JP5703203B2 - Water-insoluble lignin and thermosetting resin molding material containing the same - Google Patents
Water-insoluble lignin and thermosetting resin molding material containing the same Download PDFInfo
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- JP5703203B2 JP5703203B2 JP2011266077A JP2011266077A JP5703203B2 JP 5703203 B2 JP5703203 B2 JP 5703203B2 JP 2011266077 A JP2011266077 A JP 2011266077A JP 2011266077 A JP2011266077 A JP 2011266077A JP 5703203 B2 JP5703203 B2 JP 5703203B2
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- 229920005610 lignin Polymers 0.000 title claims description 70
- 239000012778 molding material Substances 0.000 title claims description 34
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 34
- 229920005989 resin Polymers 0.000 title claims description 33
- 239000011347 resin Substances 0.000 title claims description 33
- 239000002245 particle Substances 0.000 claims description 17
- 239000005011 phenolic resin Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 241000196324 Embryophyta Species 0.000 description 13
- 238000010292 electrical insulation Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
Description
本発明は、成形材料の原料として用いた場合に、成形品に優れた耐熱性などを付与することができる水不溶性リグニン、およびそれを含有する熱硬化性樹脂成形材料に関する。 The present invention relates to a water-insoluble lignin capable of imparting excellent heat resistance and the like to a molded product when used as a raw material for the molding material, and a thermosetting resin molding material containing the same.
近年、環境保全の観点から植物由来原料のプラスチック材料への有効利用が期待されている。植物由来成分には、主としてセルロース、ヘミセルロース、リグニンなどが含まれる。このうち、リグニンは、微生物などによって分解されにくく、溶剤に不溶で、かつ不融であるため取り扱いにくいだけでなく、各種プラスチック材料との反応性に乏しい。そのため、リグニンは、プラスチック材料への有効利用という点では、これまで有用な用途が見出されていない。例えば、特許文献１にも記載のように、天然リグニンをそのままの状態で熱硬化性プラスチックの１つであるフェノール樹脂と混合しても、その成形材料は成形性が悪く、成形が困難である。 In recent years, effective use of plant-derived raw materials for plastic materials is expected from the viewpoint of environmental conservation. Plant-derived components mainly include cellulose, hemicellulose, lignin and the like. Of these, lignin is not easily decomposed by microorganisms, is insoluble in solvents, and is infusible, so that it is difficult to handle, and it has poor reactivity with various plastic materials. Therefore, lignin has not found a useful use so far in terms of effective use for plastic materials. For example, as described in Patent Document 1, even when natural lignin is mixed with a phenol resin, which is one of thermosetting plastics, as it is, the molding material has poor moldability and is difficult to mold. .
そこで、特許文献１には、リグニンと、フェノールまたはその誘導体と、アルデヒド類とを有機酸の存在下で反応させて得られるリグニン変性ノボラック型フェノール樹脂の製造方法が記載されている。 Thus, Patent Document 1 describes a method for producing a lignin-modified novolak-type phenol resin obtained by reacting lignin, phenol or a derivative thereof, and aldehydes in the presence of an organic acid.
特許文献１では、リグニンを酸分解し低分子量化して反応性を持たせ、フェノール樹脂と複合化させている。しかし、リグニンの低分子量化には、酸分解の場合は中和するなど煩雑な作業や相応の設備が必要であり、一般的には膨大なエネルギー（コスト）や大規模な設備が必要なため、低分子量化したリグニンを用いた樹脂成形材料や成形品は現実的に使用できるものではない。 In Patent Document 1, lignin is acid-decomposed to have a low molecular weight so as to have reactivity, and is combined with a phenol resin. However, lowering the molecular weight of lignin requires complicated operations such as neutralization in the case of acid decomposition and appropriate equipment, and generally requires enormous energy (cost) and large-scale equipment. In addition, a resin molding material or a molded product using lignin having a low molecular weight cannot be practically used.
さらに、特許文献２〜４には、リグニンをエポキシ化やエステル化したものなど変性リグニンを用いた樹脂組成物が記載されている。しかし、これらの樹脂組成物は、成形品とした場合に、必ずしも満足できる耐熱性、機械的強度および耐水性が得られるものではない。 Furthermore, Patent Documents 2 to 4 describe resin compositions using modified lignin such as those obtained by epoxidizing or esterifying lignin. However, these resin compositions do not always provide satisfactory heat resistance, mechanical strength and water resistance when formed into molded articles.
本発明の課題は、成形材料の原料として用いた場合に、成形品に優れた耐熱性、機械的強度、線膨張係数、電気絶縁性および耐水性を付与することができる水不溶性リグニンを提供することである。 An object of the present invention is to provide a water-insoluble lignin capable of imparting excellent heat resistance, mechanical strength, linear expansion coefficient, electrical insulation and water resistance to a molded product when used as a raw material for a molding material. That is.
本発明者らは、上記課題を解決するべく鋭意検討を行った結果、以下の構成からなる解決手段を見出し、本発明を完成するに至った。
（１）２３０μｍ以下（但し、０μｍを除く）の平均粒径を有する、水不溶性リグニン。
（２）リグニンが、草本系植物由来である、（１）に記載の水不溶性リグニン。
（３）リグニンが、Ｈ型の基本骨格を１０質量％以上の割合で含有する、（１）または（２）に記載の水不溶性リグニン。
（４）上記（１）〜（３）のいずれかの項に記載の水不溶性リグニンと熱硬化性樹脂とを含有する、熱硬化性樹脂成形材料。
（５）前記熱硬化性樹脂１００質量部に対して、前記水不溶性リグニンを１０〜３００質量部の割合で含有する、（４）に記載の熱硬化性樹脂成形材料。
（６）前記熱硬化性樹脂が、ノボラック型フェノール樹脂である、（４）または（５）に記載の熱硬化性樹脂成形材料。
（７）上記（４）〜（６）のいずれかの項に記載の熱硬化性樹脂成形材料を成形して得られる、成形品。
As a result of intensive studies to solve the above problems, the present inventors have found a solution means having the following configuration, and have completed the present invention.
(1) Water-insoluble lignin having an average particle size of 230 μm or less (excluding 0 μm).
(2) The water-insoluble lignin according to (1), wherein the lignin is derived from a herbaceous plant.
(3) The water-insoluble lignin according to (1) or (2), wherein the lignin contains an H-type basic skeleton in a proportion of 10% by mass or more.
(4) A thermosetting resin molding material containing the water-insoluble lignin according to any one of (1) to (3) and a thermosetting resin.
(5) The thermosetting resin molding material according to (4), containing 10 to 300 parts by mass of the water-insoluble lignin with respect to 100 parts by mass of the thermosetting resin.
(6) The thermosetting resin molding material according to (4) or (5), wherein the thermosetting resin is a novolac type phenol resin.
(7) A molded product obtained by molding the thermosetting resin molding material according to any one of (4) to (6) above.
本発明に係る特定の平均粒径を有する水不溶性リグニンは、成形材料の原料として用いた場合に、成形品に優れた耐熱性、機械的強度、線膨張係数、電気絶縁性および耐水性を付与することができるという効果が得られる。また、本発明の熱硬化性樹脂成形材料は、これまで殆ど廃棄処分されていたリグニンの有効利用を図ったバイオマスを含む熱硬化性樹脂成形材料であるため、環境保全にも役立つ。さらに、リグニンを低分子化することなくそのままの状態で用いることができるため、リグニンの低コストでの利用が可能になる。 The water-insoluble lignin having a specific average particle size according to the present invention imparts excellent heat resistance, mechanical strength, linear expansion coefficient, electrical insulation and water resistance to molded products when used as a raw material for molding materials. The effect that it can do is acquired. Moreover, since the thermosetting resin molding material of the present invention is a thermosetting resin molding material containing biomass in which lignin, which has been almost disposed of up to now, has been effectively used, is useful for environmental conservation. Furthermore, since the lignin can be used as it is without reducing its molecular weight, the lignin can be used at low cost.
本発明の水不溶性リグニンは、２３０μｍ以下（但し、０μｍを除く）の平均粒径を有する。 The water-insoluble lignin of the present invention has an average particle size of 230 μm or less (excluding 0 μm).
リグニンは、例えば、ソーダ法によるパルプ製造など、パルプから紙を製造する際に排出される「黒液」と称する廃液中に含まれる。リグニンの基本骨格は、主としてＧ型、Ｓ型およびＨ型が存在する。なお、式中の矢印（→）は、反応性の高い炭素原子を示す。 Lignin is contained in a waste liquid called “black liquor” that is discharged when paper is produced from pulp, for example, pulp production by a soda method. The basic skeleton of lignin mainly includes G type, S type and H type. In addition, the arrow (->) in a formula shows a highly reactive carbon atom.
一般的に、針葉樹のパルプ廃液から得られるリグニンは、Ｇ型を基本骨格とし、広葉樹のパルプ廃液から得られるリグニンは、Ｇ型およびＳ型を基本骨格とする。すなわち、木本系植物由来のリグニンは、Ｈ型を基本骨格とするリグニンを含まない。 Generally, lignin obtained from coniferous pulp waste liquor has G-type basic skeleton, and lignin obtained from hardwood pulp waste liquor has G-type and S-type basic skeleton. That is, lignin derived from woody plants does not contain lignin having H-type basic skeleton.
一方、草本系植物由来のリグニンは、Ｈ型、Ｇ型およびＳ型の全てを含み、Ｈ型を含有する点で木本系植物由来のリグニンと基本骨格が異なる。 On the other hand, herbaceous plant-derived lignin includes all of H-type, G-type and S-type, and differs in basic skeleton from wood-based plant-derived lignin in that it contains H-type.
Ｇ型がフェノール骨格部分のオルト位にメトキシ基（−ＯＣＨ3）を１つ有し、Ｓ型がオルト位にメトキシ基を２つ有しているのに対し、Ｈ型は、オルト位にメトキシ基を有していない。そのため、Ｈ型を含む草本系植物由来のリグニンは、Ｈ型を含まない木本系植物由来のリグニンよりも芳香核のオルト位の修飾が少ないため、高い反応性を有する。 The G type has one methoxy group (—OCH 3 ) at the ortho position of the phenol skeleton, and the S type has two methoxy groups at the ortho position, whereas the H type has a methoxy group at the ortho position. Does not have a group. Therefore, the herbaceous plant-derived lignin containing the H type has a higher reactivity than the lignin derived from the woody plant not containing the H type, because the ortho-position modification of the aromatic nucleus is less.
したがって、本発明に用いられるリグニンは、草本系植物由来のリグニンが好ましく、麦わら、稲わらなど由来のリグニンがより好ましい。また、本発明に用いられるリグニンは、好ましくはＨ型の基本骨格を９質量％以上、より好ましくは１０質量％以上の割合で含有する。Ｈ型の割合が多いほど、リグニンの反応性は高くなる。なお、本発明に用いられるリグニンは、草本系植物由来のリグニンに限定されるわけではなく、草本系植物由来のリグニンと木本系植物由来のリグニンとを、混合して用いてもよく、木本系植物由来のリグニンのみを用いてもよい。 Therefore, the lignin used in the present invention is preferably a lignin derived from a herbaceous plant, more preferably a lignin derived from wheat straw, rice straw or the like. The lignin used in the present invention preferably contains an H-type basic skeleton in a proportion of 9% by mass or more, more preferably 10% by mass or more. The greater the proportion of H type, the higher the lignin reactivity. Note that the lignin used in the present invention is not limited to lignin derived from a herbaceous plant, and a lignin derived from a herbaceous plant and a lignin derived from a woody plant may be used in combination. Only lignin derived from this plant may be used.
原料となるリグニンは、例えば、乾燥粉末の形態で用いられる。乾燥方法は特に限定されず、粉末化の前後いずれに行ってもよい。例えば、乾燥炉を用い、１００〜２００℃で２０分〜２時間程度乾燥すればよい。 The lignin used as a raw material is used in the form of a dry powder, for example. The drying method is not particularly limited, and may be performed before or after powdering. For example, what is necessary is just to dry for about 20 minutes-2 hours at 100-200 degreeC using a drying furnace.
リグニンの粉末化は、ボールミル、ハンマーミル、ロールミルなど通常の粉砕装置だけでなく、ジェットミル（例えば、旋回流型ジェットミル、対向型ジェットミル、壁衝突型ジェットミルなど）、オングミル、乳鉢、多段石臼型混練押出機などを用いて行ってもよい。特に本発明の水不溶性リグニンは、２３０μｍ以下の平均粒径を有するため、１段階で２３０μｍ以下の平均粒径となるように粉砕してもよく、多段階で粉砕してもよい。多段階で粉砕する場合、最初の粉砕で、例えば５００〜１０００μｍ程度に粉砕し、その後の粉砕工程で２３０μｍ以下の所望の平均粒径に微粉砕すればよい。 Lignin powdering is not limited to normal mills such as ball mills, hammer mills, roll mills, but also jet mills (eg swirling jet mills, opposed jet mills, wall impingement jet mills), ong mills, mortars, multistages You may perform using a mortar type kneading extruder. In particular, since the water-insoluble lignin of the present invention has an average particle size of 230 μm or less, it may be pulverized so as to have an average particle size of 230 μm or less in one step, or may be pulverized in multiple steps. When pulverizing in multiple stages, it may be pulverized to a desired average particle size of 230 μm or less in the subsequent pulverization step in the initial pulverization, for example, to about 500 to 1000 μm.
本発明に係る水不溶性リグニンの平均粒径が２３０μｍを超える場合、粒子が大きくなるため、耐熱性、機械的強度、電気絶縁性および耐水性が低下する傾向にある。また、平均粒径は、好ましくは２１０μｍ以下、より好ましくは１５０μｍ以下であり、好ましくは７μｍ以上、より好ましくは１０μｍ以上である。 When the average particle size of the water-insoluble lignin according to the present invention exceeds 230 μm, the particles become large, so that the heat resistance, mechanical strength, electrical insulation and water resistance tend to decrease. The average particle size is preferably 210 μm or less, more preferably 150 μm or less, preferably 7 μm or more, more preferably 10 μm or more.
さらに、本発明の熱硬化性樹脂成形材料（以下、単に「本発明の成形材料」と記載する場合がある）は、熱硬化性樹脂および上記水不溶性リグニンを含有する。 Furthermore, the thermosetting resin molding material of the present invention (hereinafter sometimes simply referred to as “the molding material of the present invention”) contains a thermosetting resin and the water-insoluble lignin.
熱硬化性樹脂は特に限定されず、例えば、ノボラック型フェノール樹脂、レゾール型フェノール樹脂、エポキシ樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂などが挙げられる。これらの中でも、ノボラック型フェノール樹脂が好ましい。熱硬化性樹脂は、単独で用いてもよく併用してもよい。 A thermosetting resin is not specifically limited, For example, a novolak type phenol resin, a resol type phenol resin, an epoxy resin, a melamine resin, a urea resin, an unsaturated polyester resin etc. are mentioned. Among these, a novolac type phenol resin is preferable. Thermosetting resins may be used alone or in combination.
本発明の成形材料に含有される熱硬化性樹脂および水不溶性リグニンの含有量は特に限定されない。例えば、熱硬化性樹脂１００質量部に対して、本発明の水不溶性リグニンは好ましくは１０〜３００質量部、より好ましくは２０〜２００質量部の割合で含有する。熱硬化性樹脂および水不溶性リグニンをこのような割合で含有すると、成形材料の粘度も上昇しにくく良好な成形性を有し、さらに得られる成形品の耐熱性、機械的強度、線膨張係数、電気絶縁性および耐水性をより向上させることができる。 The contents of the thermosetting resin and water-insoluble lignin contained in the molding material of the present invention are not particularly limited. For example, the water-insoluble lignin of the present invention is preferably contained in an amount of 10 to 300 parts by mass, more preferably 20 to 200 parts by mass with respect to 100 parts by mass of the thermosetting resin. When the thermosetting resin and the water-insoluble lignin are contained in such a ratio, the viscosity of the molding material is not easily increased, and the molding product has good moldability, and further the heat resistance, mechanical strength, linear expansion coefficient of the obtained molded product, Electrical insulation and water resistance can be further improved.
本発明の成形材料は、一般的に熱硬化性樹脂組成物に添加される充填剤（木粉、パルプなど）、硬化剤（ヘキサメチレンテトラミンなど）、着色剤、可塑剤、安定剤、離型剤（ステアリン酸亜鉛、金属石鹸など）などの添加剤を含有してもよい。添加剤の含有量は、本発明の効果を阻害しない範囲であれば特に限定されず、例えば充填剤は、熱硬化性樹脂１００質量部に対して、好ましくは１０〜３００質量部、より好ましくは２０〜２００質量部の割合で含有する。 The molding material of the present invention generally comprises a filler (wood flour, pulp, etc.), a curing agent (hexamethylenetetramine, etc.), a colorant, a plasticizer, a stabilizer, a mold release agent, which are added to the thermosetting resin composition. You may contain additives, such as an agent (zinc stearate, metal soap, etc.). The content of the additive is not particularly limited as long as the effect of the present invention is not impaired. For example, the filler is preferably 10 to 300 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the thermosetting resin. It is contained at a ratio of 20 to 200 parts by mass.
本発明の成形材料は、通常の熱硬化性樹脂と同様、トランスファ成形、圧縮成形などの一般的な成形方法によって、成形品に加工される。得られた成形品は、優れた耐熱性、機械的強度、線膨張係数、電気絶縁性および耐水性を有する。 The molding material of the present invention is processed into a molded product by a general molding method such as transfer molding or compression molding as in the case of ordinary thermosetting resins. The obtained molded product has excellent heat resistance, mechanical strength, linear expansion coefficient, electrical insulation and water resistance.
以下、実施例および比較例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples.
（調製例：水不溶性リグニンの調製）
麦わらを原料とするパルプ製造過程で生成した廃液から、草本系リグニン（Ｈ型の基本骨格を１０質量％含有）を得た。この草本系リグニンを粉砕して、２１０μｍの平均粒径を有する水不溶性リグニンを得た。
(Preparation example: Preparation of water-insoluble lignin)
A herbaceous lignin (containing 10% by mass of an H-type basic skeleton) was obtained from the waste liquid produced in the pulp production process using straw as a raw material. This herbaceous lignin was pulverized to obtain a water-insoluble lignin having an average particle diameter of 210 μm.
（実施例１）
まず、上記調製例で得られた水不溶性リグニンを、低分子化などのさらなる処理を施さずに、乳鉢を用いて１０μｍの平均粒径となるように粉砕した。次いで、この１０μｍの平均粒径を有する水不溶性リグニン１５０質量部、ノボラック型フェノール樹脂３００質量部、木粉２２５質量部、硬化剤としてヘキサメチレンテトラミン５４質量部、および内部離型剤としてステアリン酸亜鉛４．５質量部を混合し、２本ロールにて１００〜１１０℃で３分間混練して、熱硬化性樹脂成形材料を得た。
(Example 1)
First, the water-insoluble lignin obtained in the above preparation example was pulverized so as to have an average particle size of 10 μm using a mortar without further treatment such as lowering the molecular weight. Next, 150 parts by mass of water-insoluble lignin having an average particle size of 10 μm, 300 parts by mass of novolac-type phenol resin, 225 parts by mass of wood flour, 54 parts by mass of hexamethylenetetramine as a curing agent, and zinc stearate as an internal mold release agent 4.5 parts by mass were mixed and kneaded for 3 minutes at 100 to 110 ° C. with two rolls to obtain a thermosetting resin molding material.
（実施例２〜５）
水不溶性リグニンの平均粒径を、表１に記載の平均粒径となるように粉砕して用い、表１に記載の成分を表１に記載の割合で混合したこと以外は、実施例１と同様にしてそれぞれ熱硬化性樹脂成形材料を得た。
(Examples 2 to 5)
Example 1 except that the average particle size of the water-insoluble lignin was pulverized to the average particle size described in Table 1 and the components described in Table 1 were mixed in the proportions described in Table 1. Similarly, a thermosetting resin molding material was obtained.
調製例で得た草本系リグニンを粉砕して、２５０μｍの平均粒径を有する水不溶性リグニンを得た。この２５０μｍの平均粒径を有する水不溶性リグニンを用いたこと以外は、実施例１と同様にして熱硬化性樹脂成形材料を得た。 The herbaceous lignin obtained in the preparation example was pulverized to obtain a water-insoluble lignin having an average particle size of 250 μm. A thermosetting resin molding material was obtained in the same manner as in Example 1 except that this water-insoluble lignin having an average particle diameter of 250 μm was used.
実施例１〜５および比較例１で得られた成形材料を、トランスファ成形法を用いて、１７０℃で１５分の条件で成形を行い、成形品を得た。 The molding materials obtained in Examples 1 to 5 and Comparative Example 1 were molded at 170 ° C. for 15 minutes using a transfer molding method to obtain molded products.
＜成形材料の成形性評価＞
実施例１〜５および比較例１で得られた成形材料について、示差走査熱量分析（ＤＳＣ）挙動、溶融粘弾性挙動および熱重量分析（ＴＧ−ＤＴＡ）挙動を調べた。その結果、いずれの成形材料についても硬化特性に差は認められず、成形性に優れていた。
<Moldability evaluation of molding materials>
The molding materials obtained in Examples 1 to 5 and Comparative Example 1 were examined for differential scanning calorimetry (DSC) behavior, melt viscoelastic behavior and thermogravimetric analysis (TG-DTA) behavior. As a result, no difference was found in the curing characteristics of any molding material, and the moldability was excellent.
＜成形品の物性評価＞
実施例１〜５および比較例１で得られた成形材料を用いて得られた成形品について、（１）耐熱性（ガラス転移温度（Ｔｇ））、（２）耐熱性（荷重たわみ温度）、（３）機械的強度、（４）線膨張係数、（５）電気絶縁性および（６）耐水性を評価した。結果を表１に示す。
<Evaluation of physical properties of molded products>
For molded products obtained using the molding materials obtained in Examples 1 to 5 and Comparative Example 1, (1) heat resistance (glass transition temperature (Tg)), (2) heat resistance (deflection temperature under load), (3) Mechanical strength, (4) linear expansion coefficient, (5) electrical insulation and (6) water resistance were evaluated. The results are shown in Table 1.
（１）耐熱性（ガラス転移温度（Ｔｇ））
エスアイアイ・ナノテクノロジー（株）製のＤＭＳ１１０を用いて、固体動的粘弾性を測定した（周波数１Ｈｚ、昇温速度２℃／分）。固体動的粘弾性測定から得られるｔａｎδ曲線のピーク温度を、Ｔｇとした。
(1) Heat resistance (glass transition temperature (Tg))
Solid dynamic viscoelasticity was measured using a DMS110 manufactured by SII Nanotechnology (frequency 1 Hz, temperature rising rate 2 ° C./min). The peak temperature of the tan δ curve obtained from the solid dynamic viscoelasticity measurement was defined as Tg.
（２）耐熱性（荷重たわみ温度）
ＡＳＴＭ Ｄ６４８に準じて、昇温速度２℃／分、荷重１８．５ｋｇ／ｃｍ2で、標準たわみ量（０．２５ｍｍ）に到達したときの温度を測定した。
(2) Heat resistance (deflection temperature under load)
According to ASTM D648, the temperature when the standard deflection amount (0.25 mm) was reached was measured at a heating rate of 2 ° C./min and a load of 18.5 kg / cm 2 .
（３）機械的強度
ＪＩＳ Ｋ６９１１に準じて、クロスヘッド速度３ｍｍ／分およびスパン１００ｍｍにて曲げ強度を測定した。
(3) Mechanical strength In accordance with JIS K6911, the bending strength was measured at a crosshead speed of 3 mm / min and a span of 100 mm.
（４）線膨張係数
エスアイアイ・ナノテクノロジー（株）製のＴＭＡ／ＳＳ６０００を用い、窒素雰囲気下、圧縮モード、昇温速度２℃／分で熱機械分析（ＴＭＡ）を行い、得られるＴＭＡ曲線の傾きから１００℃での線膨張係数を求めた。
(4) Coefficient of linear expansion Using TMA / SS6000 manufactured by SII NanoTechnology Co., Ltd., TMA curve obtained by performing thermomechanical analysis (TMA) in a compressed atmosphere at a heating rate of 2 ° C / min in a nitrogen atmosphere The linear expansion coefficient at 100 ° C. was determined from the slope of.
（５）電気絶縁性
ＪＩＳ Ｋ６９１１に準じて、横河−Ｈｅｗｌｅｔｔ−Ｐａｃｋａｒｄ社製のＨＰ４３３９Ａを用いて体積抵抗率（Ω・ｃｍ）を測定した。
(5) Electrical insulation In accordance with JIS K6911, volume resistivity (Ω · cm) was measured using HP4339A manufactured by Yokogawa-Hewlett-Packard.
（６）耐水性
成形品の質量と、沸騰水に２時間浸漬した後の成形品の質量とを測定し、その比率によって吸水率を算出した。吸水率が低いほど水分が吸収されにくく、耐水性に優れることを示す。
(6) Water resistance The mass of the molded product and the mass of the molded product after being immersed in boiling water for 2 hours were measured, and the water absorption was calculated from the ratio. The lower the water absorption, the less water is absorbed and the better the water resistance.
表１に示すように、実施例１〜５の成形材料を用いて得られた成形品は、比較例１で得られた成形品と比べて、耐熱性、機械的強度、電気絶縁性および耐水性に優れていることがわかる。また、線膨張係数も小さいことがわかる。 As shown in Table 1, the molded products obtained using the molding materials of Examples 1 to 5 were higher in heat resistance, mechanical strength, electrical insulation and water resistance than the molded products obtained in Comparative Example 1. It turns out that it is excellent in property. Moreover, it turns out that a linear expansion coefficient is also small.
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