JP2010007001A - Unsaturated polyester resin composition - Google Patents
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- JP2010007001A JP2010007001A JP2008169762A JP2008169762A JP2010007001A JP 2010007001 A JP2010007001 A JP 2010007001A JP 2008169762 A JP2008169762 A JP 2008169762A JP 2008169762 A JP2008169762 A JP 2008169762A JP 2010007001 A JP2010007001 A JP 2010007001A
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Abstract
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本発明はバイオマス由来の原料からなる不飽和ポリエステル樹脂組成物に関する。 The present invention relates to an unsaturated polyester resin composition comprising a biomass-derived raw material.
近年、環境問題に対する社会的な関心が高まっており、絶縁材料、あるいは接着材料などに用いられる熱硬化性樹脂に対しても、環境への負荷の低減が要求されてきている。一般に、電気絶縁用などに広く用いられる不飽和ポリエステル樹脂は、作業性、および硬化物の可とう性は優れるものの、エポキシ樹脂と比べて、耐熱性、あるいは接着性がやや低いという問題があった。また、特許文献１には、バインダ成分としてセルロース，リグニン等のバイオマスを主成分として含有することを特徴とするモールド材料について記載されている。特許文献２には、木質素材，木質素材抽出物の少なくとも一方を導入したスイッチギヤ課電部の固体絶縁物について記載されている。特許文献３には、リグニンのフェノール誘導体を用いたポリウレタン組成物について記載されている。 In recent years, there has been an increasing social interest in environmental problems, and there has been a demand for reducing the burden on the environment for thermosetting resins used for insulating materials or adhesive materials. In general, unsaturated polyester resins widely used for electrical insulation have excellent workability and flexibility of cured products, but have a problem that heat resistance or adhesion is slightly lower than epoxy resins. . Patent Document 1 describes a molding material characterized in that it contains biomass such as cellulose and lignin as a main component as a binder component. Patent Document 2 describes a solid insulator of a switchgear charging section in which at least one of a wood material and a wood material extract is introduced. Patent Document 3 describes a polyurethane composition using a phenol derivative of lignin.
特許文献１、および特許文献２には、バイオマスを主成分として含有するのみで、耐熱性，接着性については考慮されていなかった。また、特許文献３には、耐熱性，接着性について記載があるものの、ポリウレタン樹脂に関するものであり、ポリオール成分として用いるリグノフェノールの分子量が大きく、不飽和ポリエステル樹脂の原料として用いるにあたっては作業性が悪くなるという問題があった。 Patent Documents 1 and 2 only contain biomass as a main component, and heat resistance and adhesiveness were not considered. Patent Document 3 describes heat resistance and adhesiveness, but relates to a polyurethane resin. The molecular weight of lignophenol used as a polyol component is large, and workability is high when used as a raw material for unsaturated polyester resin. There was a problem of getting worse.
本発明の目的は、接着性，耐熱性に優れ、かつ二酸化炭素排出量を減らすことにより環境への負荷を低減することが可能な不飽和ポリエステル樹脂組成物を提供することにある。 An object of the present invention is to provide an unsaturated polyester resin composition that is excellent in adhesiveness and heat resistance and that can reduce the burden on the environment by reducing carbon dioxide emission.
本発明の不飽和ポリエステル樹脂組成物は、分子量が１３００以下のリグニン又はリグニン由来のリグノフェノールと、１分子中に少なくとも１個の二重結合を持つ二価のカルボン酸との重合反応によって得られる不飽和ポリエステル成分を含むことを特徴とする。 The unsaturated polyester resin composition of the present invention is obtained by a polymerization reaction of lignin having a molecular weight of 1300 or less or lignophenol derived from lignin and a divalent carboxylic acid having at least one double bond in one molecule. It contains an unsaturated polyester component.
また、本発明の不飽和ポリエステル樹脂組成物は、１分子中にフェノール性水酸基を平均２〜４個持つリグニン又はフェノール性水酸基を平均２〜４個持つリグニン由来のリグノフェノールと、１分子中に少なくとも１個の二重結合を持つ二価のカルボン酸との重合反応によって得られる不飽和ポリエステル成分を含むことを特徴とする。 The unsaturated polyester resin composition of the present invention comprises lignin derived from lignin having an average of 2 to 4 phenolic hydroxyl groups in one molecule or lignin derived from lignin having an average of 2 to 4 phenolic hydroxyl groups in one molecule. It comprises an unsaturated polyester component obtained by a polymerization reaction with a divalent carboxylic acid having at least one double bond.
また、本発明の不飽和ポリエステル樹脂組成物は、分子量が６００〜１３００のリグニン又は分子量が６００〜１３００のリグニン由来のリグノフェノールと、１分子中に少なくとも１個の二重結合を持つ二価のカルボン酸との重合反応によって得られる不飽和ポリエステル成分を含むことを特徴とする。 The unsaturated polyester resin composition of the present invention is a divalent lignin derived from lignin having a molecular weight of 600 to 1300 or lignin having a molecular weight of 600 to 1300 and a divalent having at least one double bond in one molecule. It contains an unsaturated polyester component obtained by a polymerization reaction with a carboxylic acid.
また、本発明の不飽和ポリエステル樹脂組成物は、１分子中にフェノール性水酸基を平均２〜４個持つリグニン又は１分子中にフェノール性水酸基を平均２〜４個持つリグニン由来のリグノフェノールと、１分子中に少なくとも１個の二重結合を持つ二価のカルボン酸との重合反応によって得られる不飽和ポリエステル成分、および二重結合を持つ化合物を含むことを特徴とする。 Further, the unsaturated polyester resin composition of the present invention is a lignin derived from lignin having an average of 2 to 4 phenolic hydroxyl groups in one molecule or lignin derived from lignin having an average of 2 to 4 phenolic hydroxyl groups in one molecule; It contains an unsaturated polyester component obtained by a polymerization reaction with a divalent carboxylic acid having at least one double bond in one molecule, and a compound having a double bond.
リグニンは、天然の化合物であり、一例として下記の式（１）の化学構造式で表される。このリグニンから、例えばメタノール等の溶媒で抽出することにより、１分子中にフェノール性水酸基を平均２〜４個持つ低分子量（分子量１３００以下、好ましくは６００〜１３００）のリグニンが得られる。低分子量のリグニンの化学構造式の一例を下式（２）に示す。分子中にフェノール性水酸基の他に、アルコール性水酸基を複数持ち、また、ベンゼン環を複数有する化合物である。 Lignin is a natural compound, and is represented by the chemical structural formula of the following formula (1) as an example. By extracting from this lignin with a solvent such as methanol, for example, a low molecular weight (molecular weight of 1300 or less, preferably 600 to 1300) lignin having an average of 2 to 4 phenolic hydroxyl groups in one molecule can be obtained. An example of the chemical structural formula of low molecular weight lignin is shown in the following formula (2). In addition to the phenolic hydroxyl group, the compound has a plurality of alcoholic hydroxyl groups and a plurality of benzene rings.
また、リグニン由来の化合物として、下式（３）で表される上記リグノフェノールが知られている。式（３）は、リグノフェノールの化学構造式である。例えばメタノール等の溶媒で抽出することにより低分子量のリグニンのリグニン同様に、１分子中にフェノール性水酸基を平均２〜４個持つ上記リグノフェノールが得られる。分子中にフェノール性水酸基の他に、アルコール性水酸基を複数持ち、また、ベンゼン環を複数有する化合物である。 Moreover, the said lignophenol represented by the following Formula (3) is known as a compound derived from lignin. Formula (3) is a chemical structural formula of lignophenol. For example, by extracting with a solvent such as methanol, the above lignophenol having an average of 2 to 4 phenolic hydroxyl groups in one molecule can be obtained in the same manner as lignin of low molecular weight lignin. In addition to the phenolic hydroxyl group, the compound has a plurality of alcoholic hydroxyl groups and a plurality of benzene rings.
本発明によれば、接着性，耐熱性に優れ、かつ二酸化炭素排出量を減らすことにより環境への負荷を低減することができる不飽和ポリエステル樹脂組成物を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, it is excellent in adhesiveness and heat resistance, and can provide the unsaturated polyester resin composition which can reduce the load to an environment by reducing a carbon dioxide discharge.
次に、本発明の実施例の不飽和ポリエステル樹脂組成物について説明する。 Next, the unsaturated polyester resin composition of the Example of this invention is demonstrated.
メタノールで抽出した、式（２）に示したような化学構造を持つ、フェノール性水酸基が平均２〜４個の低分子量のリグニン（分子量１３００以下、好ましくは６００〜１３００）と、１分子中に少なくとも１個の二重結合を持つ二価のカルボン酸との重合反応によって、直線状の不飽和ポリエステル化合物を合成することができる。同様に、式（３）に示したような化学構造を持つ、１分子中にフェノール性水酸基を平均２〜４個持つ前記リグノフェノールと、１分子中に少なくとも１個の二重結合を持つ二価のカルボン酸との重合反応によって、不飽和ポリエステル化合物を合成することができる。いずれも、分子中に複数のアルコール性水酸基を持つが、アルコール性水酸基より反応性の高いフェノール性水酸基のみがカルボン酸と反応する反応条件を選ぶことで、直線状の不飽和ポリエステル化合物を合成することができる。得られた不飽和ポリエステルを含む不飽和ポリエステル樹脂組成物は、分子中に残った複数のアルコール性水酸基によって、高い接着性を持つ。また、分子中に複数のベンゼン環を持つため、硬化した樹脂は高い耐熱性を示す。 A low molecular weight lignin (molecular weight of 1300 or less, preferably 600 to 1300) having an average of 2 to 4 phenolic hydroxyl groups extracted with methanol and having a chemical structure as shown in formula (2), and in one molecule A linear unsaturated polyester compound can be synthesized by a polymerization reaction with a divalent carboxylic acid having at least one double bond. Similarly, the lignophenol having a chemical structure represented by the formula (3) having an average of 2 to 4 phenolic hydroxyl groups in one molecule and two having at least one double bond in one molecule. An unsaturated polyester compound can be synthesized by a polymerization reaction with a valent carboxylic acid. All have a plurality of alcoholic hydroxyl groups in the molecule, but a linear unsaturated polyester compound is synthesized by selecting reaction conditions in which only phenolic hydroxyl groups that are more reactive than alcoholic hydroxyl groups react with carboxylic acids. be able to. The unsaturated polyester resin composition containing the obtained unsaturated polyester has high adhesiveness due to a plurality of alcoholic hydroxyl groups remaining in the molecule. In addition, since the molecule has a plurality of benzene rings, the cured resin exhibits high heat resistance.
（実施例１，２），（比較例１）
平均分子量が約１０００のリグニンと無水マレイン酸とを重合させることにより、不飽和ポリエステル樹脂Ａを得た。また、平均分子量が約１０００のリグノフェノールと無水マレイン酸とを重合させることにより、不飽和ポリエステル樹脂Ｂを得た。
(Examples 1 and 2), (Comparative Example 1)
Unsaturated polyester resin A was obtained by polymerizing lignin having an average molecular weight of about 1000 and maleic anhydride. Moreover, unsaturated polyester resin B was obtained by polymerizing lignophenol having an average molecular weight of about 1000 and maleic anhydride.
不飽和ポリエステル樹脂Ａ，不飽和ポリエステル樹脂Ｂ，各々５０重量部に対してスチレンを５０重量部加え、硬化触媒としてジクミルパーオキサイドを１．５重量部加えた後、１６０℃で１ｈ加熱して硬化した。比較例として、市販のイミド系の不飽和ポリエステル樹脂１００重量部に硬化触媒としてジクミルパーオキサイドを１．５重量部加えた後、１６０℃で１ｈ加熱して硬化した。得られた硬化樹脂の特性を表１にまとめた。表１は、不飽和ポリエステル樹脂組成物の硬化物の特性を示している。 Add 50 parts by weight of styrene to 50 parts by weight of unsaturated polyester resin A and unsaturated polyester resin B, respectively, add 1.5 parts by weight of dicumyl peroxide as a curing catalyst, and then heat at 160 ° C. for 1 hour. Cured. As a comparative example, 1.5 parts by weight of dicumyl peroxide as a curing catalyst was added to 100 parts by weight of a commercially available imide-based unsaturated polyester resin and then cured by heating at 160 ° C. for 1 h. The properties of the resulting cured resin are summarized in Table 1. Table 1 shows the characteristics of the cured product of the unsaturated polyester resin composition.
ガラス転移温度は、（株）真空理工製ＴＭＡ１５００を用いて、縦５mm×横５mm×厚さ５mmに切り出し、圧縮モードにおいて厚さ方向の熱伸び量を測定して、線膨張係数の不連続点から評価した。 The glass transition temperature was cut into 5mm x 5mm x 5mm thickness using TMA1500 manufactured by Vacuum Riko Co., Ltd., and the thermal expansion in the thickness direction was measured in compression mode. It was evaluated from.
接着性は、ＪＩＳ Ｋ６８５１に準じて、２枚の標準試験鋼板を接着した。１６０℃で１ｈ加熱して硬化した後、（株）島津製作所製定変位速度負荷試験機オートグラフＩＳ−２０Ｔを用いて，引張速度５mm／minで測定した。 Adhesiveness adhered two standard test steel plates according to JIS K6851. After curing by heating at 160 ° C. for 1 h, measurement was performed at a tensile speed of 5 mm / min using a constant displacement speed load tester, Autograph IS-20T, manufactured by Shimadzu Corporation.
また、耐熱温度指数は、熱劣化により曲げ特性が５０％に低下する時間を寿命点として評価した。曲げ特性は５mmの樹脂板を１５mm×１２０mmに切り出し、（株）島津製作所製定変位速度負荷試験機オートグラフＩＳ−２０Ｔを用いて、３点曲げ試験法により、スパン間距離８０mm，曲げ速度５mm／minで測定した。 In addition, the heat resistant temperature index was evaluated using the time required for the bending property to drop to 50% due to thermal deterioration as a life point. Bending characteristics were obtained by cutting a 5 mm resin plate into 15 mm x 120 mm and using a constant displacement speed load tester, Autograph IS-20T, manufactured by Shimadzu Corp., using a three-point bending test method, span distance of 80 mm, bending speed of 5 mm / Measured in min.
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| JP2012153797A (en) * | 2011-01-26 | 2012-08-16 | Hitachi Ltd | Plant-based polycarbonate resin and production method thereof |
| US20150197667A1 (en) * | 2014-01-15 | 2015-07-16 | Ppg Industries Ohio, Inc. | Polyester polymers comprising lignin |
| CN113563572A (en) * | 2021-07-28 | 2021-10-29 | 黄山市源润新材料科技有限公司 | Polyester resin for mixed 70/30 powder coating and preparation method thereof |
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| US20150197667A1 (en) * | 2014-01-15 | 2015-07-16 | Ppg Industries Ohio, Inc. | Polyester polymers comprising lignin |
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| CN113563572A (en) * | 2021-07-28 | 2021-10-29 | 黄山市源润新材料科技有限公司 | Polyester resin for mixed 70/30 powder coating and preparation method thereof |
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