WO2012046482A1 - Lignin-added thermosetting resin - Google Patents
Lignin-added thermosetting resin Download PDFInfo
- Publication number
- WO2012046482A1 WO2012046482A1 PCT/JP2011/065559 JP2011065559W WO2012046482A1 WO 2012046482 A1 WO2012046482 A1 WO 2012046482A1 JP 2011065559 W JP2011065559 W JP 2011065559W WO 2012046482 A1 WO2012046482 A1 WO 2012046482A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lignin
- thermosetting resin
- added
- herbaceous
- resin
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
-
- 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
Definitions
- the present invention relates to a thermosetting resin to which lignin is added, which is useful as a biomass thermosetting resin.
- Plant-derived components mainly include cellulose, hemicellulose, lignin and the like.
- lignin has not had a useful use so far because of its indegradability by microorganisms and the like.
- it has attracted attention as an additive for thermoplastic resins and thermosetting resins.
- Patent Document 1 describes a resin composition containing a thermoplastic resin and a heat-flowable phenolized lignin.
- Patent Document 2 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.
- the thermal fluidity and reactivity of lignin are low, so that denaturation by lignin does not proceed sufficiently.
- the resulting lignin-modified resin molding material has poor moldability, and the resulting molded product also has the problem of poor mechanical strength.
- lignin As a general method of using lignin, it has been mainly used to make lignin low molecular weight so that it can be melted or solubilized in a solvent.
- low molecular weight of lignin is difficult to put into practical use because it requires large-scale equipment and a large cost.
- thermosetting resins which are one of plastic materials, have been used in a wide range of fields such as various electric fields and automobile fields.
- fields such as various electric fields and automobile fields.
- mechanical strength, heat resistance, and electrical insulation of molded products There is a need for further improvements.
- the main subject of this invention is using a lignin as it is, without providing a low molecular weight, and providing a biomass thermosetting resin.
- Another object of the present invention is to provide a thermosetting resin having improved properties such as mechanical strength, heat resistance and electrical insulation.
- thermosetting resin molded products obtained by adding herbaceous lignin to thermosetting resins, among other lignins, have mechanical strength and heat resistance.
- the inventors have found that various properties such as property and electrical insulation are improved, and have completed the present invention.
- the lignin-added thermosetting resin of the present invention contains a thermosetting resin and a herbaceous lignin.
- the present invention also provides a lignin-added thermosetting resin molded product prepared from a molding material prepared from the lignin-added thermosetting resin and molded into a predetermined shape using the molding material.
- the lignin-added thermosetting resin of the present invention has improved properties such as mechanical strength, heat resistance, and electrical insulation as compared with a normal thermosetting resin. Moreover, since the lignin-added thermosetting resin of the present invention is a biomass thermosetting resin that has been used for the effective use of lignin that has been almost discarded, it is useful for environmental conservation. In addition, since lignin can be used as it is without reducing its molecular weight, lignin can be used at low cost.
- thermosetting resin of the present invention contains a phenol resin and a herbaceous lignin as main components.
- thermosetting resin in the present invention is not particularly limited, and for example, a novolac phenol resin or a resol phenol resin can be used alone or in combination.
- other general thermosetting resins such as an epoxy resin, a melamine resin, a urea resin, and an unsaturated polyester resin can also be used.
- herbaceous lignin is particularly used as lignin.
- Lignin is generally classified into woody lignin derived from wood and herbaceous lignin derived from rice straw or wheat straw, and is contained in a waste liquid called black liquor when producing paper from pulp.
- Herbaceous lignin extracted from black liquor discharged from the pulp production process by the soda method using rice straw or wheat straw as a raw material is used as a raw material.
- Herbaceous lignin differs greatly in basic skeleton from woody lignin. That is, the basic skeleton of lignin in the waste liquid is mainly composed of G type, S type, and H type as shown in the following formula. In the formula, an arrow ( ⁇ ) indicates a highly reactive carbon atom.
- Woody lignin obtained from coniferous pulp waste liquor has G-type basic skeleton. Woody lignin obtained from hardwood pulp waste liquid has G-type and S-type basic skeletons.
- herbaceous lignin has G-type, S-type, and H-type basic skeletons, and the basic skeleton differs greatly from wood-based lignin in that it contains H-type.
- the feature of this H type is that the G type has one methoxy group and two S types in the ortho position in the phenol basic skeleton, whereas the H type has no methoxy group. . Therefore, herbaceous lignin containing H type has high reactivity because it has less modification of aromatic nuclei than woody lignin containing G type and S type.
- herbaceous lignin is preferably added in a dry powder form. Drying may be performed before or after powdering.
- the drying conditions are not particularly limited. For example, the drying may be performed in a drying furnace at 100 to 200 ° C. for about 20 minutes to 2 hours.
- the apparatus that can be used in the pulverization process is not particularly limited.
- a swirling flow jet mill, an opposed jet mill, a wall collision jet mill, and the like A jet mill, an ong mill, a mortar, a multi-stage mortar type kneading extruder and the like can be used.
- the average particle size of the herbaceous lignin is 0.1 to 1000 ⁇ m, preferably 0.1 to 500 ⁇ m.
- the particle size of the herbaceous lignin exceeds the above range, there is a possibility that a sufficient thermosetting resin modification effect cannot be obtained. On the other hand, if it is below the above range, the particles may aggregate and be unable to be dispersed well in the resin.
- thermosetting resin of the present invention 10 to 300 parts by weight, preferably 20 to 200 parts by weight of herbaceous lignin is added to 100 parts by weight of the thermosetting resin. Is good.
- the amount of herbaceous lignin exceeds the above range, the content of the thermosetting resin is relatively lowered, so that the viscosity of the resulting molding material is increased, and molding is difficult by molding methods such as transfer molding. .
- it is below the above range it may be difficult to improve the properties of the thermosetting resin such as mechanical strength, heat resistance, and electrical insulation.
- fillers, curing agents, and other additives that are added to ordinary thermosetting resin molding materials can be blended without any particular limitation.
- the filler for example, wood powder or pulp can be used.
- other additives include colorants, plasticizers, stabilizers, mold release agents (metal soaps such as zinc stearate), and the like.
- the blending amount of the filler is 10 to 300 parts by mass, preferably 20 to 200 parts by mass with respect to the total amount of the thermosetting resin and the herbaceous lignin.
- a molding material is prepared by blending various additives with the above-described lignin-added thermosetting resin, and a lignin-added thermosetting resin molded product molded into a predetermined shape using the molding material is obtained.
- the molding can be performed under the same molding conditions using a molding method similar to that of a normal thermosetting resin such as transfer molding or compression molding.
- the obtained molded article has improved characteristics such as mechanical strength such as bending strength, heat resistance, and electrical insulation.
- Example 1 Novart phenol resin molding material
- a herbaceous lignin having an average particle size of 60 ⁇ m was obtained from the waste liquid produced in the pulp manufacturing process using straw as a raw material.
- each component was mixed in the blending amounts shown in the following table. These blended components were mixed and then kneaded for 5 minutes at 100 to 110 ° C. with two rolls to obtain a lignin-added phenol resin molding material.
- Example 1 A lignin-added phenol resin molding material was obtained in the same manner as in Example 1 except that woody lignin was used instead of the herbaceous lignin. The used woody lignin is obtained by drying lignin recovered from the waste liquid produced in the pulp manufacturing process.
- Example 2 A phenol resin molding material was obtained in the same manner as in Example 1 except that herbaceous lignin was not added and each component was mixed in the blending amounts shown in the following table.
- volume resistivity In accordance with JIS K6911, volume resistivity (le ⁇ cm) was measured using HP4339A manufactured by Yokogawa-Hewlett-Packard. (6) Dielectric constant Using an impedance analyzer E4991A manufactured by Agilent Technologies, the dielectric constant at a frequency of 1 GHz was measured by a capacitance method. (7) Water resistance (water absorption) For the water absorption, the initial weight and the increase in weight after being immersed in boiling water for 2 hours were measured, and the water absorption was calculated from the ratio. These evaluation results are shown in Table 3.
- the molded product obtained using the molding material of Example 1 has substantially the same heat resistance as the molded product obtained in Comparative Example 1, but has excellent mechanical strength. I understand that. Moreover, it turns out that the molded article obtained using the molding material of Example 1 is superior also about electrical insulation and water resistance. On the other hand, when compared with the conventional phenol resin molded product obtained in Comparative Example 2, the molded product obtained in Example 1 has almost the same mechanical strength, but has heat resistance, electrical insulation and dielectric properties. It can be seen that the linear expansion coefficient is small and improved.
- Example 2 (Resol-based phenolic resin molding material) Using the same herbaceous lignin used in Example 1, this was mixed with a resole phenolic resin in a 1: 1 weight ratio in methanol, and then the methanol was removed to obtain a lignin-added phenolic resin molding material. It was. This phenolic resin molding material was molded by compression molding at 200 ° C. for 15 minutes to obtain a molded product. This molded product had high heat resistance.
- the glass transition temperature Tg of the cured product of only resole was 263 ° C.
- the Tg of the lignin-added phenol resin cured product was 267 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Provided is a lignin-added thermosetting resin such as a novolac type or resol type phenolic resin, which is a biomass thermosetting resin that contains a herbaceous lignin in the form of a dried powder and has improved characteristics such as mechanical strength, heat resistance, electric insulation and water resistance. A lignin-added thermosetting resin molded article is provided by molding the lignin-added thermosetting resin into a predetermined shape.
Description
本発明は、バイオマス熱硬化性樹脂として有用な、リグニンを添加した熱硬化性樹脂に関する。
The present invention relates to a thermosetting resin to which lignin is added, which is useful as a biomass thermosetting resin.
近年、環境保全の観点から植物由来の材料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、リグニン等が含まれる。このうち、リグニンは、微生物等による難分解性のために、これまで有用な用途を有していなかった。しかし、近年、熱可塑性樹脂や熱硬化性樹脂の添加剤として注目されている。
In recent years, effective use of plant-derived materials is expected from the viewpoint of environmental conservation. Plant-derived components mainly include cellulose, hemicellulose, lignin and the like. Among these, lignin has not had a useful use so far because of its indegradability by microorganisms and the like. However, in recent years, it has attracted attention as an additive for thermoplastic resins and thermosetting resins.
例えば、特許文献１には、熱可塑性樹脂と熱流動性のフェノール化リグニンとを含有する樹脂組成物が記載されている。また、特許文献２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。
For example, Patent Document 1 describes a resin composition containing a thermoplastic resin and a heat-flowable phenolized lignin. Patent Document 2 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.
しかしながら、各種樹脂に単にリグニンを添加しただけでは、リグニンの熱流動性と反応性が低いため、リグニンによる変性が十分進行しない。その結果、得られるリグニン変性樹脂成形材料は成形性が悪く、得られる成形品も機械的強度が悪くなるという問題があった。
However, when lignin is simply added to various resins, the thermal fluidity and reactivity of lignin are low, so that denaturation by lignin does not proceed sufficiently. As a result, the resulting lignin-modified resin molding material has poor moldability, and the resulting molded product also has the problem of poor mechanical strength.
そのため、リグニンの一般的な利用方法としては、リグニンを低分子化して溶融可能にするか、あるいは溶剤に可溶化させて用いるのが主であった。しかし、リグニンの低分子化は、大規模な設備と多大なコストが必要となるため、実用化は困難であった。
Therefore, as a general method of using lignin, it has been mainly used to make lignin low molecular weight so that it can be melted or solubilized in a solvent. However, low molecular weight of lignin is difficult to put into practical use because it requires large-scale equipment and a large cost.
一方、プラスチック材料の１つである熱硬化性樹脂は、従来から、各種電気分野、自動車分野等の幅広い分野で使用されているが、成形品の機械的強度、耐熱性、電気絶縁性等のさらなる向上が求められている。
On the other hand, thermosetting resins, which are one of plastic materials, have been used in a wide range of fields such as various electric fields and automobile fields. However, such as mechanical strength, heat resistance, and electrical insulation of molded products There is a need for further improvements.
本発明の主たる課題は、リグニンを低分子化することなくそのままの状態で利用して、バイオマス熱硬化性樹脂を提供することである。
本発明の他の課題は、機械的強度、耐熱性、電気絶縁性等の諸特性が改善された熱硬化性樹脂を提供することである。 The main subject of this invention is using a lignin as it is, without providing a low molecular weight, and providing a biomass thermosetting resin.
Another object of the present invention is to provide a thermosetting resin having improved properties such as mechanical strength, heat resistance and electrical insulation.
本発明の他の課題は、機械的強度、耐熱性、電気絶縁性等の諸特性が改善された熱硬化性樹脂を提供することである。 The main subject of this invention is using a lignin as it is, without providing a low molecular weight, and providing a biomass thermosetting resin.
Another object of the present invention is to provide a thermosetting resin having improved properties such as mechanical strength, heat resistance and electrical insulation.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、リグニンの中でも特に草本系リグニンを熱硬化性樹脂に添加して得られる熱硬化性樹脂成形品は、機械的強度、耐熱性、電気絶縁性等の諸特性が改善されることを見出し、本発明を完成するに至った。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that thermosetting resin molded products obtained by adding herbaceous lignin to thermosetting resins, among other lignins, have mechanical strength and heat resistance. The inventors have found that various properties such as property and electrical insulation are improved, and have completed the present invention.
すなわち、本発明のリグニン添加熱硬化性樹脂は、熱硬化性樹脂および草本系リグニンを含有する。
また、本発明は、上記リグニン添加熱硬化性樹脂から成形材料を作製し、この成形材料を用いて所定形状に成形したリグニン添加熱硬化性樹脂成形品を提供するものである。 That is, the lignin-added thermosetting resin of the present invention contains a thermosetting resin and a herbaceous lignin.
The present invention also provides a lignin-added thermosetting resin molded product prepared from a molding material prepared from the lignin-added thermosetting resin and molded into a predetermined shape using the molding material.
また、本発明は、上記リグニン添加熱硬化性樹脂から成形材料を作製し、この成形材料を用いて所定形状に成形したリグニン添加熱硬化性樹脂成形品を提供するものである。 That is, the lignin-added thermosetting resin of the present invention contains a thermosetting resin and a herbaceous lignin.
The present invention also provides a lignin-added thermosetting resin molded product prepared from a molding material prepared from the lignin-added thermosetting resin and molded into a predetermined shape using the molding material.
本発明のリグニン添加熱硬化性樹脂は、通常の熱硬化性樹脂に比べて、機械的強度、耐熱性、電気絶縁性等の諸特性が向上する。しかも、本発明のリグニン添加熱硬化性樹脂は、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熱硬化性樹脂であるため、環境保全にも役立つ。また、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 lignin-added thermosetting resin of the present invention has improved properties such as mechanical strength, heat resistance, and electrical insulation as compared with a normal thermosetting resin. Moreover, since the lignin-added thermosetting resin of the present invention is a biomass thermosetting resin that has been used for the effective use of lignin that has been almost discarded, it is useful for environmental conservation. In addition, since lignin can be used as it is without reducing its molecular weight, lignin can be used at low cost.
以下、本発明のリグニン添加熱硬化性樹脂を詳細に説明する。本発明の熱硬化性樹脂は、フェノール樹脂および草本系リグニンを主要構成成分とする。
Hereinafter, the lignin-added thermosetting resin of the present invention will be described in detail. The thermosetting resin of the present invention contains a phenol resin and a herbaceous lignin as main components.
本発明における熱硬化性樹脂としては、特に限定されるものではなく、例えばノボラック系フェノール樹脂またはレゾール系フェノール樹脂を単独または混合して使用することができる。また、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の他の一般的な熱硬化性樹脂も用いることができる。
The thermosetting resin in the present invention is not particularly limited, and for example, a novolac phenol resin or a resol phenol resin can be used alone or in combination. In addition, other general thermosetting resins such as an epoxy resin, a melamine resin, a urea resin, and an unsaturated polyester resin can also be used.
本発明においては、リグニンとして特に草本系リグニンを使用する。リグニンは、一般に木材由来の木本系リグニンと、稲わらや麦わら等由来の草本系リグニンに大別され、パルプから紙を製造する場合に、黒液と呼ばれる廃液に含有されるものである。
In the present invention, herbaceous lignin is particularly used as lignin. Lignin is generally classified into woody lignin derived from wood and herbaceous lignin derived from rice straw or wheat straw, and is contained in a waste liquid called black liquor when producing paper from pulp.
本発明では、稲わらや麦わら等を原料とする、ソーダ法によるパルプ製造過程から排出された黒液などから抽出した草本系リグニンを原料として使用する。草本系リグニンは木本系リグニンと基本骨格が大きく異なる。すなわち、廃液中のリグニンの基本骨格は、主として以下の式に示すように、Ｇ型、Ｓ型、Ｈ型からなる。なお、式中、矢印（→）は反応性の高い炭素原子を示す。
Ｇ型：
Ｓ型：
Ｈ型：
In the present invention, herbaceous lignin extracted from black liquor discharged from the pulp production process by the soda method using rice straw or wheat straw as a raw material is used as a raw material. Herbaceous lignin differs greatly in basic skeleton from woody lignin. That is, the basic skeleton of lignin in the waste liquid is mainly composed of G type, S type, and H type as shown in the following formula. In the formula, an arrow (→) indicates a highly reactive carbon atom.
G type:
S type:
Type H:
Ｇ型：
G type:
針葉樹のパルプ廃液から得られる木本系リグニンは、Ｇ型を基本骨格とする。広葉樹のパルプ廃液から得られる木本系リグニンは、Ｇ型とＳ型を基本骨格とする。
Woody lignin obtained from coniferous pulp waste liquor has G-type basic skeleton. Woody lignin obtained from hardwood pulp waste liquid has G-type and S-type basic skeletons.
これに対して、草本系リグニンは、Ｇ型、Ｓ型およびＨ型を基本骨格とし、Ｈ型を含有する点で木本系リグニンと基本骨格が大きく異なる。
このＨ型の特徴は、Ｇ型がフェノール基本骨格中のオルソ位にメトキシ基を１つ、Ｓ型が２つ有しているのに対して、Ｈ型にはメトキシ基が存在しないことである。そのため、Ｈ型を含む草本系リグニンは、Ｇ型、Ｓ型を含む木本系リグニンと比較して、芳香核の修飾が少ないため、高い反応性を有する。 In contrast, herbaceous lignin has G-type, S-type, and H-type basic skeletons, and the basic skeleton differs greatly from wood-based lignin in that it contains H-type.
The feature of this H type is that the G type has one methoxy group and two S types in the ortho position in the phenol basic skeleton, whereas the H type has no methoxy group. . Therefore, herbaceous lignin containing H type has high reactivity because it has less modification of aromatic nuclei than woody lignin containing G type and S type.
このＨ型の特徴は、Ｇ型がフェノール基本骨格中のオルソ位にメトキシ基を１つ、Ｓ型が２つ有しているのに対して、Ｈ型にはメトキシ基が存在しないことである。そのため、Ｈ型を含む草本系リグニンは、Ｇ型、Ｓ型を含む木本系リグニンと比較して、芳香核の修飾が少ないため、高い反応性を有する。 In contrast, herbaceous lignin has G-type, S-type, and H-type basic skeletons, and the basic skeleton differs greatly from wood-based lignin in that it contains H-type.
The feature of this H type is that the G type has one methoxy group and two S types in the ortho position in the phenol basic skeleton, whereas the H type has no methoxy group. . Therefore, herbaceous lignin containing H type has high reactivity because it has less modification of aromatic nuclei than woody lignin containing G type and S type.
また、草本系リグニンは、乾燥した粉末形態で添加するのがよい。乾燥は、粉末化の前後いずれであってもよい。乾燥条件は特に限定されないが、例えば乾燥炉で１００～２００℃で２０分～２時間程度、乾燥を行えばよい。
Also, herbaceous lignin is preferably added in a dry powder form. Drying may be performed before or after powdering. The drying conditions are not particularly limited. For example, the drying may be performed in a drying furnace at 100 to 200 ° C. for about 20 minutes to 2 hours.
草本系リグニンの粉末化は、例えばボールミルなどで所定の粒度に粉砕すればよい。粉末化工程において用いることができる装置としては特に限定されないが、例えば、ボールミル、ハンマーミル、ロールミルなどの通常の粉砕装置のほか、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のジェットミル、オングミル、乳鉢、多段石臼型混練押出機などを用いることができる。
草本系リグニンの平均粒径は、０．１～１０００μm、好ましくは０．１～５００μmであるのがよい。草本系リグニンの粒度が上記範囲を超える場合は、充分な熱硬化性樹脂の改質効果が得られないおそれがある。一方、上記範囲を下回る場合は、粒子が凝集して樹脂中にうまく分散できない可能性がある。 What is necessary is just to grind | pulverize herbaceous lignin to a predetermined particle size, for example with a ball mill etc. The apparatus that can be used in the pulverization process is not particularly limited. For example, in addition to ordinary pulverization apparatuses such as a ball mill, a hammer mill, and a roll mill, a swirling flow jet mill, an opposed jet mill, a wall collision jet mill, and the like A jet mill, an ong mill, a mortar, a multi-stage mortar type kneading extruder and the like can be used.
The average particle size of the herbaceous lignin is 0.1 to 1000 μm, preferably 0.1 to 500 μm. When the particle size of the herbaceous lignin exceeds the above range, there is a possibility that a sufficient thermosetting resin modification effect cannot be obtained. On the other hand, if it is below the above range, the particles may aggregate and be unable to be dispersed well in the resin.
草本系リグニンの平均粒径は、０．１～１０００μm、好ましくは０．１～５００μmであるのがよい。草本系リグニンの粒度が上記範囲を超える場合は、充分な熱硬化性樹脂の改質効果が得られないおそれがある。一方、上記範囲を下回る場合は、粒子が凝集して樹脂中にうまく分散できない可能性がある。 What is necessary is just to grind | pulverize herbaceous lignin to a predetermined particle size, for example with a ball mill etc. The apparatus that can be used in the pulverization process is not particularly limited. For example, in addition to ordinary pulverization apparatuses such as a ball mill, a hammer mill, and a roll mill, a swirling flow jet mill, an opposed jet mill, a wall collision jet mill, and the like A jet mill, an ong mill, a mortar, a multi-stage mortar type kneading extruder and the like can be used.
The average particle size of the herbaceous lignin is 0.1 to 1000 μm, preferably 0.1 to 500 μm. When the particle size of the herbaceous lignin exceeds the above range, there is a possibility that a sufficient thermosetting resin modification effect cannot be obtained. On the other hand, if it is below the above range, the particles may aggregate and be unable to be dispersed well in the resin.
次に、本発明のリグニン添加熱硬化性樹脂を製造するにあたっては、熱硬化性樹脂１００質量部に対して、草本系リグニンを１０～３００質量部、好ましくは２０～２００質量部を添加するのがよい。
草本系リグニンの添加量が上記範囲を超える場合は、熱硬化性樹脂の含有量が相対的に低下するので、得られる成形材料の粘度が上昇し、トランスファ成形などの成形法では成形が難しくなる。一方、上記範囲を下回る場合は機械的強度、耐熱性、電気絶縁性といった熱硬化性樹脂のもつ特性を改善することが困難になるおそれがある。 Next, in producing the lignin-added thermosetting resin of the present invention, 10 to 300 parts by weight, preferably 20 to 200 parts by weight of herbaceous lignin is added to 100 parts by weight of the thermosetting resin. Is good.
When the amount of herbaceous lignin exceeds the above range, the content of the thermosetting resin is relatively lowered, so that the viscosity of the resulting molding material is increased, and molding is difficult by molding methods such as transfer molding. . On the other hand, if it is below the above range, it may be difficult to improve the properties of the thermosetting resin such as mechanical strength, heat resistance, and electrical insulation.
草本系リグニンの添加量が上記範囲を超える場合は、熱硬化性樹脂の含有量が相対的に低下するので、得られる成形材料の粘度が上昇し、トランスファ成形などの成形法では成形が難しくなる。一方、上記範囲を下回る場合は機械的強度、耐熱性、電気絶縁性といった熱硬化性樹脂のもつ特性を改善することが困難になるおそれがある。 Next, in producing the lignin-added thermosetting resin of the present invention, 10 to 300 parts by weight, preferably 20 to 200 parts by weight of herbaceous lignin is added to 100 parts by weight of the thermosetting resin. Is good.
When the amount of herbaceous lignin exceeds the above range, the content of the thermosetting resin is relatively lowered, so that the viscosity of the resulting molding material is increased, and molding is difficult by molding methods such as transfer molding. . On the other hand, if it is below the above range, it may be difficult to improve the properties of the thermosetting resin such as mechanical strength, heat resistance, and electrical insulation.
草本系リグニンに加えて、さらに通常の熱硬化性樹脂成形材料に添加される充填剤、硬化剤、その他の添加剤を特別な制限なく配合することができる。
充填剤としては、例えば木粉、パルプなどを用いることができる。その他の添加剤としては、例えば、着色剤、可塑剤、安定剤、離型剤（ステアリン酸亜鉛などの金属石鹸）などが挙げられる。
前記充填剤の配合量は、熱硬化性樹脂および草本系リグニンの総量に対して１０～３００質量部、好ましくは２０～２００質量部であるのがよい。 In addition to the herbaceous lignin, fillers, curing agents, and other additives that are added to ordinary thermosetting resin molding materials can be blended without any particular limitation.
As the filler, for example, wood powder or pulp can be used. Examples of other additives include colorants, plasticizers, stabilizers, mold release agents (metal soaps such as zinc stearate), and the like.
The blending amount of the filler is 10 to 300 parts by mass, preferably 20 to 200 parts by mass with respect to the total amount of the thermosetting resin and the herbaceous lignin.
充填剤としては、例えば木粉、パルプなどを用いることができる。その他の添加剤としては、例えば、着色剤、可塑剤、安定剤、離型剤（ステアリン酸亜鉛などの金属石鹸）などが挙げられる。
前記充填剤の配合量は、熱硬化性樹脂および草本系リグニンの総量に対して１０～３００質量部、好ましくは２０～２００質量部であるのがよい。 In addition to the herbaceous lignin, fillers, curing agents, and other additives that are added to ordinary thermosetting resin molding materials can be blended without any particular limitation.
As the filler, for example, wood powder or pulp can be used. Examples of other additives include colorants, plasticizers, stabilizers, mold release agents (metal soaps such as zinc stearate), and the like.
The blending amount of the filler is 10 to 300 parts by mass, preferably 20 to 200 parts by mass with respect to the total amount of the thermosetting resin and the herbaceous lignin.
本発明おいては、前記したリグニン添加熱硬化性樹脂に各種添加剤を配合して成形材料を作製し、この成形材料を用いて所定形状に成形されたリグニン添加熱硬化性樹脂成形品を得る。成形は、例えばトランスファ成形や圧縮成形のような通常の熱硬化性樹脂と同様な成形方法を用いて同様な成形条件で成形することができる。そして、得られた成形品は、曲げ強度などの機械的強度、耐熱性、電気絶縁性等の諸特性が向上している。
In the present invention, a molding material is prepared by blending various additives with the above-described lignin-added thermosetting resin, and a lignin-added thermosetting resin molded product molded into a predetermined shape using the molding material is obtained. . The molding can be performed under the same molding conditions using a molding method similar to that of a normal thermosetting resin such as transfer molding or compression molding. The obtained molded article has improved characteristics such as mechanical strength such as bending strength, heat resistance, and electrical insulation.
以下、実施例を挙げて本発明をより詳細に説明するが、本発明は以下の実施例によって限定されるものではない。
［実施例１］
（ノボラック系フェノール樹脂成形材料）
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平均粒径６０μｍの草本系リグニンを得た。
このリグニンを用いて、下表に示す配合量で各成分を混合した。
これらの配合成分を、混合後、２本ロールにて１００～１１０℃で５分間混練して、リグニン添加フェノール樹脂成形材料を得た。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited by a following example.
[Example 1]
(Novolac phenol resin molding material)
A herbaceous lignin having an average particle size of 60 μm was obtained from the waste liquid produced in the pulp manufacturing process using straw as a raw material.
Using this lignin, each component was mixed in the blending amounts shown in the following table.
These blended components were mixed and then kneaded for 5 minutes at 100 to 110 ° C. with two rolls to obtain a lignin-added phenol resin molding material.
［実施例１］
（ノボラック系フェノール樹脂成形材料）
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平均粒径６０μｍの草本系リグニンを得た。
このリグニンを用いて、下表に示す配合量で各成分を混合した。
[Example 1]
(Novolac phenol resin molding material)
A herbaceous lignin having an average particle size of 60 μm was obtained from the waste liquid produced in the pulp manufacturing process using straw as a raw material.
Using this lignin, each component was mixed in the blending amounts shown in the following table.
［比較例１］
草本系リグニンに代えて、木本系リグニンを用いた他は、実施例１と同様にしてリグニン添加フェノール樹脂成形材料を得た。使用した木本系リグニンは、パルプ製造過程で生成した廃液から回収したリグニンを乾燥したものである。 [Comparative Example 1]
A lignin-added phenol resin molding material was obtained in the same manner as in Example 1 except that woody lignin was used instead of the herbaceous lignin. The used woody lignin is obtained by drying lignin recovered from the waste liquid produced in the pulp manufacturing process.
草本系リグニンに代えて、木本系リグニンを用いた他は、実施例１と同様にしてリグニン添加フェノール樹脂成形材料を得た。使用した木本系リグニンは、パルプ製造過程で生成した廃液から回収したリグニンを乾燥したものである。 [Comparative Example 1]
A lignin-added phenol resin molding material was obtained in the same manner as in Example 1 except that woody lignin was used instead of the herbaceous lignin. The used woody lignin is obtained by drying lignin recovered from the waste liquid produced in the pulp manufacturing process.
［比較例２］
草本系リグニンを添加せず、下表に示す配合量で各成分を混合した他は、実施例１と同様にしてフェノール樹脂成形材料を得た。
[Comparative Example 2]
A phenol resin molding material was obtained in the same manner as in Example 1 except that herbaceous lignin was not added and each component was mixed in the blending amounts shown in the following table.
草本系リグニンを添加せず、下表に示す配合量で各成分を混合した他は、実施例１と同様にしてフェノール樹脂成形材料を得た。
A phenol resin molding material was obtained in the same manner as in Example 1 except that herbaceous lignin was not added and each component was mixed in the blending amounts shown in the following table.
［Ｉ］成形性評価
実施例１および比較例１、２で得たフェノール樹脂成形材料について、示差走査熱量分析（ＤＳＣ）挙動、溶融粘弾性挙動、熱重量分析（ＴＧ－ＤＴＡ）挙動を調べた。その結果、硬化特性に差は認められず、リグニンを添加していないフェノール樹脂成形材料（比較例２）とほぼ同等であった。 [I] Moldability Evaluation The phenol resin molding materials obtained in Example 1 and Comparative Examples 1 and 2 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, which was almost the same as that of the phenol resin molding material to which lignin was not added (Comparative Example 2).
実施例１および比較例１、２で得たフェノール樹脂成形材料について、示差走査熱量分析（ＤＳＣ）挙動、溶融粘弾性挙動、熱重量分析（ＴＧ－ＤＴＡ）挙動を調べた。その結果、硬化特性に差は認められず、リグニンを添加していないフェノール樹脂成形材料（比較例２）とほぼ同等であった。 [I] Moldability Evaluation The phenol resin molding materials obtained in Example 1 and Comparative Examples 1 and 2 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, which was almost the same as that of the phenol resin molding material to which lignin was not added (Comparative Example 2).
［ＩＩ］成形品の物性評価
実施例１および比較例１、２で得たフェノール樹脂成形材料について、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。得られた成形品の物性を評価した。評価方法は以下の通りである。
（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、固体動的粘弾性測定（周波数１Ｈｚ、昇温速度２℃／分）を行った。ガラス転移温度（Ｔｇ）は、固体動的粘弾性測定から得られるｔａｎδ曲線のピーク温度とした。
（２）機械的強度（曲げ強度）
ＪＩＳ Ｋ６９１１に従い、クロスヘッド速度３ｍｍ／分、スパン１００ｍｍにて曲げ強度の測定を行った。
（３）耐熱性（荷重たわみ温度）
ＡＳＴＭ Ｄ６４８に従い、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。
（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。
（５）電気絶縁性（体積抵抗率）
ＪＩＳ Ｋ６９１１に従い、横河-Ｈｅｗｌｅｔｔ－Ｐａｃｋａｒｄ社製のＨＰ４３３９Ａを用いて体積抵抗率（ル・ｃｍ）を測定した。
（６）誘電率
アジレントテクノロジー（株）製のインピーダンスアナライザーＥ４９９１Ａを用い、周波数１ＧＨｚにおける誘電率を容量法にて測定した。
（７）耐水性（吸水率）
吸水率は、初期の重量と、沸騰水に２時間浸漬した後の重量増加とを測定し、その比率により吸水率を算出した。
これらの評価結果を表３に示す。
[II] Evaluation of physical properties of molded products The phenol resin molding materials obtained in Example 1 and Comparative Examples 1 and 2 were molded at 170 ° C for 15 minutes using a transfer molding method to obtain molded products. . The physical properties of the obtained molded product were evaluated. The evaluation method is as follows.
(1) Heat resistance (glass transition temperature (Tg))
Solid dynamic viscoelasticity measurement (frequency: 1 Hz, temperature increase rate: 2 ° C./min) was performed using DMS110 manufactured by SII Nanotechnology. The glass transition temperature (Tg) was the peak temperature of the tan δ curve obtained from the solid dynamic viscoelasticity measurement.
(2) Mechanical strength (bending 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.
(3) 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 .
(4) Coefficient of linear expansion TMA curve obtained by TMA / SS6000 manufactured by SII NanoTechnology Co., Ltd., thermomechanical analysis (TMA) in nitrogen mode, compression mode, heating rate 2 ° C / min. The linear expansion coefficient at 100 ° C. was determined from the slope of.
(5) Electrical insulation (volume resistivity)
In accordance with JIS K6911, volume resistivity (le · cm) was measured using HP4339A manufactured by Yokogawa-Hewlett-Packard.
(6) Dielectric constant Using an impedance analyzer E4991A manufactured by Agilent Technologies, the dielectric constant at a frequency of 1 GHz was measured by a capacitance method.
(7) Water resistance (water absorption)
For the water absorption, the initial weight and the increase in weight after being immersed in boiling water for 2 hours were measured, and the water absorption was calculated from the ratio.
These evaluation results are shown in Table 3.
実施例１および比較例１、２で得たフェノール樹脂成形材料について、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。得られた成形品の物性を評価した。評価方法は以下の通りである。
（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、固体動的粘弾性測定（周波数１Ｈｚ、昇温速度２℃／分）を行った。ガラス転移温度（Ｔｇ）は、固体動的粘弾性測定から得られるｔａｎδ曲線のピーク温度とした。
（２）機械的強度（曲げ強度）
ＪＩＳ Ｋ６９１１に従い、クロスヘッド速度３ｍｍ／分、スパン１００ｍｍにて曲げ強度の測定を行った。
（３）耐熱性（荷重たわみ温度）
ＡＳＴＭ Ｄ６４８に従い、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。
（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。
（５）電気絶縁性（体積抵抗率）
ＪＩＳ Ｋ６９１１に従い、横河-Ｈｅｗｌｅｔｔ－Ｐａｃｋａｒｄ社製のＨＰ４３３９Ａを用いて体積抵抗率（ル・ｃｍ）を測定した。
（６）誘電率
アジレントテクノロジー（株）製のインピーダンスアナライザーＥ４９９１Ａを用い、周波数１ＧＨｚにおける誘電率を容量法にて測定した。
（７）耐水性（吸水率）
吸水率は、初期の重量と、沸騰水に２時間浸漬した後の重量増加とを測定し、その比率により吸水率を算出した。
これらの評価結果を表３に示す。
(1) Heat resistance (glass transition temperature (Tg))
Solid dynamic viscoelasticity measurement (frequency: 1 Hz, temperature increase rate: 2 ° C./min) was performed using DMS110 manufactured by SII Nanotechnology. The glass transition temperature (Tg) was the peak temperature of the tan δ curve obtained from the solid dynamic viscoelasticity measurement.
(2) Mechanical strength (bending 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.
(3) 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 .
(4) Coefficient of linear expansion TMA curve obtained by TMA / SS6000 manufactured by SII NanoTechnology Co., Ltd., thermomechanical analysis (TMA) in nitrogen mode, compression mode, heating rate 2 ° C / min. The linear expansion coefficient at 100 ° C. was determined from the slope of.
(5) Electrical insulation (volume resistivity)
In accordance with JIS K6911, volume resistivity (le · cm) was measured using HP4339A manufactured by Yokogawa-Hewlett-Packard.
(6) Dielectric constant Using an impedance analyzer E4991A manufactured by Agilent Technologies, the dielectric constant at a frequency of 1 GHz was measured by a capacitance method.
(7) Water resistance (water absorption)
For the water absorption, the initial weight and the increase in weight after being immersed in boiling water for 2 hours were measured, and the water absorption was calculated from the ratio.
These evaluation results are shown in Table 3.
表３から、実施例１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較して、耐熱性はほぼ同等であるが、機械的強度が優れていることがわかる。また、電気絶縁性および耐水性についても、実施例１の成形材料を用いて得られた成形品の方が優れていることがわかる。
一方、比較例２で得られた従来のフェノール樹脂成形品と比較すると、実施例１で得られた成形品は、機械的強度はほぼ同等であるが、耐熱性、電気絶縁性および誘電性が向上し、かつ線膨張係数も小さいことがわかる。 From Table 3, the molded product obtained using the molding material of Example 1 has substantially the same heat resistance as the molded product obtained in Comparative Example 1, but has excellent mechanical strength. I understand that. Moreover, it turns out that the molded article obtained using the molding material of Example 1 is superior also about electrical insulation and water resistance.
On the other hand, when compared with the conventional phenol resin molded product obtained in Comparative Example 2, the molded product obtained in Example 1 has almost the same mechanical strength, but has heat resistance, electrical insulation and dielectric properties. It can be seen that the linear expansion coefficient is small and improved.
一方、比較例２で得られた従来のフェノール樹脂成形品と比較すると、実施例１で得られた成形品は、機械的強度はほぼ同等であるが、耐熱性、電気絶縁性および誘電性が向上し、かつ線膨張係数も小さいことがわかる。 From Table 3, the molded product obtained using the molding material of Example 1 has substantially the same heat resistance as the molded product obtained in Comparative Example 1, but has excellent mechanical strength. I understand that. Moreover, it turns out that the molded article obtained using the molding material of Example 1 is superior also about electrical insulation and water resistance.
On the other hand, when compared with the conventional phenol resin molded product obtained in Comparative Example 2, the molded product obtained in Example 1 has almost the same mechanical strength, but has heat resistance, electrical insulation and dielectric properties. It can be seen that the linear expansion coefficient is small and improved.
｛実施例２｝
（レゾール系フェノール樹脂成形材料）
実施例１で使用したのと同じ草本系リグニンを用いて、これをメタノール中でレゾール系フェノール樹脂と１：１の重量比で混合したのち、メタノールを除去し、リグニン添加フェノール樹脂成形材料を得た。
このフェノール樹脂成形材料を圧縮成形法にて２００℃で１５分間成形して、成形品を得た。この成形品は耐熱性の高いものであった。すなわち、固体動的粘弾性試験の結果、レゾールのみの硬化物のガラス転移温度Ｔｇは２６３℃、リグニン添加フェノール樹脂硬化物のＴｇは２６７℃であった。 {Example 2}
(Resol-based phenolic resin molding material)
Using the same herbaceous lignin used in Example 1, this was mixed with a resole phenolic resin in a 1: 1 weight ratio in methanol, and then the methanol was removed to obtain a lignin-added phenolic resin molding material. It was.
This phenolic resin molding material was molded by compression molding at 200 ° C. for 15 minutes to obtain a molded product. This molded product had high heat resistance. That is, as a result of the solid dynamic viscoelasticity test, the glass transition temperature Tg of the cured product of only resole was 263 ° C., and the Tg of the lignin-added phenol resin cured product was 267 ° C.
（レゾール系フェノール樹脂成形材料）
実施例１で使用したのと同じ草本系リグニンを用いて、これをメタノール中でレゾール系フェノール樹脂と１：１の重量比で混合したのち、メタノールを除去し、リグニン添加フェノール樹脂成形材料を得た。
このフェノール樹脂成形材料を圧縮成形法にて２００℃で１５分間成形して、成形品を得た。この成形品は耐熱性の高いものであった。すなわち、固体動的粘弾性試験の結果、レゾールのみの硬化物のガラス転移温度Ｔｇは２６３℃、リグニン添加フェノール樹脂硬化物のＴｇは２６７℃であった。 {Example 2}
(Resol-based phenolic resin molding material)
Using the same herbaceous lignin used in Example 1, this was mixed with a resole phenolic resin in a 1: 1 weight ratio in methanol, and then the methanol was removed to obtain a lignin-added phenolic resin molding material. It was.
This phenolic resin molding material was molded by compression molding at 200 ° C. for 15 minutes to obtain a molded product. This molded product had high heat resistance. That is, as a result of the solid dynamic viscoelasticity test, the glass transition temperature Tg of the cured product of only resole was 263 ° C., and the Tg of the lignin-added phenol resin cured product was 267 ° C.
Claims (5)
- 熱硬化性樹脂および草本系リグニンを含有する、ことを特徴とするリグニン添加熱硬化性樹脂。 A lignin-added thermosetting resin characterized by containing a thermosetting resin and a herbaceous lignin.
- 前記熱硬化性樹脂が、ノボラック系またはレゾール系のフェノール樹脂である請求項１に記載のリグニン添加熱硬化性樹脂。 2. The lignin-added thermosetting resin according to claim 1, wherein the thermosetting resin is a novolac-based or resol-based phenol resin.
- 前記草本系リグニンが、乾燥した粉末形態で添加される請求項１または２に記載のリグニン添加熱硬化性樹脂。 The lignin-added thermosetting resin according to claim 1 or 2, wherein the herbaceous lignin is added in a dry powder form.
- 熱硬化性樹脂１００重量部に対して、草本系リグニンを１０～３００重量部を添加した請求項１～３のいずれかに記載のリグニン添加熱硬化性樹脂。 The lignin-added thermosetting resin according to any one of claims 1 to 3, wherein 10 to 300 parts by weight of herbaceous lignin is added to 100 parts by weight of the thermosetting resin.
- 請求項１～４のいずれかに記載のリグニン添加熱硬化性樹脂を用いて所定形状に成形したことを特徴とするリグニン添加熱硬化性樹脂成形品。 A lignin-added thermosetting resin molded product, which is molded into a predetermined shape using the lignin-added thermosetting resin according to any one of claims 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-227411 | 2010-10-07 | ||
| JP2010227411A JP5879027B2 (en) | 2010-10-07 | 2010-10-07 | Lignin-added thermosetting resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012046482A1 true WO2012046482A1 (en) | 2012-04-12 |
Family
ID=45927483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2011/065559 WO2012046482A1 (en) | 2010-10-07 | 2011-07-07 | Lignin-added thermosetting resin |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5879027B2 (en) |
| TW (1) | TW201215643A (en) |
| WO (1) | WO2012046482A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015174894A (en) * | 2014-03-14 | 2015-10-05 | 住友ベークライト株式会社 | Thermosetting resin composition and method of manufacturing the same |
| WO2016027537A1 (en) * | 2014-08-18 | 2016-02-25 | 日立化成株式会社 | Resin composition and molded object |
| WO2016194600A1 (en) * | 2015-06-02 | 2016-12-08 | ハリマ化成株式会社 | Resin composition, method for producing resin composition, and molded article |
| CN110891960A (en) * | 2017-08-10 | 2020-03-17 | 出光兴产株式会社 | Method for producing modified lignin and modified polyphenol, and resin composition material using modified lignin |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016060813A (en) * | 2014-09-17 | 2016-04-25 | 出光興産株式会社 | Thermosetting resin composition |
| EP3222665A4 (en) * | 2014-11-20 | 2018-05-30 | Sumitomo Bakelite Co.,Ltd. | Lignin resin composition, cured object, and molded object |
| WO2019026825A1 (en) | 2017-07-31 | 2019-02-07 | 東レ株式会社 | Method for producing lignin |
| WO2019031610A1 (en) * | 2017-08-10 | 2019-02-14 | 出光興産株式会社 | Modified lignin manufacturing method, modified lignin, and modified lignin-including resin composition material |
| BR102018077399A8 (en) * | 2018-12-28 | 2021-06-15 | Suzano Papel E Celulose S A | resol type phenolic resins, synthesis process of said resins and their use |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225325A (en) * | 2005-02-17 | 2006-08-31 | Toyota Auto Body Co Ltd | Production method of phenolized lignin |
| JP2008156601A (en) * | 2006-12-01 | 2008-07-10 | Toyota Auto Body Co Ltd | Lignin-modified novolac type phenolic resin, method of producing the same, and phenolic resin molding material |
| JP2008266210A (en) * | 2007-04-20 | 2008-11-06 | Toyota Auto Body Co Ltd | Method for producing phenolized lignin |
| JP2009167306A (en) * | 2008-01-17 | 2009-07-30 | Panasonic Corp | Mold material and molded product |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5256813B2 (en) * | 2008-03-25 | 2013-08-07 | 住友ベークライト株式会社 | Lignin resin composition and molding material |
-
2010
- 2010-10-07 JP JP2010227411A patent/JP5879027B2/en not_active Expired - Fee Related
-
2011
- 2011-07-07 WO PCT/JP2011/065559 patent/WO2012046482A1/en active Application Filing
- 2011-08-19 TW TW100129733A patent/TW201215643A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225325A (en) * | 2005-02-17 | 2006-08-31 | Toyota Auto Body Co Ltd | Production method of phenolized lignin |
| JP2008156601A (en) * | 2006-12-01 | 2008-07-10 | Toyota Auto Body Co Ltd | Lignin-modified novolac type phenolic resin, method of producing the same, and phenolic resin molding material |
| JP2008266210A (en) * | 2007-04-20 | 2008-11-06 | Toyota Auto Body Co Ltd | Method for producing phenolized lignin |
| JP2009167306A (en) * | 2008-01-17 | 2009-07-30 | Panasonic Corp | Mold material and molded product |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015174894A (en) * | 2014-03-14 | 2015-10-05 | 住友ベークライト株式会社 | Thermosetting resin composition and method of manufacturing the same |
| WO2016027537A1 (en) * | 2014-08-18 | 2016-02-25 | 日立化成株式会社 | Resin composition and molded object |
| WO2016194600A1 (en) * | 2015-06-02 | 2016-12-08 | ハリマ化成株式会社 | Resin composition, method for producing resin composition, and molded article |
| CN110891960A (en) * | 2017-08-10 | 2020-03-17 | 出光兴产株式会社 | Method for producing modified lignin and modified polyphenol, and resin composition material using modified lignin |
| US11518886B2 (en) | 2017-08-10 | 2022-12-06 | Idemitsu Kosan Co., Ltd. | Modified lignin, modified polyphenol manufacturing method, and modified lignin-including resin composition material |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201215643A (en) | 2012-04-16 |
| JP2012082255A (en) | 2012-04-26 |
| JP5879027B2 (en) | 2016-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5879027B2 (en) | Lignin-added thermosetting resin | |
| JP5671430B2 (en) | Modified lignin and phenolic resin molding material containing the same | |
| JP2023024831A (en) | Modified lignin manufacturing method, modified lignin, and modified lignin-containing resin composition material | |
| JP5703203B2 (en) | Water-insoluble lignin and thermosetting resin molding material containing the same | |
| JP2023024830A (en) | Methods for producing modified lignin and modified polyphenol, and resin composition material using modified lignin | |
| Deli et al. | Blends of unsaturated polyester and phenolic resins for application as fire-resistant matrices in fibre-reinforced composites. Part 1: identifying compatible, co-curable resin mixtures | |
| WO2015178103A1 (en) | Resin composition and method for producing same | |
| JP2021123717A (en) | Resin composition | |
| JP2015193860A (en) | Lignin-added thermosetting resin | |
| JP6645440B2 (en) | Lignin resin composition, cured product and molded product | |
| JP4355979B2 (en) | Phenolic resin molding composition | |
| JP2015048361A (en) | Lignin resin composition, resin molded article, prepreg, and molding material | |
| JP4402499B2 (en) | Thermosetting biomass resin composition and molded product thereof | |
| JP6624884B2 (en) | Biomass phenol liquefied resin | |
| JP2011132339A (en) | Thermosetting molding material and molded product | |
| JP4355981B2 (en) | Phenolic resin molding composition | |
| JP6792105B2 (en) | Phenolic liquefied resin | |
| JP5374187B2 (en) | Melamine resin molding material | |
| JP2014084450A (en) | Modified lignin and thermosetting resin molding material containing the same | |
| JPH10120870A (en) | Phenolic resin molding material | |
| JP5381573B2 (en) | Thermosetting resin molding material | |
| JP5402142B2 (en) | Phenolic resin molding material | |
| JP2003253088A (en) | Phenol resin molding material | |
| CN113150491A (en) | Bakelite flour material for manufacturing commutator | |
| JP2016222835A (en) | Resin composition, manufacturing method of resin composition and molded article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11830416 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 11830416 Country of ref document: EP Kind code of ref document: A1 |