WO2016063972A1 - Resin additive, resin composition using same, and production method therefor - Google Patents
Resin additive, resin composition using same, and production method therefor Download PDFInfo
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- WO2016063972A1 WO2016063972A1 PCT/JP2015/079950 JP2015079950W WO2016063972A1 WO 2016063972 A1 WO2016063972 A1 WO 2016063972A1 JP 2015079950 W JP2015079950 W JP 2015079950W WO 2016063972 A1 WO2016063972 A1 WO 2016063972A1
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- fullerene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
- C07C13/64—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings with a bridged ring system
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Definitions
- the present invention relates to a resin additive, a resin composition using the same, and a method for producing the resin composition.
- Patent Document 1 As a method of uniformly dispersing fullerenes in a polyester resin, a method of mixing fullerenes in a polyester resin as a solution, and a polyester resin by performing a polycondensation reaction in a fullerene solution. A method of obtaining is disclosed.
- solvents that can dissolve fullerenes and can be used for the mixing or the polymerization are limited to some aromatic solvents such as benzene and toluene.
- Resins that can be dissolved and mixed with fullerenes are also limited to polyester resins.
- fullerenes are known to trap radicals and suppress radical reactions. Therefore, the polymerization reaction in the presence of fullerene as in Patent Document 1 is limited to a polymerization reaction that does not use a radical reaction.
- Patent Document 2 discloses that dispersibility can be improved by using fullerene hydroxide which is easily dissolved in more solvent than fullerene.
- fullerene derivatives such as fullerene hydroxide are usually less effective in trapping radicals than fullerene, and the improvement in physical and thermal strength is limited.
- Fullerene can be uniformly dispersed in the resulting resin by mixing fullerene as a solution with the resin or its polymerization raw material, but there are limited solvents and resins to which this method can be applied.
- the present invention provides a resin additive composition in which fullerene can be dispersed and contained in various resins, a resin composition using the same, and a method for producing the resin composition.
- the present invention includes the following inventions.
- a resin additive comprising an organic solvent solution of a fullerene derivative in which an indene which may have a substituent is added to a fullerene skeleton.
- the organic solvent is one solvent or a mixed solvent selected from N-methyl-2-pyrrolidone, ethyl acetate, butyl acetate, methyl ethyl ketone, propylene glycol monomethyl ether acetate and cyclohexanone.
- the resin additive as described in.
- the resin additive according to [1] or [2], wherein the fullerene derivative is represented by the following formula (1).
- the step of obtaining the resin mixture includes a step of obtaining a mixture of a material that is polymerized into a resin and the resin additive (hereinafter referred to as “raw material mixture”), and a step of polymerizing the material in the raw material mixture.
- raw material mixture a material that is polymerized into a resin and the resin additive
- the manufacturing method of the resin composition as described in the preceding clause [5] which has these.
- the method for producing a resin composition according to [7] wherein the resin is a thermoplastic resin.
- a resin composition comprising a thermally decomposed product of a fullerene derivative in which an indene which may have a substituent is added to a fullerene skeleton, and a resin.
- a fullerene derivative-containing resin composition comprising a fullerene derivative in which indene, which may have a substituent, is added to the fullerene skeleton, and a resin.
- fullerenes can be dispersed and contained in various resins.
- the resin additive of the present invention comprises an organic solvent solution of a fullerene derivative (hereinafter sometimes simply referred to as “fullerene derivative”) in which an indene which may have a substituent is added to the fullerene skeleton.
- fullerene derivative a fullerene derivative in which an indene which may have a substituent is added to the fullerene skeleton.
- the organic solvent is a solvent that can dissolve the fullerene derivative.
- a more preferable solvent is a solvent that can sufficiently dissolve both the resin and fullerene derivative used, and depends on the combination of the resin and fullerene derivative used.
- NMP N-methyl-2-pyrrolidone
- PGMA propylene glycol monomethyl ether acetate
- One kind of solvent or a plurality of kinds of mixed solvents may be mentioned.
- the resin additive of the present invention can be applied to various resins using a resin production method described later.
- an indene which may have a substituent is added to the fullerene skeleton (hereinafter, “an indene which may have a substituent” is simply referred to as “addition group”). There is also.) By making fullerene into such a derivative, it can be dissolved in various solvents, and since radical trapping ability is suppressed, it can be added during radical polymerization described later.
- the substituent is not essential, but is preferably selected in order to enhance the solubility of the fullerene derivative in the organic solvent.
- a hydrophilic substituent such as a polyethylene glycol chain (for example, a polyethylene glycol chain having 4 to 10 carbon atoms) may be introduced.
- a hydrophobic substituent such as a hydrocarbon chain (for example, a hydrocarbon chain having 1 to 12 carbon atoms) may be introduced.
- a plurality of the additional groups are added to the fullerene skeleton.
- the number of additions is larger, the fullerene derivative is more easily dissolved in an organic solvent, so that the choice of usable solvents can be expanded, and the radical trapping ability of the fullerene derivative can be further suppressed.
- the upper limit of the number of additions increases as the size of the fullerene skeleton increases.
- Fullerenes having various sizes from about C 60 to about C 200 are known. For example, when C 60 which is the smallest fullerene skeleton among various fullerenes but has excellent availability is used, The upper limit of is about 20.
- the addition number is preferably 2 to 10 and more preferably 2 to 4 in view of ease of introduction of the addition group.
- fullerene derivatives include fullerene derivatives represented by the following formula (1).
- FLN in Formula (1) represents a fullerene skeleton, n represents an integer of 1 or more, and Ar 1 represents a benzene ring which may have a substituent.
- FLN in the formula (1) is preferably a C 60 , C 70 skeleton.
- Ar 1 is preferably a benzene ring.
- n preferably contains one to three of the fullerene derivatives represented by the above formula (1), more preferably all of them.
- n contains any of the fullerene derivatives represented by the formula (1) of 1 to 3
- the content of each fullerene derivative contained in the fullerene derivative is 10 to 60% by mass, and the total amount is 90% It is preferable that it is ⁇ 100%.
- the manufacturing method of the resin composition of this invention has the process of obtaining the resin mixture which consists of a mixture of resin and the said resin additive, and the process of removing a solvent from the said resin mixture.
- the method for obtaining the resin mixture is not particularly limited, but it is preferable that the resin additive of the present invention and the resin are mixed in a liquid state in order to obtain good dispersibility of the fullerene derivative in the resin.
- a method of directly dissolving the resin in the resin additive a method of dissolving the resin in a solvent capable of dissolving the resin, and a method of mixing with the resin additive can be given.
- resin is a thermoplastic resin, the method etc. which mix the molten thermoplastic resin and the said resin additive are mentioned.
- a method of obtaining the resin mixture there is a method of obtaining a raw material mixture composed of a mixture of a material that is polymerized into a resin and the resin additive, and polymerizing the material in the raw material mixture.
- the polymerization method polycondensation, polyaddition, ionic polymerization, and radical polymerization are possible. Since the fullerene derivative has suppressed radical trapping ability, the polymerization form may be radical polymerization.
- Step of removing the solvent from the resin mixture The method for removing the solvent from the resin mixture is not particularly limited, and examples thereof include heating, decompression and / or air drying. Usually, the solvent is removed within the range of the temperature and time of thermal decomposition of the fullerene derivative described later. After removing the solvent from the resin mixture, a fullerene derivative-containing resin composition is obtained before performing the pyrolysis step described below.
- fullerene derivatives (Thermal decomposition process of fullerene derivatives) It is known that an indene adduct of fullerene decomposes into fullerene and indene when heated. In the present invention, using this property, the fullerene derivative in the resin mixture and / or the fullerene derivative-containing resin composition is thermally decomposed to produce fullerene in the composition. In addition, fullerene is superior in radical trapping ability to fullerene derivatives.
- the thermal decomposition is preferably performed in the fullerene derivative-containing resin composition in order to prevent aggregation of the fullerene generated.
- the method of obtaining the resin mixture is a method of obtaining a raw material mixture composed of a mixture of a material that becomes a resin by polymerization and the resin additive, and polymerizing the material in the raw material mixture. Is preferred.
- the thermal decomposition temperature is preferably higher than the temperature at which the fullerene derivative is decomposed and lower than the temperature at which damage to the resin can be tolerated. Depending on the type of the resin, it is more preferably 120 ° C. to 350 ° C. More preferably.
- the thermal decomposition time is preferably within a time over which most of the fullerene derivative is decomposed and within which the damage to the resin can be tolerated. Depending on the heating temperature, the type of resin, etc. More preferably, it is 20 to 50 hours.
- the thermal decomposition does not need to be performed continuously, and may be divided into a plurality of times.
- the thermal decomposition step is provided because it is rarely heated in a generally used environment. It is preferable that heating similar to the above thermal decomposition is performed at the time of molding and / or before molding.
- the resin composition that has undergone the thermal decomposition step includes a thermal decomposition product of the fullerene derivative.
- the decomposition product is usually indene which may have a substituent added to fullerene and the fullerene derivative.
- the fullerene content in the resin composition is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass, and further preferably 0.02% by mass to 0.5%. % By mass.
- the fullerene content in the resin composition can be adjusted by adjusting the thermal decomposition conditions or the mixing ratio of the fullerene derivative and the resin.
- the resin contained in the resin composition of the present invention may be any resin that can use the resin additive, such as polyolefin, polystyrene, polyimide, polyamide, polyimide, polyphenylene sulfide, polymethyl methacrylate, and polycarbonate. Is mentioned.
- Example 1 (Synthesis of fullerene derivatives) Fullerene C 60 ( 10 g) and indene (32 g) were reacted by refluxing in 120 mL of o-dichlorobenzene for 20 hours. The solution after the reaction was filtered using silica gel. While stirring, 500 mL of methanol was added dropwise to the filtrate to precipitate a solid. The precipitated solid was washed with methanol to obtain 10 g of a black solid as the target product 1.
- the target compound 1 was analyzed by HPLC for the composition ratio of fullerene, fullerene indene monoadduct, diadduct, and triad or higher adduct. As a result, the composition ratio was 0.9% by mass of fullerene, 32.7% by mass of a monoadduct, 50.4% by mass of a diadduct, and 15.9% by mass of a triadduct or more.
- the target compound 1 is found to dissolve in many solvents that C 60 is not dissolved.
- Example 2 (Measurement of 10% mass loss temperature) Using TG-DTA2000SR manufactured by NETZSCH, a temperature at which the mass of the sample was reduced by 10% was obtained under the air at a heating rate of 10 ° C./min using about 200 mg of the resin composition as a sample. (Measurement of glass transition point (Tg) of resin composition) The temperature of the endothermic peak was obtained using a Mettler DSC-1.
- Thermosetting resin As the resin additive 1 of the present invention, an NMP solution in which 0.1% by mass of the target product 1 was dissolved was prepared.
- a polyimide resin 10 g of bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl] methane was used and dissolved in 20 g of resin additive 1. .
- This solution was heated at 180 ° C. for 24 hours under nitrogen to obtain a solid content.
- the obtained solid content was heated at 250 ° C. for 24 hours to evaporate NMP, and the fullerene derivative was thermally decomposed.
- Table 2 shows the measurement results of the obtained resin composition.
- Comparative Example 2 The same operation and measurement as in Example 2 were performed except that NMP was used in place of the resin additive 1. As a result, a transparent cured product was obtained as the resin composition. Table 2 shows the measurement results of the obtained resin composition.
- Comparative Example 3 The same operation and measurement as in Example 2 were performed except that an NMP dispersion in which 0.1% by mass of fullerene (frontier carbon NM-ST-F) was used instead of the resin additive 1 was used. As a result, a turbid brown cured product was obtained as a resin composition. Table 2 shows the measurement results of the obtained resin composition.
- Example 3 (Thermoplastic resin) 10 g of polymethyl methacrylate was dissolved in 50 g of resin additive 1 at 120 ° C. The solvent was distilled off for 24 hours at 120 ° C. under reduced pressure to obtain a transparent brown cured product as a resin composition. The same measurement as in Example 2 was performed, and the measurement result of the obtained resin composition is shown in Table 3.
- Comparative Example 4 The same operation and measurement as in Example 3 were performed except that NMP was used instead of the resin additive 1. As a result, a transparent cured product was obtained as the resin composition. The measurement results of the obtained resin composition are shown in Table 3.
- Comparative Example 5 The same operation and measurement as in Example 3 were performed except that an NMP dispersion in which 0.1% by mass of fullerene (frontier carbon NM-ST-F) was used instead of the resin additive 1 was used. As a result, a turbid brown cured product was obtained as a resin composition. The measurement results of the obtained resin composition are shown in Table 3.
- Example 4 (Radical polymerization) As the resin additive 2 of the present invention, a toluene solution in which 0.1% by mass of the target product 1 was dissolved was prepared. 50 g of styrene monomer is mixed with 50 g of resin additive 2, and this is heated at 100 ° C. for 12 hours to perform thermal radical polymerization and evaporation of the solvent, and then the resulting solid is heated at 250 ° C. for 24 hours. Thermal decomposition of the fullerene derivative was performed. As a result, a transparent brown cured product was obtained as the resin composition. Table 4 shows the measurement results of the resin composition obtained as a result of the same measurement as in Example 2.
- Comparative Example 6 The same operation as in Example 4 was performed except that a toluene solution in which 0.1% by mass of fullerene (Frontier Carbon NM-ST-F) was used in place of the resin additive 2, but the polymerization was performed. The cured product could not be obtained.
- Comparative Example 7 The operation and measurement were performed in the same manner as in Example 4 except that the resin additive 2 was not mixed with styrene. As a result, a transparent brown cured product was obtained as the resin composition. Table 4 shows the measurement results of the obtained resin composition.
- the resin composition obtained can greatly increase both Tg and 10% mass reduction temperature even if it is a resin that has been difficult to obtain fullerene addition effects until now. Yes (each example).
- the resin additive of the present invention can be added to a resin raw material, and the raw material can be radically polymerized to obtain a resin composition (Example 4).
Abstract
Provided are: a resin additive composition that enables a fullerene to be dispersed and contained in various resins; a resin composition using the same; and a production method for said resin composition. The present invention uses a resin additive comprising an organic solvent solution of a fullerene derivative in which optionally substituted indene is added to a fullerene structure.
Description
樹脂添加剤及びそれを用いた樹脂組成物及び該樹脂組成物の製造方法に関する。
本願は、２０１４年１０月２４日に、日本に出願された特願２０１４－２１７３４１号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a resin additive, a resin composition using the same, and a method for producing the resin composition.
This application claims priority based on Japanese Patent Application No. 2014-217341 filed in Japan on October 24, 2014, the contents of which are incorporated herein by reference.
本願は、２０１４年１０月２４日に、日本に出願された特願２０１４－２１７３４１号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a resin additive, a resin composition using the same, and a method for producing the resin composition.
This application claims priority based on Japanese Patent Application No. 2014-217341 filed in Japan on October 24, 2014, the contents of which are incorporated herein by reference.
樹脂にフラーレンを十分分散して添加した際の効果として、物理的、熱的強度が向上することが知られている。特許文献１には、フラーレン類をポリエステル系樹脂中に均一に分散させる方法として、フラーレン類を溶液としてポリエステル系樹脂に混合する方法、及び、フラーレン類溶液中で重縮合反応を行いポリエステル系樹脂を得る方法が開示されている。
It is known that physical and thermal strengths are improved as an effect when fullerene is sufficiently dispersed and added to a resin. In Patent Document 1, as a method of uniformly dispersing fullerenes in a polyester resin, a method of mixing fullerenes in a polyester resin as a solution, and a polyester resin by performing a polycondensation reaction in a fullerene solution. A method of obtaining is disclosed.
しかし、フラーレン類を溶解させ、かつ、前記混合または前記重合に使用できる溶剤は、ベンゼンやトルエンなどの一部の芳香族系溶媒に限られる。また、フラーレン類を溶解させて混合できる樹脂もポリエステル系樹脂に限定されている。
However, solvents that can dissolve fullerenes and can be used for the mixing or the polymerization are limited to some aromatic solvents such as benzene and toluene. Resins that can be dissolved and mixed with fullerenes are also limited to polyester resins.
また、フラーレンはラジカルをトラップし、ラジカル反応を抑制することが知られている。したがって、特許文献１のようにフラーレン存在下で重合反応ができるのは、ラジカル反応を用いない重合反応に限られる。
Also, fullerenes are known to trap radicals and suppress radical reactions. Therefore, the polymerization reaction in the presence of fullerene as in Patent Document 1 is limited to a polymerization reaction that does not use a radical reaction.
特許文献２では、フラーレンより多くの溶媒に溶解しやすい水酸化フラーレンを用いることで、分散性を向上させることができることが開示されている。しかし、水酸化フラーレンなどのフラーレン誘導体では、通常、フラーレンよりもラジカルをトラップする効果が少なく、物理的、熱的強度の向上は限定的となってしまう。
Patent Document 2 discloses that dispersibility can be improved by using fullerene hydroxide which is easily dissolved in more solvent than fullerene. However, fullerene derivatives such as fullerene hydroxide are usually less effective in trapping radicals than fullerene, and the improvement in physical and thermal strength is limited.
フラーレンを溶液として、樹脂またはその重合原料に混合することで、得られる樹脂中にフラーレンを均一に分散できるが、この方法を適用できる溶媒や樹脂は限られていた。
Fullerene can be uniformly dispersed in the resulting resin by mixing fullerene as a solution with the resin or its polymerization raw material, but there are limited solvents and resins to which this method can be applied.
本発明は、多種の樹脂にフラーレンを分散して含有させることができる樹脂添加剤組成物及びそれを用いた樹脂組成物及び該樹脂組成物の製造方法を提供する。
The present invention provides a resin additive composition in which fullerene can be dispersed and contained in various resins, a resin composition using the same, and a method for producing the resin composition.
すなわち、本発明は以下の発明を含む。
That is, the present invention includes the following inventions.
［１］ 置換基を有してもよいインデンがフラーレン骨格に付加しているフラーレン誘導体の有機溶媒溶液からなる樹脂添加剤。
［２］ 前記有機溶媒が、Ｎ－メチル－２－ピロリドン、酢酸エチル、酢酸ブチル、メチルエチルケトン、プロピレングリコールモノメチルエーテルアセテート及びシクロヘキサノンから選ばれる、１種の溶媒または複数種の混合溶媒である前項［１］に記載の樹脂添加剤。
［３］ 前記フラーレン誘導体が下記式（１）で表される前項［１］または［２］に記載の樹脂添加剤。
（式（１）中のＦＬＮはフラーレン骨格を示し、ｎは１以上の整数を示し、Ａｒ１は、置換基を有していてもよいベンゼン環を示す。）
［４］ 置換基を有してもよいインデンがフラーレン骨格に複数付加している前項［１］～［３］のいずれかに記載の樹脂添加剤。
［５］ 樹脂と前項［１］～［４］のいずれかに記載の樹脂添加剤との混合物（以下「樹脂混合物」という。）を得る工程および前記樹脂混合物から溶媒を除去する工程を有する樹脂組成物の製造方法。
［６］ 前記樹脂混合物を得る工程が、重合して樹脂となる材料と前記樹脂添加剤との混合物（以下「原料混合物」という。）を得る工程および前記原料混合物中の前記材料を重合する工程を有する前項［５］に記載の樹脂組成物の製造方法。
［７］ さらに、前記樹脂混合物を１２０～３５０℃で１～１００時間加熱する工程を有する前項［５］または［６］に記載の樹脂組成物の製造方法。
［８］ 前記樹脂が熱可塑性樹脂である前項［７］に記載の樹脂組成物の製造方法。
［９］ 置換基を有してもよいインデンがフラーレン骨格に付加しているフラーレン誘導体の熱分解物及び樹脂を含む樹脂組成物。
［１０］ 前記熱分解物が、置換基を有してもよいインデンとフラーレンである前項［９］に記載の樹脂組成物。
［１１］ 前記樹脂組成物が、ポリオレフィン、ポリスチレン、ポリイミド、ポリアミド、ポリフェニレンスルファイド、ポリメタクリル酸メチル及びポリカーボネートから選ばれる少なくとも１種を含む前項［９］～［１０］に記載の樹脂組成物。
［１２］ 置換基を有してもよいインデンがフラーレン骨格に付加しているフラーレン誘導体及び樹脂を含むフラレーン誘導体含有樹脂組成物。
［１３］ ［６］～［９］に記載の製造方法で得られる樹脂組成物。 [1] A resin additive comprising an organic solvent solution of a fullerene derivative in which an indene which may have a substituent is added to a fullerene skeleton.
[2] In the preceding item, the organic solvent is one solvent or a mixed solvent selected from N-methyl-2-pyrrolidone, ethyl acetate, butyl acetate, methyl ethyl ketone, propylene glycol monomethyl ether acetate and cyclohexanone. ] The resin additive as described in.
[3] The resin additive according to [1] or [2], wherein the fullerene derivative is represented by the following formula (1).
(FLN in Formula (1) represents a fullerene skeleton, n represents an integer of 1 or more, and Ar 1 represents a benzene ring which may have a substituent.)
[4] The resin additive as described in any one of [1] to [3] above, wherein a plurality of indenes which may have a substituent are added to the fullerene skeleton.
[5] A resin having a step of obtaining a mixture of the resin and the resin additive according to any one of [1] to [4] (hereinafter referred to as “resin mixture”) and a step of removing the solvent from the resin mixture. A method for producing the composition.
[6] The step of obtaining the resin mixture includes a step of obtaining a mixture of a material that is polymerized into a resin and the resin additive (hereinafter referred to as “raw material mixture”), and a step of polymerizing the material in the raw material mixture. The manufacturing method of the resin composition as described in the preceding clause [5] which has these.
[7] The method for producing a resin composition according to [5] or [6] above, further comprising a step of heating the resin mixture at 120 to 350 ° C. for 1 to 100 hours.
[8] The method for producing a resin composition according to [7], wherein the resin is a thermoplastic resin.
[9] A resin composition comprising a thermally decomposed product of a fullerene derivative in which an indene which may have a substituent is added to a fullerene skeleton, and a resin.
[10] The resin composition according to [9], wherein the thermal decomposition product is indene and fullerene which may have a substituent.
[11] The resin composition as described in [9] to [10] above, wherein the resin composition contains at least one selected from polyolefin, polystyrene, polyimide, polyamide, polyphenylene sulfide, polymethyl methacrylate, and polycarbonate.
[12] A fullerene derivative-containing resin composition comprising a fullerene derivative in which indene, which may have a substituent, is added to the fullerene skeleton, and a resin.
[13] A resin composition obtained by the production method according to [6] to [9].
［２］ 前記有機溶媒が、Ｎ－メチル－２－ピロリドン、酢酸エチル、酢酸ブチル、メチルエチルケトン、プロピレングリコールモノメチルエーテルアセテート及びシクロヘキサノンから選ばれる、１種の溶媒または複数種の混合溶媒である前項［１］に記載の樹脂添加剤。
［３］ 前記フラーレン誘導体が下記式（１）で表される前項［１］または［２］に記載の樹脂添加剤。
［４］ 置換基を有してもよいインデンがフラーレン骨格に複数付加している前項［１］～［３］のいずれかに記載の樹脂添加剤。
［５］ 樹脂と前項［１］～［４］のいずれかに記載の樹脂添加剤との混合物（以下「樹脂混合物」という。）を得る工程および前記樹脂混合物から溶媒を除去する工程を有する樹脂組成物の製造方法。
［６］ 前記樹脂混合物を得る工程が、重合して樹脂となる材料と前記樹脂添加剤との混合物（以下「原料混合物」という。）を得る工程および前記原料混合物中の前記材料を重合する工程を有する前項［５］に記載の樹脂組成物の製造方法。
［７］ さらに、前記樹脂混合物を１２０～３５０℃で１～１００時間加熱する工程を有する前項［５］または［６］に記載の樹脂組成物の製造方法。
［８］ 前記樹脂が熱可塑性樹脂である前項［７］に記載の樹脂組成物の製造方法。
［９］ 置換基を有してもよいインデンがフラーレン骨格に付加しているフラーレン誘導体の熱分解物及び樹脂を含む樹脂組成物。
［１０］ 前記熱分解物が、置換基を有してもよいインデンとフラーレンである前項［９］に記載の樹脂組成物。
［１１］ 前記樹脂組成物が、ポリオレフィン、ポリスチレン、ポリイミド、ポリアミド、ポリフェニレンスルファイド、ポリメタクリル酸メチル及びポリカーボネートから選ばれる少なくとも１種を含む前項［９］～［１０］に記載の樹脂組成物。
［１２］ 置換基を有してもよいインデンがフラーレン骨格に付加しているフラーレン誘導体及び樹脂を含むフラレーン誘導体含有樹脂組成物。
［１３］ ［６］～［９］に記載の製造方法で得られる樹脂組成物。 [1] A resin additive comprising an organic solvent solution of a fullerene derivative in which an indene which may have a substituent is added to a fullerene skeleton.
[2] In the preceding item, the organic solvent is one solvent or a mixed solvent selected from N-methyl-2-pyrrolidone, ethyl acetate, butyl acetate, methyl ethyl ketone, propylene glycol monomethyl ether acetate and cyclohexanone. ] The resin additive as described in.
[3] The resin additive according to [1] or [2], wherein the fullerene derivative is represented by the following formula (1).
[4] The resin additive as described in any one of [1] to [3] above, wherein a plurality of indenes which may have a substituent are added to the fullerene skeleton.
[5] A resin having a step of obtaining a mixture of the resin and the resin additive according to any one of [1] to [4] (hereinafter referred to as “resin mixture”) and a step of removing the solvent from the resin mixture. A method for producing the composition.
[6] The step of obtaining the resin mixture includes a step of obtaining a mixture of a material that is polymerized into a resin and the resin additive (hereinafter referred to as “raw material mixture”), and a step of polymerizing the material in the raw material mixture. The manufacturing method of the resin composition as described in the preceding clause [5] which has these.
[7] The method for producing a resin composition according to [5] or [6] above, further comprising a step of heating the resin mixture at 120 to 350 ° C. for 1 to 100 hours.
[8] The method for producing a resin composition according to [7], wherein the resin is a thermoplastic resin.
[9] A resin composition comprising a thermally decomposed product of a fullerene derivative in which an indene which may have a substituent is added to a fullerene skeleton, and a resin.
[10] The resin composition according to [9], wherein the thermal decomposition product is indene and fullerene which may have a substituent.
[11] The resin composition as described in [9] to [10] above, wherein the resin composition contains at least one selected from polyolefin, polystyrene, polyimide, polyamide, polyphenylene sulfide, polymethyl methacrylate, and polycarbonate.
[12] A fullerene derivative-containing resin composition comprising a fullerene derivative in which indene, which may have a substituent, is added to the fullerene skeleton, and a resin.
[13] A resin composition obtained by the production method according to [6] to [9].
本発明の樹脂添加剤、または、本発明の樹脂組成物の製造方法を用いることにより、多種の樹脂にフラーレンを分散して含有させることができる。
By using the resin additive of the present invention or the method for producing the resin composition of the present invention, fullerenes can be dispersed and contained in various resins.
（樹脂添加剤）
本発明の樹脂添加剤は、置換基を有してもよいインデンがフラーレン骨格に付加しているフラーレン誘導体（以下、単に「フラーレン誘導体」と言うことがある。）の有機溶媒溶液からなる。 (Resin additive)
The resin additive of the present invention comprises an organic solvent solution of a fullerene derivative (hereinafter sometimes simply referred to as “fullerene derivative”) in which an indene which may have a substituent is added to the fullerene skeleton.
本発明の樹脂添加剤は、置換基を有してもよいインデンがフラーレン骨格に付加しているフラーレン誘導体（以下、単に「フラーレン誘導体」と言うことがある。）の有機溶媒溶液からなる。 (Resin additive)
The resin additive of the present invention comprises an organic solvent solution of a fullerene derivative (hereinafter sometimes simply referred to as “fullerene derivative”) in which an indene which may have a substituent is added to the fullerene skeleton.
（有機溶媒）
前記有機溶媒としては、前記フラーレン誘導体を溶解可能な溶媒である。より好ましい溶媒は、使用する樹脂及びフラーレン誘導体の両方を十分に溶解し得る溶媒であり、使用する樹脂及びフラーレン誘導体の組み合わせに依存する。例えば、Ｎ－メチル－２－ピロリドン（以下「ＮＭＰ」ということがある。）、酢酸エチル、酢酸ブチル、メチルエチルケトン、プロピレングリコールモノメチルエーテルアセテート（以下「ＰＧＭＡ」ということがある。）及びシクロヘキサノンから選ばれる、１種の溶媒または複数種の混合溶媒が挙げられる。 (Organic solvent)
The organic solvent is a solvent that can dissolve the fullerene derivative. A more preferable solvent is a solvent that can sufficiently dissolve both the resin and fullerene derivative used, and depends on the combination of the resin and fullerene derivative used. For example, N-methyl-2-pyrrolidone (hereinafter sometimes referred to as “NMP”), ethyl acetate, butyl acetate, methyl ethyl ketone, propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as “PGMA”) and cyclohexanone. One kind of solvent or a plurality of kinds of mixed solvents may be mentioned.
前記有機溶媒としては、前記フラーレン誘導体を溶解可能な溶媒である。より好ましい溶媒は、使用する樹脂及びフラーレン誘導体の両方を十分に溶解し得る溶媒であり、使用する樹脂及びフラーレン誘導体の組み合わせに依存する。例えば、Ｎ－メチル－２－ピロリドン（以下「ＮＭＰ」ということがある。）、酢酸エチル、酢酸ブチル、メチルエチルケトン、プロピレングリコールモノメチルエーテルアセテート（以下「ＰＧＭＡ」ということがある。）及びシクロヘキサノンから選ばれる、１種の溶媒または複数種の混合溶媒が挙げられる。 (Organic solvent)
The organic solvent is a solvent that can dissolve the fullerene derivative. A more preferable solvent is a solvent that can sufficiently dissolve both the resin and fullerene derivative used, and depends on the combination of the resin and fullerene derivative used. For example, N-methyl-2-pyrrolidone (hereinafter sometimes referred to as “NMP”), ethyl acetate, butyl acetate, methyl ethyl ketone, propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as “PGMA”) and cyclohexanone. One kind of solvent or a plurality of kinds of mixed solvents may be mentioned.
これらの溶媒は、樹脂を製造する過程において広く使用される溶媒である。そのため、本発明の樹脂添加剤は、後述の樹脂製造方法を用いて、多種の樹脂に適用することができる。
These solvents are widely used in the process of producing a resin. Therefore, the resin additive of the present invention can be applied to various resins using a resin production method described later.
（フラーレン誘導体）
本発明の樹脂添加剤に用いるフラーレン誘導体は、置換基を有してもよいインデンがフラーレン骨格に付加している（以下「置換基を有してもよいインデン」を単に「付加基」ということもある。）。フラーレンをこのような誘導体にすることにより、多種の溶媒に溶解させることができるようになり、また、ラジカルトラップ能が抑制されるので後述するラジカル重合時に添加できるようになる。 (Fullerene derivative)
In the fullerene derivative used in the resin additive of the present invention, an indene which may have a substituent is added to the fullerene skeleton (hereinafter, “an indene which may have a substituent” is simply referred to as “addition group”). There is also.) By making fullerene into such a derivative, it can be dissolved in various solvents, and since radical trapping ability is suppressed, it can be added during radical polymerization described later.
本発明の樹脂添加剤に用いるフラーレン誘導体は、置換基を有してもよいインデンがフラーレン骨格に付加している（以下「置換基を有してもよいインデン」を単に「付加基」ということもある。）。フラーレンをこのような誘導体にすることにより、多種の溶媒に溶解させることができるようになり、また、ラジカルトラップ能が抑制されるので後述するラジカル重合時に添加できるようになる。 (Fullerene derivative)
In the fullerene derivative used in the resin additive of the present invention, an indene which may have a substituent is added to the fullerene skeleton (hereinafter, “an indene which may have a substituent” is simply referred to as “addition group”). There is also.) By making fullerene into such a derivative, it can be dissolved in various solvents, and since radical trapping ability is suppressed, it can be added during radical polymerization described later.
前記置換基は、必須ではないが、フラーレン誘導体の前記有機溶媒への溶解性を高めるために適切に選択されることが好ましい。例えば、極性溶媒への溶解性を高めるには、ポリエチレングリコール鎖（例えば、炭素数４～１０のポリエチレングリコール鎖）などの親水性の置換基を導入すればよい。逆に、非極性溶媒への溶解性を高めるには、炭化水素鎖（例えば、炭素数１～１２の炭化水素鎖）などの疎水性の置換基を導入すればよい。
The substituent is not essential, but is preferably selected in order to enhance the solubility of the fullerene derivative in the organic solvent. For example, in order to increase the solubility in a polar solvent, a hydrophilic substituent such as a polyethylene glycol chain (for example, a polyethylene glycol chain having 4 to 10 carbon atoms) may be introduced. Conversely, in order to increase the solubility in a nonpolar solvent, a hydrophobic substituent such as a hydrocarbon chain (for example, a hydrocarbon chain having 1 to 12 carbon atoms) may be introduced.
前記付加基は、その複数がフラーレン骨格に付加していることが好ましい。付加数が多い方が、フラーレン誘導体がより有機溶媒に溶解しやすくなるので使用可能な溶媒の選択肢を広げることができ、また、フラーレン誘導体のラジカルトラップ能をさらに抑えることができる。なお、付加数の上限は、フラーレン骨格の大きさが大きいほど多くなる。フラーレンはＣ６０からＣ２００程度まで種々の大きさのものが知られており、例えば、種々のフラーレンの中で最も小さいフラーレン骨格ではあるが入手性に優れるＣ６０を用いた場合、前記付加数の上限は約２０である。ただし、付加基の導入のしやすさから、付加数は２～１０が好ましく、２～４がより好ましい。
It is preferable that a plurality of the additional groups are added to the fullerene skeleton. When the number of additions is larger, the fullerene derivative is more easily dissolved in an organic solvent, so that the choice of usable solvents can be expanded, and the radical trapping ability of the fullerene derivative can be further suppressed. Note that the upper limit of the number of additions increases as the size of the fullerene skeleton increases. Fullerenes having various sizes from about C 60 to about C 200 are known. For example, when C 60 which is the smallest fullerene skeleton among various fullerenes but has excellent availability is used, The upper limit of is about 20. However, the addition number is preferably 2 to 10 and more preferably 2 to 4 in view of ease of introduction of the addition group.
より具体的なフラーレン誘導体の例としては、下記式（１）で表されるフラーレン誘導体が挙げられる。
（式（１）中のＦＬＮはフラーレン骨格を示し、ｎは１以上の整数を示し、Ａｒ１は、置換基を有していてもよいベンゼン環を示す。）
式（１）中のＦＬＮがＣ６０、Ｃ７０の骨格であることが好ましい。
Ａｒ１はベンゼン環であることが好ましい。
ｎは１～３の前記式（１）で表されるフラーレン誘導体をいずれか単独に含むことが好ましく、何れも含むことがより好ましい。
ｎは１～３の前記式（１）で表されるフラーレン誘導体を何れも含む場合、前記フラーレン誘導体に含まれる各フラーレン誘導体の含有量が１０～６０質量％であり、かつ合計量が９０％～１００％であることが好ましい。 More specific examples of fullerene derivatives include fullerene derivatives represented by the following formula (1).
(FLN in Formula (1) represents a fullerene skeleton, n represents an integer of 1 or more, and Ar 1 represents a benzene ring which may have a substituent.)
FLN in the formula (1) is preferably a C 60 , C 70 skeleton.
Ar 1 is preferably a benzene ring.
n preferably contains one to three of the fullerene derivatives represented by the above formula (1), more preferably all of them.
In the case where n contains any of the fullerene derivatives represented by the formula (1) of 1 to 3, the content of each fullerene derivative contained in the fullerene derivative is 10 to 60% by mass, and the total amount is 90% It is preferable that it is ˜100%.
式（１）中のＦＬＮがＣ６０、Ｃ７０の骨格であることが好ましい。
Ａｒ１はベンゼン環であることが好ましい。
ｎは１～３の前記式（１）で表されるフラーレン誘導体をいずれか単独に含むことが好ましく、何れも含むことがより好ましい。
ｎは１～３の前記式（１）で表されるフラーレン誘導体を何れも含む場合、前記フラーレン誘導体に含まれる各フラーレン誘導体の含有量が１０～６０質量％であり、かつ合計量が９０％～１００％であることが好ましい。 More specific examples of fullerene derivatives include fullerene derivatives represented by the following formula (1).
FLN in the formula (1) is preferably a C 60 , C 70 skeleton.
Ar 1 is preferably a benzene ring.
n preferably contains one to three of the fullerene derivatives represented by the above formula (1), more preferably all of them.
In the case where n contains any of the fullerene derivatives represented by the formula (1) of 1 to 3, the content of each fullerene derivative contained in the fullerene derivative is 10 to 60% by mass, and the total amount is 90% It is preferable that it is ˜100%.
（樹脂組成物の製造方法）
本発明の樹脂組成物の製造方法は、樹脂と前記樹脂添加剤との混合物からなる樹脂混合物を得る工程および前記樹脂混合物から溶媒を除去する工程を有する。 (Production method of resin composition)
The manufacturing method of the resin composition of this invention has the process of obtaining the resin mixture which consists of a mixture of resin and the said resin additive, and the process of removing a solvent from the said resin mixture.
本発明の樹脂組成物の製造方法は、樹脂と前記樹脂添加剤との混合物からなる樹脂混合物を得る工程および前記樹脂混合物から溶媒を除去する工程を有する。 (Production method of resin composition)
The manufacturing method of the resin composition of this invention has the process of obtaining the resin mixture which consists of a mixture of resin and the said resin additive, and the process of removing a solvent from the said resin mixture.
（樹脂混合物を得る工程）
前記樹脂混合物を得る方法は、特に限定されないが、樹脂中のフラーレン誘導体の良好な分散性を得るために、本発明の樹脂添加剤と樹脂が液体状態で混合されることが好ましい。例えば、溶媒に溶解する樹脂であれば、前記樹脂添加剤に直接樹脂を溶解する方法、樹脂を溶解可能な溶媒に樹脂を溶液して前記樹脂添加剤と混合する方法などが挙げられる。樹脂が熱可塑性樹脂であれば、溶融している熱可塑性樹脂と前記樹脂添加剤とを混合する方法などが挙げられる。 (Step of obtaining a resin mixture)
The method for obtaining the resin mixture is not particularly limited, but it is preferable that the resin additive of the present invention and the resin are mixed in a liquid state in order to obtain good dispersibility of the fullerene derivative in the resin. For example, in the case of a resin that dissolves in a solvent, a method of directly dissolving the resin in the resin additive, a method of dissolving the resin in a solvent capable of dissolving the resin, and a method of mixing with the resin additive can be given. If resin is a thermoplastic resin, the method etc. which mix the molten thermoplastic resin and the said resin additive are mentioned.
前記樹脂混合物を得る方法は、特に限定されないが、樹脂中のフラーレン誘導体の良好な分散性を得るために、本発明の樹脂添加剤と樹脂が液体状態で混合されることが好ましい。例えば、溶媒に溶解する樹脂であれば、前記樹脂添加剤に直接樹脂を溶解する方法、樹脂を溶解可能な溶媒に樹脂を溶液して前記樹脂添加剤と混合する方法などが挙げられる。樹脂が熱可塑性樹脂であれば、溶融している熱可塑性樹脂と前記樹脂添加剤とを混合する方法などが挙げられる。 (Step of obtaining a resin mixture)
The method for obtaining the resin mixture is not particularly limited, but it is preferable that the resin additive of the present invention and the resin are mixed in a liquid state in order to obtain good dispersibility of the fullerene derivative in the resin. For example, in the case of a resin that dissolves in a solvent, a method of directly dissolving the resin in the resin additive, a method of dissolving the resin in a solvent capable of dissolving the resin, and a method of mixing with the resin additive can be given. If resin is a thermoplastic resin, the method etc. which mix the molten thermoplastic resin and the said resin additive are mentioned.
さらに、前記樹脂混合物を得る方法としては、重合して樹脂となる材料と前記樹脂添加剤との混合物からなる原料混合物を得て、この原料混合物中で前記材料を重合する方法などが挙げられる。重合形式は、重縮合、重付加、イオン重合、ラジカル重合が可能である。前記フラーレン誘導体はラジカルトラップ能が抑えられているので、重合形式はラジカル重合であってもよい。
Further, as a method of obtaining the resin mixture, there is a method of obtaining a raw material mixture composed of a mixture of a material that is polymerized into a resin and the resin additive, and polymerizing the material in the raw material mixture. As the polymerization method, polycondensation, polyaddition, ionic polymerization, and radical polymerization are possible. Since the fullerene derivative has suppressed radical trapping ability, the polymerization form may be radical polymerization.
（樹脂混合物から溶媒を除去する工程）
樹脂混合物から溶媒を除去する方法は、特に限定されないが、加熱、減圧及び／又は風乾などが挙げられる。通常、後述するフラーレン誘導体の熱分解の温度・時間の範囲内で溶媒は除去される。
樹脂混合物から溶媒を除去する後、後述の熱分解工程を行う前、フラーレン誘導体含有樹脂組成物が得られる。 (Step of removing the solvent from the resin mixture)
The method for removing the solvent from the resin mixture is not particularly limited, and examples thereof include heating, decompression and / or air drying. Usually, the solvent is removed within the range of the temperature and time of thermal decomposition of the fullerene derivative described later.
After removing the solvent from the resin mixture, a fullerene derivative-containing resin composition is obtained before performing the pyrolysis step described below.
樹脂混合物から溶媒を除去する方法は、特に限定されないが、加熱、減圧及び／又は風乾などが挙げられる。通常、後述するフラーレン誘導体の熱分解の温度・時間の範囲内で溶媒は除去される。
樹脂混合物から溶媒を除去する後、後述の熱分解工程を行う前、フラーレン誘導体含有樹脂組成物が得られる。 (Step of removing the solvent from the resin mixture)
The method for removing the solvent from the resin mixture is not particularly limited, and examples thereof include heating, decompression and / or air drying. Usually, the solvent is removed within the range of the temperature and time of thermal decomposition of the fullerene derivative described later.
After removing the solvent from the resin mixture, a fullerene derivative-containing resin composition is obtained before performing the pyrolysis step described below.
（フラーレン誘導体の熱分解工程）
フラーレンのインデン付加体は、加熱をすると、フラーレンとインデンとに分解することが知られている。本発明では、この性質を利用して、前記樹脂混合物及び／又は前記フラーレン誘導体含有樹脂組成物中のフラーレン誘導体を熱分解し、該組成物中にフラーレンを生じさせる。なお、フラーレンはフラーレン誘導体よりラジカルトラップ能が優れる。 (Thermal decomposition process of fullerene derivatives)
It is known that an indene adduct of fullerene decomposes into fullerene and indene when heated. In the present invention, using this property, the fullerene derivative in the resin mixture and / or the fullerene derivative-containing resin composition is thermally decomposed to produce fullerene in the composition. In addition, fullerene is superior in radical trapping ability to fullerene derivatives.
フラーレンのインデン付加体は、加熱をすると、フラーレンとインデンとに分解することが知られている。本発明では、この性質を利用して、前記樹脂混合物及び／又は前記フラーレン誘導体含有樹脂組成物中のフラーレン誘導体を熱分解し、該組成物中にフラーレンを生じさせる。なお、フラーレンはフラーレン誘導体よりラジカルトラップ能が優れる。 (Thermal decomposition process of fullerene derivatives)
It is known that an indene adduct of fullerene decomposes into fullerene and indene when heated. In the present invention, using this property, the fullerene derivative in the resin mixture and / or the fullerene derivative-containing resin composition is thermally decomposed to produce fullerene in the composition. In addition, fullerene is superior in radical trapping ability to fullerene derivatives.
前記熱分解は、生じたフラーレンの凝集を防ぐため、前記フラーレン誘導体含有樹脂組成物中で行うのが好ましい。前記樹脂混合物を得る方法は、重合して樹脂となる材料と前記樹脂添加剤との混合物からなる原料混合物を得て、この原料混合物中で前記材料を重合する方法である場合、硬化後に行うのが好ましい。
The thermal decomposition is preferably performed in the fullerene derivative-containing resin composition in order to prevent aggregation of the fullerene generated. The method of obtaining the resin mixture is a method of obtaining a raw material mixture composed of a mixture of a material that becomes a resin by polymerization and the resin additive, and polymerizing the material in the raw material mixture. Is preferred.
前記熱分解の温度は、フラーレン誘導体が分解する温度以上で樹脂へのダメージが許容できる温度以下であることが好ましく、樹脂の種類などによるが、１２０℃～３５０℃がより好ましく、２００℃～３５０℃がさらに好ましい。熱分解の時間は、大部分のフラーレン誘導体が分解する時間以上で樹脂へのダメージが許容できる時間内であることが好ましく、加熱温度や樹脂の種類などによるが、１～１００時間の範囲内がより好ましく、２０～５０時間であることがさらに好ましい。なお、熱分解は連続して行う必要は無く、複数回に分けてもよい。
The thermal decomposition temperature is preferably higher than the temperature at which the fullerene derivative is decomposed and lower than the temperature at which damage to the resin can be tolerated. Depending on the type of the resin, it is more preferably 120 ° C. to 350 ° C. More preferably. The thermal decomposition time is preferably within a time over which most of the fullerene derivative is decomposed and within which the damage to the resin can be tolerated. Depending on the heating temperature, the type of resin, etc. More preferably, it is 20 to 50 hours. The thermal decomposition does not need to be performed continuously, and may be divided into a plurality of times.
ただし、樹脂組成物が使用される環境下で上記熱分解と同様の加熱がなされるならば、該樹脂組成物の製造工程中に熱分解する工程を設ける必要は無い。
However, if heating similar to the above thermal decomposition is performed in an environment where the resin composition is used, it is not necessary to provide a thermal decomposition step during the manufacturing process of the resin composition.
前記樹脂組成物中の樹脂が熱可塑性樹脂である場合、一般に使用される環境下で加熱されることが少ないので、前記熱分解の工程を設けることが好ましい。成形時及び／または成形前に上記熱分解と同様な加熱がなされるようにしておくとよい。
When the resin in the resin composition is a thermoplastic resin, it is preferable that the thermal decomposition step is provided because it is rarely heated in a generally used environment. It is preferable that heating similar to the above thermal decomposition is performed at the time of molding and / or before molding.
前記熱分解工程を経た樹脂組成物は、前記フラーレン誘導体の熱分解物を含む。分解物は、通常、フラーレンと前記フラーレン誘導体に付加していた置換基を有してもよいインデンとなる。このとき、樹脂組成物中のフラーレン含有量は、好ましくは０．００１質量％～１０質量％、より好ましくは０．０１質量％～１質量％、さらに好ましくは０．０２質量％～０．５質量％である。樹脂組成物中のフラーレン含有量は、熱分解条件やフラーレン誘導体と樹脂との混合比率を調整するなどして調整できる。
The resin composition that has undergone the thermal decomposition step includes a thermal decomposition product of the fullerene derivative. The decomposition product is usually indene which may have a substituent added to fullerene and the fullerene derivative. At this time, the fullerene content in the resin composition is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass, and further preferably 0.02% by mass to 0.5%. % By mass. The fullerene content in the resin composition can be adjusted by adjusting the thermal decomposition conditions or the mixing ratio of the fullerene derivative and the resin.
本発明の樹脂組成物中に含まれる樹脂としては、前記樹脂添加剤を利用できる樹脂であればよく、例えば、ポリオレフィン、ポリスチレン、ポリイミド、ポリアミド、ポリイミド、ポリフェニレンスルファイド、ポリメタクリル酸メチル及びポリカーボネート等が挙げられる。
The resin contained in the resin composition of the present invention may be any resin that can use the resin additive, such as polyolefin, polystyrene, polyimide, polyamide, polyimide, polyphenylene sulfide, polymethyl methacrylate, and polycarbonate. Is mentioned.
以下に本発明の実施例を示し、本発明をより具体的に説明する。なお、これらは説明のための単なる例示であって、本発明はこれらによって何ら制限されるものではない。
Hereinafter, examples of the present invention will be shown to describe the present invention more specifically. Note that these are merely illustrative examples, and the present invention is not limited by these.
実施例１：
（フラーレン誘導体の合成）
フラーレンＣ６０１０ｇと，インデン３２ｇとをｏ－ジクロロベンゼン１２０ｍＬ中で２０時間還流し反応させた。反応後の溶液をシリカゲルを用いてろ過した。ろ液に、攪拌しながらメタノール５００ｍＬを滴下し、固体を析出させた。析出した固体をメタノールで洗浄し、目的物１として黒色固体１０ｇを得た。 Example 1:
(Synthesis of fullerene derivatives)
Fullerene C 60 ( 10 g) and indene (32 g) were reacted by refluxing in 120 mL of o-dichlorobenzene for 20 hours. The solution after the reaction was filtered using silica gel. While stirring, 500 mL of methanol was added dropwise to the filtrate to precipitate a solid. The precipitated solid was washed with methanol to obtain 10 g of a black solid as the target product 1.
（フラーレン誘導体の合成）
フラーレンＣ６０１０ｇと，インデン３２ｇとをｏ－ジクロロベンゼン１２０ｍＬ中で２０時間還流し反応させた。反応後の溶液をシリカゲルを用いてろ過した。ろ液に、攪拌しながらメタノール５００ｍＬを滴下し、固体を析出させた。析出した固体をメタノールで洗浄し、目的物１として黒色固体１０ｇを得た。 Example 1:
(Synthesis of fullerene derivatives)
Fullerene C 60 ( 10 g) and indene (32 g) were reacted by refluxing in 120 mL of o-dichlorobenzene for 20 hours. The solution after the reaction was filtered using silica gel. While stirring, 500 mL of methanol was added dropwise to the filtrate to precipitate a solid. The precipitated solid was washed with methanol to obtain 10 g of a black solid as the target product 1.
目的物１中の、フラーレン、フラーレンのインデン一付加体、同二付加体、および同三付加体以上の多付加体組成比を、ＨＰＬＣにより分析した。その結果、フラーレン０．９質量％、一付加体３２．７質量％、二付加体５０．４質量％、三付加体以上１５．９質量％の組成比であった。
The target compound 1 was analyzed by HPLC for the composition ratio of fullerene, fullerene indene monoadduct, diadduct, and triad or higher adduct. As a result, the composition ratio was 0.9% by mass of fullerene, 32.7% by mass of a monoadduct, 50.4% by mass of a diadduct, and 15.9% by mass of a triadduct or more.
（溶解度測定）
６ｍＬのバイアル瓶に、表１に示す各溶媒２ｇと目的物１を２０ｍｇ入れ、５時間撹拌を行った。その後、０．２μｍのフィルターを用いてろ過を行った後、ＵＶ－Ｖｉｓ吸光度測定を行い、溶液の吸光度を測定した。その４２０ｎｍの吸光度を目的物が０．１質量％溶解したトルエン溶液の吸光度と比較することで、溶解度を算出した。その結果を表１に示す。 (Solubility measurement)
In a 6 mL vial, 2 g of each solvent shown in Table 1 and 20 mg of the target product 1 were placed and stirred for 5 hours. Thereafter, filtration was performed using a 0.2 μm filter, and then UV-Vis absorbance measurement was performed to measure the absorbance of the solution. The solubility was calculated by comparing the absorbance at 420 nm with the absorbance of a toluene solution in which 0.1% by mass of the target product was dissolved. The results are shown in Table 1.
６ｍＬのバイアル瓶に、表１に示す各溶媒２ｇと目的物１を２０ｍｇ入れ、５時間撹拌を行った。その後、０．２μｍのフィルターを用いてろ過を行った後、ＵＶ－Ｖｉｓ吸光度測定を行い、溶液の吸光度を測定した。その４２０ｎｍの吸光度を目的物が０．１質量％溶解したトルエン溶液の吸光度と比較することで、溶解度を算出した。その結果を表１に示す。 (Solubility measurement)
In a 6 mL vial, 2 g of each solvent shown in Table 1 and 20 mg of the target product 1 were placed and stirred for 5 hours. Thereafter, filtration was performed using a 0.2 μm filter, and then UV-Vis absorbance measurement was performed to measure the absorbance of the solution. The solubility was calculated by comparing the absorbance at 420 nm with the absorbance of a toluene solution in which 0.1% by mass of the target product was dissolved. The results are shown in Table 1.
比較例１：
目的物１の代わりにフラーレンＣ６０を用い、実施例１と同様に溶解度を算出した。
Comparative Example 1:
Solubility was calculated in the same manner as in Example 1 except that fullerene C 60 was used instead of the target product 1.
目的物１の代わりにフラーレンＣ６０を用い、実施例１と同様に溶解度を算出した。
Comparative Example 1:
Solubility was calculated in the same manner as in Example 1 except that fullerene C 60 was used instead of the target product 1.
表１の結果によれば、目的物１は、Ｃ６０が溶解しない多くの溶媒にも溶解することがわかる。
According to the results of Table 1, the target compound 1 is found to dissolve in many solvents that C 60 is not dissolved.
実施例２：
（１０％質量減少温度の測定）
ＮＥＴＺＳＣＨ社 ＴＧ－ＤＴＡ２０００ＳＲを用いて、約２００ｍｇの樹脂組成物を試料として、昇温速度１０℃／分、空気下で、試料の質量が１０％減少した温度を取得した。
（樹脂組成物のガラス転移点（Ｔｇ）測定）
メトラー社ＤＳＣ－１を用いて吸熱ピークの温度を取得した。 Example 2:
(Measurement of 10% mass loss temperature)
Using TG-DTA2000SR manufactured by NETZSCH, a temperature at which the mass of the sample was reduced by 10% was obtained under the air at a heating rate of 10 ° C./min using about 200 mg of the resin composition as a sample.
(Measurement of glass transition point (Tg) of resin composition)
The temperature of the endothermic peak was obtained using a Mettler DSC-1.
（１０％質量減少温度の測定）
ＮＥＴＺＳＣＨ社 ＴＧ－ＤＴＡ２０００ＳＲを用いて、約２００ｍｇの樹脂組成物を試料として、昇温速度１０℃／分、空気下で、試料の質量が１０％減少した温度を取得した。
（樹脂組成物のガラス転移点（Ｔｇ）測定）
メトラー社ＤＳＣ－１を用いて吸熱ピークの温度を取得した。 Example 2:
(Measurement of 10% mass loss temperature)
Using TG-DTA2000SR manufactured by NETZSCH, a temperature at which the mass of the sample was reduced by 10% was obtained under the air at a heating rate of 10 ° C./min using about 200 mg of the resin composition as a sample.
(Measurement of glass transition point (Tg) of resin composition)
The temperature of the endothermic peak was obtained using a Mettler DSC-1.
（熱硬化性樹脂）
本発明の樹脂添加剤１として、目的物１が０．１質量％溶解したＮＭＰ溶液を用意した。ポリイミド系樹脂として、ビス［４－（アリルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド）フェニル］メタン１０ｇを用い、２０ｇの樹脂添加剤１に溶解させた。この溶液を窒素下で１８０℃で２４時間加熱し固形分を得た。得られた固形分を２５０℃で２４時間加熱し、ＮＭＰを蒸散させ、フラーレン誘導体の熱分解を行った。その結果、樹脂組成物として透明な褐色の硬化物を得た。得られた樹脂組成物の測定結果を表２に示す。 (Thermosetting resin)
As the resin additive 1 of the present invention, an NMP solution in which 0.1% by mass of the target product 1 was dissolved was prepared. As a polyimide resin, 10 g of bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl] methane was used and dissolved in 20 g of resin additive 1. . This solution was heated at 180 ° C. for 24 hours under nitrogen to obtain a solid content. The obtained solid content was heated at 250 ° C. for 24 hours to evaporate NMP, and the fullerene derivative was thermally decomposed. As a result, a transparent brown cured product was obtained as the resin composition. Table 2 shows the measurement results of the obtained resin composition.
本発明の樹脂添加剤１として、目的物１が０．１質量％溶解したＮＭＰ溶液を用意した。ポリイミド系樹脂として、ビス［４－（アリルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド）フェニル］メタン１０ｇを用い、２０ｇの樹脂添加剤１に溶解させた。この溶液を窒素下で１８０℃で２４時間加熱し固形分を得た。得られた固形分を２５０℃で２４時間加熱し、ＮＭＰを蒸散させ、フラーレン誘導体の熱分解を行った。その結果、樹脂組成物として透明な褐色の硬化物を得た。得られた樹脂組成物の測定結果を表２に示す。 (Thermosetting resin)
As the resin additive 1 of the present invention, an NMP solution in which 0.1% by mass of the target product 1 was dissolved was prepared. As a polyimide resin, 10 g of bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl] methane was used and dissolved in 20 g of resin additive 1. . This solution was heated at 180 ° C. for 24 hours under nitrogen to obtain a solid content. The obtained solid content was heated at 250 ° C. for 24 hours to evaporate NMP, and the fullerene derivative was thermally decomposed. As a result, a transparent brown cured product was obtained as the resin composition. Table 2 shows the measurement results of the obtained resin composition.
比較例２
樹脂添加剤１の代わりにＮＭＰを用いたこと以外は、実施例２と同様の操作及び測定を行った。その結果、樹脂組成物として透明な硬化物を得た。得られた樹脂組成物の測定結果を表２に示す。 Comparative Example 2
The same operation and measurement as in Example 2 were performed except that NMP was used in place of the resin additive 1. As a result, a transparent cured product was obtained as the resin composition. Table 2 shows the measurement results of the obtained resin composition.
樹脂添加剤１の代わりにＮＭＰを用いたこと以外は、実施例２と同様の操作及び測定を行った。その結果、樹脂組成物として透明な硬化物を得た。得られた樹脂組成物の測定結果を表２に示す。 Comparative Example 2
The same operation and measurement as in Example 2 were performed except that NMP was used in place of the resin additive 1. As a result, a transparent cured product was obtained as the resin composition. Table 2 shows the measurement results of the obtained resin composition.
比較例３
樹脂添加剤１の代わりにフラーレン（フロンティアカーボン社ＮＭ－ＳＴ－Ｆ）を０．１質量％分散させたＮＭＰ分散液を用いたこと以外は、実施例２と同様の操作及び測定を行った。その結果、樹脂組成物として濁った褐色の硬化物を得た。得られた樹脂組成物の測定結果を表２に示す。 Comparative Example 3
The same operation and measurement as in Example 2 were performed except that an NMP dispersion in which 0.1% by mass of fullerene (frontier carbon NM-ST-F) was used instead of the resin additive 1 was used. As a result, a turbid brown cured product was obtained as a resin composition. Table 2 shows the measurement results of the obtained resin composition.
樹脂添加剤１の代わりにフラーレン（フロンティアカーボン社ＮＭ－ＳＴ－Ｆ）を０．１質量％分散させたＮＭＰ分散液を用いたこと以外は、実施例２と同様の操作及び測定を行った。その結果、樹脂組成物として濁った褐色の硬化物を得た。得られた樹脂組成物の測定結果を表２に示す。 Comparative Example 3
The same operation and measurement as in Example 2 were performed except that an NMP dispersion in which 0.1% by mass of fullerene (frontier carbon NM-ST-F) was used instead of the resin additive 1 was used. As a result, a turbid brown cured product was obtained as a resin composition. Table 2 shows the measurement results of the obtained resin composition.
実施例３：
（熱可塑性樹脂）
ポリメタクリル酸メチル１０ｇを１２０℃で５０ｇの樹脂添加剤１に溶解させた。これを減圧下１２０℃で２４時間かけて溶媒を留去し、樹脂組成物として透明な褐色の硬化物を得た。実施例２と同様の測定を行い、得られた樹脂組成物の測定結果を表３に示す。 Example 3:
(Thermoplastic resin)
10 g of polymethyl methacrylate was dissolved in 50 g of resin additive 1 at 120 ° C. The solvent was distilled off for 24 hours at 120 ° C. under reduced pressure to obtain a transparent brown cured product as a resin composition. The same measurement as in Example 2 was performed, and the measurement result of the obtained resin composition is shown in Table 3.
（熱可塑性樹脂）
ポリメタクリル酸メチル１０ｇを１２０℃で５０ｇの樹脂添加剤１に溶解させた。これを減圧下１２０℃で２４時間かけて溶媒を留去し、樹脂組成物として透明な褐色の硬化物を得た。実施例２と同様の測定を行い、得られた樹脂組成物の測定結果を表３に示す。 Example 3:
(Thermoplastic resin)
10 g of polymethyl methacrylate was dissolved in 50 g of resin additive 1 at 120 ° C. The solvent was distilled off for 24 hours at 120 ° C. under reduced pressure to obtain a transparent brown cured product as a resin composition. The same measurement as in Example 2 was performed, and the measurement result of the obtained resin composition is shown in Table 3.
比較例４：
樹脂添加剤１の代わりにＮＭＰを用いたこと以外は、実施例３と同様の操作及び測定を行った。その結果、樹脂組成物として透明な硬化物を得た。得られた樹脂組成物の測定結果を表３に示す。 Comparative Example 4:
The same operation and measurement as in Example 3 were performed except that NMP was used instead of the resin additive 1. As a result, a transparent cured product was obtained as the resin composition. The measurement results of the obtained resin composition are shown in Table 3.
樹脂添加剤１の代わりにＮＭＰを用いたこと以外は、実施例３と同様の操作及び測定を行った。その結果、樹脂組成物として透明な硬化物を得た。得られた樹脂組成物の測定結果を表３に示す。 Comparative Example 4:
The same operation and measurement as in Example 3 were performed except that NMP was used instead of the resin additive 1. As a result, a transparent cured product was obtained as the resin composition. The measurement results of the obtained resin composition are shown in Table 3.
比較例５
樹脂添加剤１の代わりにフラーレン（フロンティアカーボン社ＮＭ－ＳＴ－Ｆ）を０．１質量％分散させたＮＭＰ分散液を用いたこと以外は、実施例３と同様の操作及び測定を行った。その結果、樹脂組成物として濁った褐色の硬化物を得た。得られた樹脂組成物の測定結果を表３に示す。 Comparative Example 5
The same operation and measurement as in Example 3 were performed except that an NMP dispersion in which 0.1% by mass of fullerene (frontier carbon NM-ST-F) was used instead of the resin additive 1 was used. As a result, a turbid brown cured product was obtained as a resin composition. The measurement results of the obtained resin composition are shown in Table 3.
樹脂添加剤１の代わりにフラーレン（フロンティアカーボン社ＮＭ－ＳＴ－Ｆ）を０．１質量％分散させたＮＭＰ分散液を用いたこと以外は、実施例３と同様の操作及び測定を行った。その結果、樹脂組成物として濁った褐色の硬化物を得た。得られた樹脂組成物の測定結果を表３に示す。 Comparative Example 5
The same operation and measurement as in Example 3 were performed except that an NMP dispersion in which 0.1% by mass of fullerene (frontier carbon NM-ST-F) was used instead of the resin additive 1 was used. As a result, a turbid brown cured product was obtained as a resin composition. The measurement results of the obtained resin composition are shown in Table 3.
実施例４
（ラジカル重合）
本発明の樹脂添加剤２として、目的物１が０．１質量％溶解したトルエン溶液を用意した。スチレンモノマー５０ｇを５０ｇの樹脂添加剤２と混合し、これを１００℃で１２時間加熱して熱ラジカル重合及び溶媒の留去を行い、次に得られた固形物を２５０℃で２４時間加熱しフラーレン誘導体の熱分解を行った。その結果、樹脂組成物として透明な褐色の硬化物を得た。実施例２と同様の測定をした結果、得られた樹脂組成物の測定結果を表４に示す。 Example 4
(Radical polymerization)
As the resin additive 2 of the present invention, a toluene solution in which 0.1% by mass of the target product 1 was dissolved was prepared. 50 g of styrene monomer is mixed with 50 g of resin additive 2, and this is heated at 100 ° C. for 12 hours to perform thermal radical polymerization and evaporation of the solvent, and then the resulting solid is heated at 250 ° C. for 24 hours. Thermal decomposition of the fullerene derivative was performed. As a result, a transparent brown cured product was obtained as the resin composition. Table 4 shows the measurement results of the resin composition obtained as a result of the same measurement as in Example 2.
（ラジカル重合）
本発明の樹脂添加剤２として、目的物１が０．１質量％溶解したトルエン溶液を用意した。スチレンモノマー５０ｇを５０ｇの樹脂添加剤２と混合し、これを１００℃で１２時間加熱して熱ラジカル重合及び溶媒の留去を行い、次に得られた固形物を２５０℃で２４時間加熱しフラーレン誘導体の熱分解を行った。その結果、樹脂組成物として透明な褐色の硬化物を得た。実施例２と同様の測定をした結果、得られた樹脂組成物の測定結果を表４に示す。 Example 4
(Radical polymerization)
As the resin additive 2 of the present invention, a toluene solution in which 0.1% by mass of the target product 1 was dissolved was prepared. 50 g of styrene monomer is mixed with 50 g of resin additive 2, and this is heated at 100 ° C. for 12 hours to perform thermal radical polymerization and evaporation of the solvent, and then the resulting solid is heated at 250 ° C. for 24 hours. Thermal decomposition of the fullerene derivative was performed. As a result, a transparent brown cured product was obtained as the resin composition. Table 4 shows the measurement results of the resin composition obtained as a result of the same measurement as in Example 2.
比較例６
樹脂添加剤２の代わりにフラーレン（フロンティアカーボン社 ＮＭ－ＳＴ－Ｆ）を０．１質量％溶解させたトルエン溶液を用いたこと以外は、実施例４と同様の操作を行ったが、重合が進まず、硬化物が得られなかった。 Comparative Example 6
The same operation as in Example 4 was performed except that a toluene solution in which 0.1% by mass of fullerene (Frontier Carbon NM-ST-F) was used in place of the resin additive 2, but the polymerization was performed. The cured product could not be obtained.
樹脂添加剤２の代わりにフラーレン（フロンティアカーボン社 ＮＭ－ＳＴ－Ｆ）を０．１質量％溶解させたトルエン溶液を用いたこと以外は、実施例４と同様の操作を行ったが、重合が進まず、硬化物が得られなかった。 Comparative Example 6
The same operation as in Example 4 was performed except that a toluene solution in which 0.1% by mass of fullerene (Frontier Carbon NM-ST-F) was used in place of the resin additive 2, but the polymerization was performed. The cured product could not be obtained.
比較例７
スチレンに樹脂添加剤２を混合しなかったこと以外は実施例４と同様に操作及び測定を行った。その結果、樹脂組成物として透明な褐色の硬化物を得た。得られた樹脂組成物の測定結果を表４に示す。 Comparative Example 7
The operation and measurement were performed in the same manner as in Example 4 except that the resin additive 2 was not mixed with styrene. As a result, a transparent brown cured product was obtained as the resin composition. Table 4 shows the measurement results of the obtained resin composition.
スチレンに樹脂添加剤２を混合しなかったこと以外は実施例４と同様に操作及び測定を行った。その結果、樹脂組成物として透明な褐色の硬化物を得た。得られた樹脂組成物の測定結果を表４に示す。 Comparative Example 7
The operation and measurement were performed in the same manner as in Example 4 except that the resin additive 2 was not mixed with styrene. As a result, a transparent brown cured product was obtained as the resin composition. Table 4 shows the measurement results of the obtained resin composition.
以上のように、本発明の樹脂添加剤を用いると、今までフラーレンの添加効果を得にくかった樹脂であっても、得られる樹脂組成物はＴｇ、１０％質量減少温度共に大きく上昇させることができる（各実施例）。さらに、本発明の樹脂添加剤は、樹脂原料に添加し、該原料をラジカル重合させて樹脂組成物を得ることも可能である（実施例４）。
As described above, when the resin additive of the present invention is used, the resin composition obtained can greatly increase both Tg and 10% mass reduction temperature even if it is a resin that has been difficult to obtain fullerene addition effects until now. Yes (each example). Furthermore, the resin additive of the present invention can be added to a resin raw material, and the raw material can be radically polymerized to obtain a resin composition (Example 4).
Claims (15)
- 置換基を有してもよいインデンがフラーレン骨格に付加しているフラーレン誘導体の有機溶媒溶液からなる樹脂添加剤。 A resin additive comprising an organic solvent solution of a fullerene derivative in which an indene which may have a substituent is added to the fullerene skeleton.
- 前記有機溶媒が、Ｎ－メチル－２－ピロリドン、酢酸エチル、酢酸ブチル、メチルエチルケトン、プロピレングリコールモノメチルエーテルアセテート及びシクロヘキサノンからなる群より選ばれる少なくとも一種の溶媒である請求項１に記載の樹脂添加剤。 The resin additive according to claim 1, wherein the organic solvent is at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, ethyl acetate, butyl acetate, methyl ethyl ketone, propylene glycol monomethyl ether acetate, and cyclohexanone.
- 前記フラーレン誘導体が下記式（１）で表される請求項１または２に記載の樹脂添加剤。
- 置換基を有してもよいインデンがフラーレン骨格に複数付加している請求項１～３のいずれかに記載の樹脂添加剤。 4. The resin additive according to claim 1, wherein a plurality of indene which may have a substituent is added to the fullerene skeleton.
- 前記インデンの付加数が1つである前記フラーレン誘導体と２つである前記フラーレン誘導体と３つである前記フラーレン誘導体とを何れも含むことを特徴とする請求項１～３のいずれかに記載の樹脂添加剤。 The fullerene derivative having one indene addition number, the fullerene derivative being two, and the fullerene derivative being three are both included. Resin additive.
- 樹脂と請求項１～５のいずれかに記載の樹脂添加剤との混合物からなる樹脂混合物を得る工程と
前記樹脂混合物から溶媒を除去する工程と
を有する樹脂組成物の製造方法。 A method for producing a resin composition comprising a step of obtaining a resin mixture comprising a mixture of a resin and the resin additive according to any one of claims 1 to 5, and a step of removing a solvent from the resin mixture. - 前記樹脂混合物を得る工程が、
重合して樹脂となる材料と前記樹脂添加剤との混合物からなる原料混合物を得る工程と
前記原料混合物中の前記材料を重合する工程と
を有する請求項６に記載の樹脂組成物の製造方法。 Obtaining the resin mixture comprises:
The manufacturing method of the resin composition of Claim 6 which has the process of obtaining the raw material mixture which consists of the mixture of the material which superposes | polymerizes and becomes the resin, and the said resin additive, and the process of superposing | polymerizing the said material in the said raw material mixture. - さらに、前記樹脂混合物を１２０～３５０℃で１～１００時間加熱する工程を有する請求項６または７に記載の樹脂組成物の製造方法。 The method for producing a resin composition according to claim 6 or 7, further comprising a step of heating the resin mixture at 120 to 350 ° C for 1 to 100 hours.
- 前記樹脂が熱可塑性樹脂である請求項８に記載の樹脂組成物の製造方法。 The method for producing a resin composition according to claim 8, wherein the resin is a thermoplastic resin.
- 置換基を有してもよいインデンがフラーレン骨格に付加しているフラーレン誘導体の熱分解物及び樹脂を含む樹脂組成物。 A resin composition comprising a thermally decomposed product of a fullerene derivative in which an indene which may have a substituent is added to the fullerene skeleton, and a resin.
- 前記熱分解物が、置換基を有してもよいインデンとフラーレンである請求項１０に記載の樹脂組成物。 The resin composition according to claim 10, wherein the thermal decomposition product is indene and fullerene which may have a substituent.
- 前記フラーレン誘導体が下記式（１）で表される請求項１０または１１に記載の樹脂組成物。
- 前記樹脂が、ポリオレフィン、ポリスチレン、ポリイミド、ポリアミド、ポリフェニレンスルファイド、ポリメタクリル酸メチル及びポリカーボネートから選ばれる少なくとも１種を含む請求項１０～１２に記載の樹脂組成物。 The resin composition according to claim 10, wherein the resin contains at least one selected from polyolefin, polystyrene, polyimide, polyamide, polyphenylene sulfide, polymethyl methacrylate, and polycarbonate.
- 置換基を有してもよいインデンがフラーレン骨格に付加しているフラーレン誘導体及び樹脂を含むフラレーン誘導体含有樹脂組成物。 A fullerene derivative-containing resin composition comprising a fullerene derivative in which an indene which may have a substituent is added to the fullerene skeleton and a resin.
- 請求項６～９に記載の製造方法で得られる樹脂組成物。 A resin composition obtained by the production method according to claim 6.
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