可溶物２ｇのアセチル化処理を行い、未反応のアセチル化剤を留去し、乾燥させたものを、重クロロホルムに溶解させ、１Ｈ−ＮＭＲ（ＢＲＵＫＥＲ社製、Ｖ４００Ｍ、プロトン基本周波数４００．１３ＭＨｚ）により測定した。アセチル基由来のプロトンの積分比（フェノール性水酸基に結合したアセチル基由来：２．２〜３．０ｐｐｍ、アルコール性水酸基に結合したアセチル基由来：１．５〜２．２ｐｐｍ）からモル比を決定したところ、Ｐ／Ａ比は２．２／１．０であった。
The hydroxyl equivalent of (B) organic solvent soluble material (organic solvent soluble lignin) obtained above was determined by measuring the hydroxyl value by acetic anhydride-pyridine method and the acid value by potentiometric titration (the following hydroxyl equivalent and The unit of epoxy equivalent is gram / equivalent and is expressed in g / eq. Below).
The hydroxyl equivalent of acetone-extracted bamboo-derived (B) organic solvent solubles is 140 g / eq. Met. (B) The molar ratio of the phenolic hydroxyl group and alcoholic hydroxyl group (hereinafter referred to as P / A ratio) of the organic solvent soluble material was determined by the following method. (B) An acetylation treatment of 2 g of an organic solvent soluble material was performed, an unreacted acetylating agent was distilled off, and the dried product was dissolved in deuterated chloroform, and 1 H-NMR (manufactured by BRUKER, V400M, (Proton fundamental frequency 400.13 MHz). Determine the molar ratio from the integral ratio of protons derived from acetyl groups (derived from acetyl groups bonded to phenolic hydroxyl groups: 2.2 to 3.0 ppm, derived from acetyl groups bonded to alcoholic hydroxyl groups: 1.5 to 2.2 ppm). As a result, the P / A ratio was 2.2 / 1.0.
（有機溶剤可溶リグニンの溶剤溶解性）
溶剤溶解性としては、前記有機溶剤可溶リグニン１ｇを、有機溶剤１０ｍｌに加えて評価した。常温（２５℃）で容易に溶解した場合は○、５０〜７０℃で溶解した場合は△、加熱しても溶解しなかった場合を×として、評価した。溶剤群１としてアセトン、シクロヘキサノン、テトラヒドロフラン、溶剤群２としてメタノール、エタノール、メチルエチルケトンとして溶解性を評価した結果、溶剤群１ではいずれも○、溶剤群２ではいずれも△の判定であった。
(Solvent solubility of organic solvent soluble lignin)
The solvent solubility was evaluated by adding 1 g of the organic solvent-soluble lignin to 10 ml of the organic solvent. When it melt | dissolved easily at normal temperature (25 degreeC), it evaluated as (circle), when it melt | dissolved at 50-70 degreeC, (triangle | delta), and the case where it did not melt | dissolve even if heated was evaluated. As a result of evaluating the solubility as acetone, cyclohexanone, tetrahydrofuran as the solvent group 1 and methanol, ethanol, and methyl ethyl ketone as the solvent group 2, the solvent group 1 was evaluated as ◯ and the solvent group 2 as △.
元素分析法によって測定された上記（Ｂ）有機溶剤可溶物（有機溶剤可溶リグニン）中の硫黄原子の含有率は０．１質量％であった。さらに示差屈折計を備えたゲルパーミエイションクロマトグラフィー（ＧＰＣ）にて有機溶剤可溶リグニンの分子量を測定した。多分散度の小さいポリスチレンを標準試料として用い、移動相をテトラヒドロフランとして使用し、カラムとして株式会社日立ハイテクノロジーズ製ゲルパックＧＬ−Ａ１２０ＳとＧＬ−Ａ１７０Ｓとを直列に接続して分子量測定を行った。その重量平均分子量は２４００であった。また、（Ｃ）有機溶剤不溶物中の硫黄原子の含有率は０．１質量％であった。 The content of sulfur atoms in the organic solvent-soluble matter (B) (organic solvent-soluble lignin) measured by elemental analysis was 0.1% by mass. Furthermore, the molecular weight of the organic solvent-soluble lignin was measured by gel permeation chromatography (GPC) equipped with a differential refractometer. Polystyrene having a low polydispersity was used as a standard sample, the mobile phase was used as tetrahydrofuran, and gel packs GL-A120S and GL-A170S manufactured by Hitachi High-Technologies Corporation were connected in series as columns to perform molecular weight measurement. Its weight average molecular weight was 2400. Moreover, the content rate of the sulfur atom in (C) organic solvent insoluble matter was 0.1 mass%.
〔樹脂組成物の作製〕
前記（Ｂ）有機溶剤可溶物（有機溶剤可溶リグニン）１００ｇ、前記（Ｃ）有機溶剤不溶物（繊維物質）１００ｇに、硬化剤としてヘキサメチレンジイソシアネート（和光純薬工業株式会社）３５ｇ、硬化促進剤としてジラウリン酸ジブチルすず（ＩＶ）（和光純薬工業株式会社）２ｇを加え、７０℃加熱ロールで２分混練した。得られた半硬化物を粉砕機により平均粒子径１ｍｍの粒子（粉砕物）に粉砕し、（Ｂ）有機溶剤可溶物を４２質量％、（Ｃ）有機溶剤不溶物を４２質量％含む樹脂組成物を得た。
[Preparation of resin composition]
100 g of (B) organic solvent soluble material (organic solvent soluble lignin), 100 g of (C) organic solvent insoluble material (fiber material), 35 g of hexamethylene diisocyanate (Wako Pure Chemical Industries, Ltd.) as a curing agent, curing 2 g of dibutyltin dilaurate (IV) (Wako Pure Chemical Industries, Ltd.) was added as an accelerator and kneaded with a 70 ° C. heating roll for 2 minutes. The obtained semi-cured product is pulverized into particles (pulverized product) having an average particle diameter of 1 mm by a pulverizer, and (B) a resin containing 42% by mass of an organic solvent soluble material and (C) 42% by mass of an organic solvent insoluble material. A composition was obtained.
〔成形体の作製〕
１８０℃に加熱したコンプレッション成形機の金型へ前記に得られた樹脂組成物を充填し、１５ＭＰａ、５分加圧し、硬化させ、成形体を得た。さらに２００℃で４時間硬化処理し、十分に硬化させた。実施例１と同様にして成形体の難燃性を評価した結果ＨＢレベルを満たしていた。また、抗菌性を評価した結果、成形体の抗菌活性値は大腸菌、黄色ブドウ球菌に対して、それぞれ３．７、２．８であった。よって、得られた成形体は、難燃性、抗菌性ありであった。また、ガラス転移温度は２２０℃であった。
[Production of molded body]
A mold of a compression molding machine heated to 180 ° C. was filled with the resin composition obtained above, pressurized at 15 MPa for 5 minutes, and cured to obtain a molded body. Further, it was cured at 200 ° C. for 4 hours and sufficiently cured. As a result of evaluating the flame retardancy of the molded body in the same manner as in Example 1, the HB level was satisfied. Moreover, as a result of evaluating antibacterial properties, the antibacterial activity values of the molded products were 3.7 and 2.8 against Escherichia coli and Staphylococcus aureus, respectively. Therefore, the obtained molded body was flame retardant and antibacterial. The glass transition temperature was 220 ° C.
〔実施例３〕
〔樹脂組成物の作製〕
実施例１記載の（Ａ）水不溶物５０ｇ、実施例２記載の（Ｂ）有機溶剤可溶物１００ｇ、ヘキサメチレンテトラミンを１０ｇ、硬化促進剤として酸化マグネシウムを１ｇ、離型剤としてステアリン酸０．０５ｇを添加し、９０℃、加熱ロールで５分混練した。得られた半硬化物を粉砕機により平均粒子径２ｍｍの粒子（粉砕物）に粉砕し、（Ａ）水不溶物を３１質量％、（Ｂ）有機溶剤可溶物を６２質量％含む樹脂組成物を得た。
Example 3
[Preparation of resin composition]
50 g of (A) water-insoluble matter described in Example 1, 100 g of soluble matter in (B) organic solvent described in Example 2, 10 g of hexamethylenetetramine, 1 g of magnesium oxide as a curing accelerator, 0 stearic acid as a release agent .05 g was added and kneaded at 90 ° C. with a heating roll for 5 minutes. The obtained semi-cured product is pulverized into particles having a mean particle diameter of 2 mm (pulverized product) by a pulverizer, and (A) 31% by mass of water-insoluble material and (B) 62% by mass of organic solvent-soluble material. I got a thing.
〔成形体の作製〕
実施例１と同様の条件で成形を行った結果、良好な成形体を得た。実施例１と同様にして成形体の難燃性を評価した結果ＨＢレベルを満たしていた。また、抗菌性を評価した結果、成形体の抗菌活性値は大腸菌、黄色ブドウ球菌に対して、それぞれ５．３、４．５であった。よって、得られた成形体は、難燃性、抗菌性ありであった。ガラス転移温度は１８０℃であった。
[Production of molded body]
As a result of molding under the same conditions as in Example 1, a good molded body was obtained. As a result of evaluating the flame retardancy of the molded body in the same manner as in Example 1, the HB level was satisfied. Moreover, as a result of evaluating antibacterial properties, the antibacterial activity values of the molded products were 5.3 and 4.5 for Escherichia coli and Staphylococcus aureus, respectively. Therefore, the obtained molded body was flame retardant and antibacterial. The glass transition temperature was 180 ° C.
〔比較例１〕
（Ｂ）有機溶剤可溶物（有機溶剤可溶リグニン）リグニンの代わりにリグニンスルホン酸塩（バニレックスＮ、日本製紙株式会社製）を用いた。元素分析によって測定された上記リグニンスルホン酸塩中の硫黄原子の含有率は３質量％であった。重量平均分子量を株式会社島津製作所製高速液体クロマトグラフィー（Ｃ−Ｒ４Ａ）により測定し、標準ポリスチレンを用いた検量線により換算して求めた。移動相をＤＭＦ＋ＬｉＢｒ（０．０６ｍｏｌ／Ｌ）＋リン酸（０．０６ｍｏｌ／Ｌ）として使用し、カラムとして株式会社日立ハイテクノロジーズ製ゲルパックＧＬ−Ｓ３００ＭＤＴ−５を２つ直列に接続して分子量測定を行った。その重量平均分子量は１１０００であった。
[Comparative Example 1]
(B) Organic solvent soluble material (organic solvent soluble lignin) Lignin sulfonate (Vanilex N, manufactured by Nippon Paper Industries Co., Ltd.) was used instead of lignin. The content of sulfur atoms in the lignin sulfonate measured by elemental analysis was 3% by mass. The weight average molecular weight was measured by high performance liquid chromatography (C-R4A) manufactured by Shimadzu Corporation and calculated by a calibration curve using standard polystyrene. The mobile phase was used as DMF + LiBr (0.06 mol / L) + phosphoric acid (0.06 mol / L), and two gel packs GL-S300MDT-5 manufactured by Hitachi High-Technologies Corporation were connected in series as a column for molecular weight measurement. went. Its weight average molecular weight was 11,000.
前記リグニンスルホン酸塩２００ｇにクレゾールノボラック型エポキシ樹脂１５０ｇ（ＹＤＣＮ−７００−１０、東都化成株式会社製、エポキシ当量２１０ｇ／ｅｑ．）、キュアゾール２ＰＺ−ＣＮ２ｇ（四国化成工業株式会社製、１−シアノエチル−２−フェニルイミダゾール）を添加し、加熱ロール（温度１８０℃）で３分混練した。その結果、リグニンスルホン酸とエポキシ樹脂が相分離し、均一な樹脂組成物が得られなかった。 200 g of the above lignin sulfonate, 150 g of cresol novolak type epoxy resin (YDCN-700-10, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210 g / eq.), Curazole 2PZ-CN 2 g (manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-cyanoethyl- 2-phenylimidazole) was added and kneaded for 3 minutes with a heated roll (temperature 180 ° C.). As a result, the lignin sulfonic acid and the epoxy resin were phase-separated and a uniform resin composition could not be obtained.
〔比較例２〕
リグニンスルホン酸塩４００ｇに硬化剤としてヘキサメチレンジイソシアネート（和光純薬工業株式会社）７０ｇ、硬化促進剤としてジラウリン酸ジブチルすず（ＩＶ）（和光純薬工業株式会社）４ｇを加え、７０℃加熱ロールで２分混練した。その結果、リグニンスルホン酸とイソシアネートが相分離し、均一な樹脂組成物が得られなかった。
[Comparative Example 2]
Add 400 g of lignin sulfonate to 70 g of hexamethylene diisocyanate (Wako Pure Chemical Industries, Ltd.) as a curing agent and 4 g of dibutyltin dilaurate (IV) (Wako Pure Chemical Industries, Ltd.) as a curing accelerator, Kneaded for 2 minutes. As a result, lignin sulfonic acid and isocyanate were phase-separated and a uniform resin composition could not be obtained.
〔比較例３〕
リグニンスルホン酸塩４００ｇに硬化剤としてヘキサメチレンテトラミンを４０ｇ、硬化促進剤として酸化マグネシウムを２ｇ、離型剤としてステアリン酸０．５ｇを添加し、９０℃、加熱ロールで５分混練した。リグニンスルホン酸塩とヘキサメチレンテトラミンは反応性が悪く、良好な樹脂組成物が得られなかった。
[Comparative Example 3]
40 g of hexamethylenetetramine as a curing agent, 2 g of magnesium oxide as a curing accelerator, and 0.5 g of stearic acid as a release agent were added to 400 g of lignin sulfonate, and kneaded with a heating roll at 90 ° C. for 5 minutes. Lignin sulfonate and hexamethylenetetramine had poor reactivity, and a good resin composition could not be obtained.
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Also Published As
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| JP5652646B2 (en) | 2015-01-14 |
| JP2011218775A (en) | 2011-11-04 |
| JP2011218777A (en) | 2011-11-04 |
| JP2011219723A (en) | 2011-11-04 |
| JP5741904B2 (en) | 2015-07-01 |
| JP2011219718A (en) | 2011-11-04 |
| JP2011219728A (en) | 2011-11-04 |
| JP2011219725A (en) | 2011-11-04 |
| JP5582346B2 (en) | 2014-09-03 |
| JP2011219715A (en) | 2011-11-04 |
| JP2011219734A (en) | 2011-11-04 |
| JP5618136B2 (en) | 2014-11-05 |
| JP5861856B2 (en) | 2016-02-16 |
| JP2011219717A (en) | 2011-11-04 |
| JP5720924B2 (en) | 2015-05-20 |
| JP2011219716A (en) | 2011-11-04 |
| JP5641302B2 (en) | 2014-12-17 |
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