WO2019009325A1 - Sizing agent, method for manufacturing same, fiber, and fiber tow - Google Patents
Sizing agent, method for manufacturing same, fiber, and fiber tow Download PDFInfo
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- WO2019009325A1 WO2019009325A1 PCT/JP2018/025346 JP2018025346W WO2019009325A1 WO 2019009325 A1 WO2019009325 A1 WO 2019009325A1 JP 2018025346 W JP2018025346 W JP 2018025346W WO 2019009325 A1 WO2019009325 A1 WO 2019009325A1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
Definitions
- the present invention relates to a sizing agent containing fullerene and a method for producing the same, and a fiber coated with the sizing agent and a fiber tow containing the sizing agent.
- Fibers are prone to yarn breakage and fuzz in the manufacturing and processing steps, and also have poor adhesion to the matrix resin constituting the composite material, and adversely affect physical properties.
- Sizing agents are used for the purpose of imparting such fibers with a focusing property and adhesion to a matrix resin, and for improving the processability and physical properties when used as a composite material.
- Patent Document 1 discloses a mixture of a transition metal nanoparticle in a solvent and a dispersion and a fiber sizing agent (fiber sizing agent blending agent). Further, a method of applying the fiber sizing agent to fibers and removing the solvent is disclosed.
- Patent No. 5559868 gazette
- the nanoparticles are not only dispersed but dissolved in the fiber sizing agent, but the method is limited in terms of the improvement of the slipperiness for preventing the abrasion of the fibers by the nanoparticles.
- This invention is made in view of the said situation, Comprising: It aims at providing the sizing agent which improves the surface characteristic (slidability) of a fiber.
- the present invention includes the following inventions.
- a sizing agent for fibers in which fullerenes are dissolved [1] A sizing agent for fibers in which fullerenes are dissolved.
- a fiber tow comprising the sizing agent as described in any one of the above items [1] to [5].
- the slipperiness of the fiber is improved.
- the fullerene is dissolved in the sizing agent of the present embodiment.
- the sizing agent of the present embodiment is obtained by mixing a raw material sizing agent containing no fullerene and fullerene, and removing an insoluble component from the obtained mixed solution.
- Raw material sizing agent As a raw material sizing agent, a sizing agent that is generally marketed (usually, it can be applied directly to a fiber as a liquid product such as a solution or an emulsion) can be used, but in order to easily obtain the above effects
- a sizing agent that dissolves 0.001% by mass or more, preferably 0.01% by mass or more is preferable.
- the raw material sizing agent examples include a sizing agent containing a resin, and more specifically, at least one selected from a urethane resin, an acrylic resin, an epoxy resin, an amide resin, an ester resin and an ether resin as a main component.
- the sizing agent which contains the ester resin is preferable, Preferably the sizing agent which has ester resin as a main component is mentioned.
- the raw material sizing agent may contain a component such as a surfactant which is generally contained as a sizing agent.
- the components of the raw material sizing agent are also inherited (included) in the sizing agent obtained in the present embodiment.
- the mixing time is preferably 1 hour or more, more preferably 10 hours or more, and still more preferably 5 days or more.
- the upper limit of the mixing time is preferably about 10 days.
- the mixed solution obtained in the mixing step usually contains insoluble components such as undissolved matter of fullerene. When such unnecessary components are present, the dissolved fullerene is likely to precipitate. Therefore, the insoluble component is removed from the mixed solution to obtain the sizing agent of the present embodiment.
- insoluble components such as undissolved matter of fullerene.
- the above filtration is preferred because the apparatus is simple.
- the viscosity may be lowered by heating the liquid mixture. However, it is preferable to make heating temperature into the temperature range mentioned later.
- the sizing agent obtained in the insoluble component removing step is diluted with the raw material sizing agent used. You may
- the sizing agent of the present embodiment can be obtained as described above. From the viewpoint of the solubility of fullerene and the viscosity of the raw material sizing agent, the above steps are carried out by heating preferably to 10 ° C. or more, more preferably 50 ° C. or more, still more preferably 100 ° C. or more. However, in order to prevent the modification of the components of the raw material sizing agent, the lower temperature is better, and the above steps are preferably performed at 200 ° C. or less, more preferably 150 ° C. or less. That is, each of the steps is preferably performed in the range of 10 to 200 ° C.
- the content of the fullerene in the sizing agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, in order to easily obtain the above-described effects. Further, the content of the fullerene in the sizing agent is preferably 1% by mass or less, more preferably 0.3% by mass or less, in the range not exceeding the saturation solubility in order to suppress precipitation of dissolved fullerenes. .
- the content of the fullerene in the sizing agent is adjusted, for example, by adjusting the mixing time in the mixing step or the addition amount of the fullerene, or by the dilution rate in the dilution step.
- the fullerene used in the present embodiment is not particularly limited, but it is preferable to use a mixture containing higher fullerenes than C 60 , C 70 and C 70 . This is because the total solubility of each fullerene species in the mixture is likely to be higher than the solubility of a single fullerene such as C 60 or C 70 .
- the fibers of the present embodiment are coated with the sizing agent of the present embodiment.
- the fiber of the present embodiment can be obtained by applying or immersing the above-mentioned sizing agent to the fiber as the raw material.
- the fiber used as the said raw material is not specifically limited, The fiber in which the sizing agent is generally used can be mentioned, More specifically, glass fiber, a synthetic fiber, carbon fiber, etc. can be mentioned.
- Fiber tow The fiber tow of the present embodiment includes the sizing agent of the present embodiment between the fibers constituting the fiber tow.
- the fiber tow of the present embodiment can be obtained by applying or immersing the sizing agent to the fiber tow as a raw material.
- the fibers of the present embodiment can be bundled to form the fiber tow of the present embodiment.
- the fiber used for the fiber tow used as a raw material is the same as the fiber used as the raw material used by above-mentioned this embodiment. That is, the fibers constituting the fiber tow may be glass fibers, synthetic fibers or carbon fibers.
- the fiber of the sample is supplied at a thread speed of 0.5 m / min and a treatment tension of 1000 g using a friction tester YF850 manufactured by Toray Engineering Co., Ltd., and the angle is 270 ° C.
- the coefficient of friction was calculated from equation (1) from the tension pulled by contact at 540 °, and the average value of five trials was determined.
- Coefficient of friction (tension) / (initial tension + measured tension) (1) (Examples 1 to 3) 1 g of fullerene (nanom (registered trademark) mix ST manufactured by Frontier Carbon Co., Ltd.) is mixed with 50 g of a raw material sizing agent (manufactured by Matsumoto Resin Pharmaceutical Co., Ltd., Marposol W-333, acrylic ester resin solution), and magnetic stirrer for 3 days Stir. The obtained mixed solution was filtered with a membrane filter with a pore size of 0.1 ⁇ m to obtain a sizing agent 0 with a fullerene content of 0.3% by mass.
- a raw material sizing agent manufactured by Matsumoto Resin Pharmaceutical Co., Ltd., Marposol W-333, acrylic ester resin solution
- Sizing agent 0 was diluted with the same raw material sizing agent as described above, and the content of each of the fullerenes was 0.05% by mass Sizing agent 1 (Example 1), 0.1% by mass Sizing agent 2 (Example 2) And 0.2% by mass of sizing agent 3 (Example 3).
Abstract
In the present invention, a fullerene is dissolved in a fiber sizing agent.
Description
本発明は、フラーレンを含むサイジング剤およびその製造方法、並びに、前記サイジング剤で被覆された繊維及び前記サイジング剤を含む繊維トウに関する。
The present invention relates to a sizing agent containing fullerene and a method for producing the same, and a fiber coated with the sizing agent and a fiber tow containing the sizing agent.
繊維は、製造と加工工程において糸切れや毛羽を発生しやすく、また複合材料を構成するマトリックス樹脂に対する接着性も悪く、物性面にも悪影響を与える。このような繊維に集束性やマトリックス樹脂に対する接着性を付与し、加工性や複合材料として使用する際の物性を改良する目的で、サイジング剤が使われている。
Fibers are prone to yarn breakage and fuzz in the manufacturing and processing steps, and also have poor adhesion to the matrix resin constituting the composite material, and adversely affect physical properties. Sizing agents are used for the purpose of imparting such fibers with a focusing property and adhesion to a matrix resin, and for improving the processability and physical properties when used as a composite material.
特許文献１には、溶媒中に遷移金属ナノ粒子が分散液と繊維サイジング剤との混合物（繊維サイジング剤配合剤）が開示されている。さらに、前記繊維サイジング剤配合剤を繊維へ塗布し、溶媒を除去する方法が開示されている。
Patent Document 1 discloses a mixture of a transition metal nanoparticle in a solvent and a dispersion and a fiber sizing agent (fiber sizing agent blending agent). Further, a method of applying the fiber sizing agent to fibers and removing the solvent is disclosed.
前記特許文献１の方法では、ナノ粒子は分散しているだけで繊維サイジング剤に溶解している訳ではなく、ナノ粒子による繊維の摩耗を防ぐための滑り性の向上という点では限定的であった。
According to the method of Patent Document 1, the nanoparticles are not only dispersed but dissolved in the fiber sizing agent, but the method is limited in terms of the improvement of the slipperiness for preventing the abrasion of the fibers by the nanoparticles. The
本発明は、上記事情に鑑みてなされたものであって、繊維の表面特性（滑り性）を向上させるサイジング剤を提供することを目的とする。
This invention is made in view of the said situation, Comprising: It aims at providing the sizing agent which improves the surface characteristic (slidability) of a fiber.
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］ フラーレンが溶解している繊維のサイジング剤。
[1] A sizing agent for fibers in which fullerenes are dissolved.
［２］ 前記フラーレンが、前記サイジング剤中に０．００１～１質量％含まれる前項［１］に記載のサイジング剤。
[2] The sizing agent according to the above [1], wherein the fullerene is contained in an amount of 0.001 to 1% by mass in the sizing agent.
［３］ 前記のフラーレンが、Ｃ６０、Ｃ７０及びＣ７０より高次フラーレンを含む混合物である前項［１］または［２］に記載のサイジング剤。
[3] The sizing agent according to [1] or [2] above, wherein the fullerene is a mixture containing C 60 , C 70 and higher than C 70 higher fullerenes.
［４］ 前記サイジング剤は、樹脂を含む前項［１］～［３］のいずれかに記載のサイジング剤。
[4] The sizing agent according to any one of the above [1] to [3], wherein the sizing agent comprises a resin.
［５］ 前記樹脂が、ウレタン樹脂、アクリル樹脂、エポキシ樹脂、アミド樹脂、エステル樹脂およびエーテル樹脂から選ばれる少なくとも一種である前項［４］に記載のサイジング剤。
[5] The sizing agent according to the above [4], wherein the resin is at least one selected from urethane resin, acrylic resin, epoxy resin, amide resin, ester resin and ether resin.
［６］ 前項［１］～［５］のいずれかに記載のサイジング剤の製造方法であって、フラーレンを含まない原料サイジング剤とフラーレンとを混合し混合液を得る工程と、前記混合液から不溶成分を除去する工程とを有するサイジング剤の製造方法。
[6] A method for producing a sizing agent according to any one of the preceding items [1] to [5], wherein a raw material sizing agent containing no fullerene and fullerene are mixed to obtain a mixed solution, and the mixed solution And (e) removing the insoluble component.
［７］ 前記不溶成分の除去が、前記混合液をろ過することにより行われる前項［６］に記載のサイジング剤の製造方法。
[7] The method for producing a sizing agent according to [6], wherein the removal of the insoluble component is carried out by filtering the mixed solution.
［８］ さらに、不溶成分を除去後の溶液を、原料サイジング剤で希釈する工程を有する前項［６］または［７］に記載のサイジング剤の製造方法。
[8] The method for producing a sizing agent according to [6] or [7] above, further comprising the step of diluting the solution after removal of the insoluble component with a raw material sizing agent.
［９］ 前項［１］～［５］のいずれかに記載のサイジング剤で被覆された繊維。
[9] A fiber coated with the sizing agent according to any one of the above items [1] to [5].
［１０］ 前記繊維が、ガラス繊維、合成繊維または炭素繊維である前項［９］に記載の繊維。
[10] The fiber according to the above [9], wherein the fiber is glass fiber, synthetic fiber or carbon fiber.
［１１］ 前項［１］～［５］のいずれかに記載のサイジング剤を含む繊維トウ。
[11] A fiber tow comprising the sizing agent as described in any one of the above items [1] to [5].
［１２］ 前記繊維トウを構成する繊維が、ガラス繊維、合成繊維または炭素繊維である前項［１１］に記載の繊維トウ。
[12] The fiber tow according to the above [11], wherein the fiber constituting the fiber tow is glass fiber, synthetic fiber or carbon fiber.
本発明のサイジング剤を用いることにより、繊維の滑り性が改善される。
By using the sizing agent of the present invention, the slipperiness of the fiber is improved.
以下、本発明の実施形態に係る繊維のサイジング剤及びその製造方法について説明する。
Hereinafter, a sizing agent for fibers according to an embodiment of the present invention and a method for producing the same will be described.
本実施形態のサイジング剤には、フラーレンが溶解している。本実施形態のサイジング剤は、フラーレンを含まない原料サイジング剤とフラーレンとを混合し、得られた混合液から不溶成分を除去することにより得られる。
＜原料サイジング剤＞
原料サイジング剤としては、一般に市販されているサイジング剤（通常、溶液又はエマルジョンの様な液状品として、そのまま繊維に適用できる）を用いることができるが、前述の効果を得やすくするためにフラーレンが０．００１質量％以上、好ましくは０．０１質量％以上溶解するサイジング剤が好ましい。原料サイジング剤としては、例えば、樹脂を含むサイジング剤が挙げられ、より具体的には、ウレタン樹脂、アクリル樹脂、エポキシ樹脂、アミド樹脂、エステル樹脂およびエーテル樹脂から選ばれる少なくとも１種を主成分とするサイジング剤が挙げられ、好ましくはエステル樹脂を主成分とするサイジング剤が挙げられる。 The fullerene is dissolved in the sizing agent of the present embodiment. The sizing agent of the present embodiment is obtained by mixing a raw material sizing agent containing no fullerene and fullerene, and removing an insoluble component from the obtained mixed solution.
Raw material sizing agent
As a raw material sizing agent, a sizing agent that is generally marketed (usually, it can be applied directly to a fiber as a liquid product such as a solution or an emulsion) can be used, but in order to easily obtain the above effects A sizing agent that dissolves 0.001% by mass or more, preferably 0.01% by mass or more is preferable. Examples of the raw material sizing agent include a sizing agent containing a resin, and more specifically, at least one selected from a urethane resin, an acrylic resin, an epoxy resin, an amide resin, an ester resin and an ether resin as a main component. The sizing agent which contains the ester resin is preferable, Preferably the sizing agent which has ester resin as a main component is mentioned.
＜原料サイジング剤＞
原料サイジング剤としては、一般に市販されているサイジング剤（通常、溶液又はエマルジョンの様な液状品として、そのまま繊維に適用できる）を用いることができるが、前述の効果を得やすくするためにフラーレンが０．００１質量％以上、好ましくは０．０１質量％以上溶解するサイジング剤が好ましい。原料サイジング剤としては、例えば、樹脂を含むサイジング剤が挙げられ、より具体的には、ウレタン樹脂、アクリル樹脂、エポキシ樹脂、アミド樹脂、エステル樹脂およびエーテル樹脂から選ばれる少なくとも１種を主成分とするサイジング剤が挙げられ、好ましくはエステル樹脂を主成分とするサイジング剤が挙げられる。 The fullerene is dissolved in the sizing agent of the present embodiment. The sizing agent of the present embodiment is obtained by mixing a raw material sizing agent containing no fullerene and fullerene, and removing an insoluble component from the obtained mixed solution.
Raw material sizing agent
As a raw material sizing agent, a sizing agent that is generally marketed (usually, it can be applied directly to a fiber as a liquid product such as a solution or an emulsion) can be used, but in order to easily obtain the above effects A sizing agent that dissolves 0.001% by mass or more, preferably 0.01% by mass or more is preferable. Examples of the raw material sizing agent include a sizing agent containing a resin, and more specifically, at least one selected from a urethane resin, an acrylic resin, an epoxy resin, an amide resin, an ester resin and an ether resin as a main component. The sizing agent which contains the ester resin is preferable, Preferably the sizing agent which has ester resin as a main component is mentioned.
また、原料サイジング剤には、上記樹脂の他に、サイジング剤として一般的に含まれる界面活性剤等の成分を含んでいてもよい。原料サイジング剤の成分は、本実施形態で得られるサイジング剤にも引き継がれる（含まれる）。
＜混合工程＞
通常、フラーレンの原料サイジング剤への溶解速度は早くない。そのため、前記混合は、フラーレンが十分溶解するまで行うのが好ましい。一般的な回転羽付の攪拌機を用いてフラーレンと原料サイジング剤を混合した場合、混合時間は、１時間以上が好ましく、１０時間以上がより好ましく、５日以上がさらに好ましい。ただし、飽和溶解度に近づくと溶解速度は遅くなるので、前記混合時間の上限は１０日程度とすることが好ましい。 In addition to the above resin, the raw material sizing agent may contain a component such as a surfactant which is generally contained as a sizing agent. The components of the raw material sizing agent are also inherited (included) in the sizing agent obtained in the present embodiment.
<Mixing process>
Usually, the dissolution rate of fullerene in the raw material sizing agent is not fast. Therefore, the mixing is preferably performed until the fullerene is sufficiently dissolved. When fullerene and raw material sizing agent are mixed using a general rotary feathered stirrer, the mixing time is preferably 1 hour or more, more preferably 10 hours or more, and still more preferably 5 days or more. However, since the dissolution rate becomes slower as the saturation solubility is approached, the upper limit of the mixing time is preferably about 10 days.
＜混合工程＞
通常、フラーレンの原料サイジング剤への溶解速度は早くない。そのため、前記混合は、フラーレンが十分溶解するまで行うのが好ましい。一般的な回転羽付の攪拌機を用いてフラーレンと原料サイジング剤を混合した場合、混合時間は、１時間以上が好ましく、１０時間以上がより好ましく、５日以上がさらに好ましい。ただし、飽和溶解度に近づくと溶解速度は遅くなるので、前記混合時間の上限は１０日程度とすることが好ましい。 In addition to the above resin, the raw material sizing agent may contain a component such as a surfactant which is generally contained as a sizing agent. The components of the raw material sizing agent are also inherited (included) in the sizing agent obtained in the present embodiment.
<Mixing process>
Usually, the dissolution rate of fullerene in the raw material sizing agent is not fast. Therefore, the mixing is preferably performed until the fullerene is sufficiently dissolved. When fullerene and raw material sizing agent are mixed using a general rotary feathered stirrer, the mixing time is preferably 1 hour or more, more preferably 10 hours or more, and still more preferably 5 days or more. However, since the dissolution rate becomes slower as the saturation solubility is approached, the upper limit of the mixing time is preferably about 10 days.
＜不溶成分除去工程＞
前記混合工程で得られた混合液には、フラーレンの溶け残りなど、不溶成分が通常含まれる。このような不要成分があると、溶解しているフラーレンが析出しやすい。そのため、前記混合液から不溶成分を除去して、本実施形態のサイジング剤を得る。不溶成分を除去する方法としては、孔径０．１μｍ以下のフィルターでろ過する方法、遠心分離法、などが挙げられる。装置が簡便なことから前記ろ過が好ましい。また、ろ過をし易くするために、前記混合液を加熱して粘度を下げてもよい。ただし、加熱温度は、後述する温度範囲とすることが好ましい。 <Insoluble component removal process>
The mixed solution obtained in the mixing step usually contains insoluble components such as undissolved matter of fullerene. When such unnecessary components are present, the dissolved fullerene is likely to precipitate. Therefore, the insoluble component is removed from the mixed solution to obtain the sizing agent of the present embodiment. As a method of removing an insoluble component, the method of filtering with a filter with a hole diameter of 0.1 micrometer or less, the centrifugation method, etc. are mentioned. The above filtration is preferred because the apparatus is simple. Moreover, in order to facilitate filtration, the viscosity may be lowered by heating the liquid mixture. However, it is preferable to make heating temperature into the temperature range mentioned later.
前記混合工程で得られた混合液には、フラーレンの溶け残りなど、不溶成分が通常含まれる。このような不要成分があると、溶解しているフラーレンが析出しやすい。そのため、前記混合液から不溶成分を除去して、本実施形態のサイジング剤を得る。不溶成分を除去する方法としては、孔径０．１μｍ以下のフィルターでろ過する方法、遠心分離法、などが挙げられる。装置が簡便なことから前記ろ過が好ましい。また、ろ過をし易くするために、前記混合液を加熱して粘度を下げてもよい。ただし、加熱温度は、後述する温度範囲とすることが好ましい。 <Insoluble component removal process>
The mixed solution obtained in the mixing step usually contains insoluble components such as undissolved matter of fullerene. When such unnecessary components are present, the dissolved fullerene is likely to precipitate. Therefore, the insoluble component is removed from the mixed solution to obtain the sizing agent of the present embodiment. As a method of removing an insoluble component, the method of filtering with a filter with a hole diameter of 0.1 micrometer or less, the centrifugation method, etc. are mentioned. The above filtration is preferred because the apparatus is simple. Moreover, in order to facilitate filtration, the viscosity may be lowered by heating the liquid mixture. However, it is preferable to make heating temperature into the temperature range mentioned later.
＜希釈工程＞
さらに、フラーレンの析出をし難くするために、あるいは、サイジング剤中のフラーレンの含有量を所望の濃度に調整するために、不溶成分除去工程で得たサイジング剤を、用いた原料サイジング剤で希釈してもよい。 <Dilution process>
Furthermore, in order to make precipitation of the fullerene difficult, or to adjust the content of the fullerene in the sizing agent to a desired concentration, the sizing agent obtained in the insoluble component removing step is diluted with the raw material sizing agent used. You may
さらに、フラーレンの析出をし難くするために、あるいは、サイジング剤中のフラーレンの含有量を所望の濃度に調整するために、不溶成分除去工程で得たサイジング剤を、用いた原料サイジング剤で希釈してもよい。 <Dilution process>
Furthermore, in order to make precipitation of the fullerene difficult, or to adjust the content of the fullerene in the sizing agent to a desired concentration, the sizing agent obtained in the insoluble component removing step is diluted with the raw material sizing agent used. You may
＜温度＞
以上のようにして本実施形態のサイジング剤を得ることができる。フラーレンの溶解度や原料サイジング剤の粘度の観点から、気温が低くても好ましくは１０℃以上に、より好ましくは５０℃以上、さらに好ましくは１００℃以上に加熱して前記各工程を行う。ただし、原料サイジング剤の成分の変性を防ぐためにはより低温の方が良く、好ましくは２００℃以下、より好ましくは１５０℃以下で前記各工程を行う。すなわち、前記各工程は、１０～２００℃の範囲内で行うことが好ましい。 <Temperature>
The sizing agent of the present embodiment can be obtained as described above. From the viewpoint of the solubility of fullerene and the viscosity of the raw material sizing agent, the above steps are carried out by heating preferably to 10 ° C. or more, more preferably 50 ° C. or more, still more preferably 100 ° C. or more. However, in order to prevent the modification of the components of the raw material sizing agent, the lower temperature is better, and the above steps are preferably performed at 200 ° C. or less, more preferably 150 ° C. or less. That is, each of the steps is preferably performed in the range of 10 to 200 ° C.
以上のようにして本実施形態のサイジング剤を得ることができる。フラーレンの溶解度や原料サイジング剤の粘度の観点から、気温が低くても好ましくは１０℃以上に、より好ましくは５０℃以上、さらに好ましくは１００℃以上に加熱して前記各工程を行う。ただし、原料サイジング剤の成分の変性を防ぐためにはより低温の方が良く、好ましくは２００℃以下、より好ましくは１５０℃以下で前記各工程を行う。すなわち、前記各工程は、１０～２００℃の範囲内で行うことが好ましい。 <Temperature>
The sizing agent of the present embodiment can be obtained as described above. From the viewpoint of the solubility of fullerene and the viscosity of the raw material sizing agent, the above steps are carried out by heating preferably to 10 ° C. or more, more preferably 50 ° C. or more, still more preferably 100 ° C. or more. However, in order to prevent the modification of the components of the raw material sizing agent, the lower temperature is better, and the above steps are preferably performed at 200 ° C. or less, more preferably 150 ° C. or less. That is, each of the steps is preferably performed in the range of 10 to 200 ° C.
＜フラーレン含有量＞
サイジング剤中のフラーレンの含有量は、前述の効果を得やすくするために、好ましくは０．００１質量％以上、より好ましくは０．０１質量％以上である。また、サイジング剤中のフラーレンの含有量は、溶解しているフラーレンの析出を抑えるために、飽和溶解度を超えない範囲で、好ましくは１質量％以下、より好ましくは０．３質量％以下である。 <Fullerene content>
The content of the fullerene in the sizing agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, in order to easily obtain the above-described effects. Further, the content of the fullerene in the sizing agent is preferably 1% by mass or less, more preferably 0.3% by mass or less, in the range not exceeding the saturation solubility in order to suppress precipitation of dissolved fullerenes. .
サイジング剤中のフラーレンの含有量は、前述の効果を得やすくするために、好ましくは０．００１質量％以上、より好ましくは０．０１質量％以上である。また、サイジング剤中のフラーレンの含有量は、溶解しているフラーレンの析出を抑えるために、飽和溶解度を超えない範囲で、好ましくは１質量％以下、より好ましくは０．３質量％以下である。 <Fullerene content>
The content of the fullerene in the sizing agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, in order to easily obtain the above-described effects. Further, the content of the fullerene in the sizing agent is preferably 1% by mass or less, more preferably 0.3% by mass or less, in the range not exceeding the saturation solubility in order to suppress precipitation of dissolved fullerenes. .
サイジング剤中のフラーレンの含有量は、例えば、前記混合工程での混合時間やフラーレンの添加量を調整することにより、あるいは、前記希釈工程での希釈率により調整する。
＜フラーレン＞
本実施形態で用いるフラーレンは特に限定されないが、Ｃ６０、Ｃ７０及びＣ７０より高次フラーレンを含む混合物を用いることが好ましい。これは、Ｃ６０やＣ７０など単一のフラーレンの溶解度よりも、前記混合物の各フラーレン種の合計の溶解度の方が高くなりやすいためである。
＜繊維＞
本実施形態の繊維は、本実施形態のサイジング剤で被覆されている。原料となる繊維に、前記サイジング剤を塗布または浸漬等することにより、本実施形態の繊維を得ることができる。 The content of the fullerene in the sizing agent is adjusted, for example, by adjusting the mixing time in the mixing step or the addition amount of the fullerene, or by the dilution rate in the dilution step.
<Fullerene>
The fullerene used in the present embodiment is not particularly limited, but it is preferable to use a mixture containing higher fullerenes than C 60 , C 70 and C 70 . This is because the total solubility of each fullerene species in the mixture is likely to be higher than the solubility of a single fullerene such as C 60 or C 70 .
<Fiber>
The fibers of the present embodiment are coated with the sizing agent of the present embodiment. The fiber of the present embodiment can be obtained by applying or immersing the above-mentioned sizing agent to the fiber as the raw material.
＜フラーレン＞
本実施形態で用いるフラーレンは特に限定されないが、Ｃ６０、Ｃ７０及びＣ７０より高次フラーレンを含む混合物を用いることが好ましい。これは、Ｃ６０やＣ７０など単一のフラーレンの溶解度よりも、前記混合物の各フラーレン種の合計の溶解度の方が高くなりやすいためである。
＜繊維＞
本実施形態の繊維は、本実施形態のサイジング剤で被覆されている。原料となる繊維に、前記サイジング剤を塗布または浸漬等することにより、本実施形態の繊維を得ることができる。 The content of the fullerene in the sizing agent is adjusted, for example, by adjusting the mixing time in the mixing step or the addition amount of the fullerene, or by the dilution rate in the dilution step.
<Fullerene>
The fullerene used in the present embodiment is not particularly limited, but it is preferable to use a mixture containing higher fullerenes than C 60 , C 70 and C 70 . This is because the total solubility of each fullerene species in the mixture is likely to be higher than the solubility of a single fullerene such as C 60 or C 70 .
<Fiber>
The fibers of the present embodiment are coated with the sizing agent of the present embodiment. The fiber of the present embodiment can be obtained by applying or immersing the above-mentioned sizing agent to the fiber as the raw material.
前記原料となる繊維は特に限定されないが、一般にサイジング剤が用いられている繊維を挙げることができ、より具体的には、ガラス繊維、合成繊維及び炭素繊維等を挙げることができる。
＜繊維トウ＞
本実施形態の繊維トウは、該繊維トウを構成する繊維間に、本実施形態のサイジング剤を含む。原料となる繊維トウに、前記サイジング剤を塗布または浸漬等することにより、本実施形態の繊維トウを得ることができる。あるいは、本実施形態の繊維を束ねて、本実施形態の繊維トウとすることもできる。なお、原料となる繊維トウに用いられる繊維は、前述の本実施形態で用いられる原料となる繊維と同様である。すなわち、繊維トウを構成する繊維は、ガラス繊維、合成繊維または炭素繊維であってもよい。 Although the fiber used as the said raw material is not specifically limited, The fiber in which the sizing agent is generally used can be mentioned, More specifically, glass fiber, a synthetic fiber, carbon fiber, etc. can be mentioned.
Fiber tow
The fiber tow of the present embodiment includes the sizing agent of the present embodiment between the fibers constituting the fiber tow. The fiber tow of the present embodiment can be obtained by applying or immersing the sizing agent to the fiber tow as a raw material. Alternatively, the fibers of the present embodiment can be bundled to form the fiber tow of the present embodiment. In addition, the fiber used for the fiber tow used as a raw material is the same as the fiber used as the raw material used by above-mentioned this embodiment. That is, the fibers constituting the fiber tow may be glass fibers, synthetic fibers or carbon fibers.
＜繊維トウ＞
本実施形態の繊維トウは、該繊維トウを構成する繊維間に、本実施形態のサイジング剤を含む。原料となる繊維トウに、前記サイジング剤を塗布または浸漬等することにより、本実施形態の繊維トウを得ることができる。あるいは、本実施形態の繊維を束ねて、本実施形態の繊維トウとすることもできる。なお、原料となる繊維トウに用いられる繊維は、前述の本実施形態で用いられる原料となる繊維と同様である。すなわち、繊維トウを構成する繊維は、ガラス繊維、合成繊維または炭素繊維であってもよい。 Although the fiber used as the said raw material is not specifically limited, The fiber in which the sizing agent is generally used can be mentioned, More specifically, glass fiber, a synthetic fiber, carbon fiber, etc. can be mentioned.
Fiber tow
The fiber tow of the present embodiment includes the sizing agent of the present embodiment between the fibers constituting the fiber tow. The fiber tow of the present embodiment can be obtained by applying or immersing the sizing agent to the fiber tow as a raw material. Alternatively, the fibers of the present embodiment can be bundled to form the fiber tow of the present embodiment. In addition, the fiber used for the fiber tow used as a raw material is the same as the fiber used as the raw material used by above-mentioned this embodiment. That is, the fibers constituting the fiber tow may be glass fibers, synthetic fibers or carbon fibers.
以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明は以下の実施例のみに限定されるものではない。
＜フラーレン濃度の測定＞
サイジング剤を試料とし、これをトルエンで希釈したものについて、以下の測定を行った。 Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to only the following examples.
<Measurement of fullerene concentration>
The following measurement was performed about what made the sizing agent the sample and diluted this with toluene.
＜フラーレン濃度の測定＞
サイジング剤を試料とし、これをトルエンで希釈したものについて、以下の測定を行った。 Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to only the following examples.
<Measurement of fullerene concentration>
The following measurement was performed about what made the sizing agent the sample and diluted this with toluene.
予めフラーレンＣ６０、Ｃ７０およびより高次フラーレンのトルエン溶液で検量線を作成した高速液体クロマトグラフィー（装置：Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｙ製高速液体クロマトグラフ１２００ Ｓｅｒｉｅｓ；カラム：ＹＭＣ製カラムＹＭＣ－ｐａｃｋ ＯＤＳ－ＡＭ；展開溶媒（体積比）：トルエン／メタノール＝５１／４９；流速：１．２ ｍＬ／ｍｉｎ；検出方法：３０８ｎｍ紫外光吸収）により測定し、試料中の各フラーレン濃度を算出し、その合計を求めた。
＜対金属高温低速摩擦係数の測定＞
繊維の滑り性の試験を対金属高温低速摩擦係数の測定により行った。すなわち、試料の繊維を、東レエンジニアリング（株）製摩擦試験機ＹＦ８５０を使用して、糸速０．５ｍ／分、処理張力１０００ｇで供給し、直径５ｃｍの固定金属ビン摩擦体に２７０℃、角度５４０°で接触させて引っ張った張力より、式（１）から摩擦係数を算出し、試行回数５回の平均の値を求めた。 High-performance liquid chromatography in which a calibration curve was prepared beforehand with a toluene solution of fullerene C 60 , C 70 and higher fullerenes (apparatus: high-performance liquid chromatograph 1200 Series manufactured by Agilent Technology; column: YMC column YMC-pack ODS-AM; Developing solvent (volume ratio): Toluene / methanol = 51/49; flow rate: 1.2 mL / min; detection method: 308 nm ultraviolet light absorption) to calculate the concentration of each fullerene in the sample and find the total The
<Measurement of friction coefficient between metal and high temperature low temperature>
A test of the slip properties of the fibers was carried out by measuring the coefficient of friction against high temperature metal. That is, the fiber of the sample is supplied at a thread speed of 0.5 m / min and a treatment tension of 1000 g using a friction tester YF850 manufactured by Toray Engineering Co., Ltd., and the angle is 270 ° C. The coefficient of friction was calculated from equation (1) from the tension pulled by contact at 540 °, and the average value of five trials was determined.
＜対金属高温低速摩擦係数の測定＞
繊維の滑り性の試験を対金属高温低速摩擦係数の測定により行った。すなわち、試料の繊維を、東レエンジニアリング（株）製摩擦試験機ＹＦ８５０を使用して、糸速０．５ｍ／分、処理張力１０００ｇで供給し、直径５ｃｍの固定金属ビン摩擦体に２７０℃、角度５４０°で接触させて引っ張った張力より、式（１）から摩擦係数を算出し、試行回数５回の平均の値を求めた。 High-performance liquid chromatography in which a calibration curve was prepared beforehand with a toluene solution of fullerene C 60 , C 70 and higher fullerenes (apparatus: high-performance liquid chromatograph 1200 Series manufactured by Agilent Technology; column: YMC column YMC-pack ODS-AM; Developing solvent (volume ratio): Toluene / methanol = 51/49; flow rate: 1.2 mL / min; detection method: 308 nm ultraviolet light absorption) to calculate the concentration of each fullerene in the sample and find the total The
<Measurement of friction coefficient between metal and high temperature low temperature>
A test of the slip properties of the fibers was carried out by measuring the coefficient of friction against high temperature metal. That is, the fiber of the sample is supplied at a thread speed of 0.5 m / min and a treatment tension of 1000 g using a friction tester YF850 manufactured by Toray Engineering Co., Ltd., and the angle is 270 ° C. The coefficient of friction was calculated from equation (1) from the tension pulled by contact at 540 °, and the average value of five trials was determined.
摩擦係数 ＝ （張力） ／ （初期張力 ＋ 測定張力） （１）
（実施例１～３）
１ｇのフラーレン（フロンティアカーボン社製 ｎａｎｏｍ（登録商標） ｍｉｘ ＳＴ）を５０ｇの原料サイジング剤（松本樹脂製薬社製、マーポゾールＷ－３３３、アクリル酸エステル系樹脂液）と混合し、３日間マグネチックスターラーで攪拌した。得られた混合液を、孔径０．１μｍのメンブランフィルターでろ過し、フラーレン含有量０．３質量％のサイジング剤０を得た。 Coefficient of friction = (tension) / (initial tension + measured tension) (1)
(Examples 1 to 3)
1 g of fullerene (nanom (registered trademark) mix ST manufactured by Frontier Carbon Co., Ltd.) is mixed with 50 g of a raw material sizing agent (manufactured by Matsumoto Resin Pharmaceutical Co., Ltd., Marposol W-333, acrylic ester resin solution), and magnetic stirrer for 3 days Stir. The obtained mixed solution was filtered with a membrane filter with a pore size of 0.1 μm to obtain a sizing agent 0 with a fullerene content of 0.3% by mass.
（実施例１～３）
１ｇのフラーレン（フロンティアカーボン社製 ｎａｎｏｍ（登録商標） ｍｉｘ ＳＴ）を５０ｇの原料サイジング剤（松本樹脂製薬社製、マーポゾールＷ－３３３、アクリル酸エステル系樹脂液）と混合し、３日間マグネチックスターラーで攪拌した。得られた混合液を、孔径０．１μｍのメンブランフィルターでろ過し、フラーレン含有量０．３質量％のサイジング剤０を得た。 Coefficient of friction = (tension) / (initial tension + measured tension) (1)
(Examples 1 to 3)
1 g of fullerene (nanom (registered trademark) mix ST manufactured by Frontier Carbon Co., Ltd.) is mixed with 50 g of a raw material sizing agent (manufactured by Matsumoto Resin Pharmaceutical Co., Ltd., Marposol W-333, acrylic ester resin solution), and magnetic stirrer for 3 days Stir. The obtained mixed solution was filtered with a membrane filter with a pore size of 0.1 μm to obtain a sizing agent 0 with a fullerene content of 0.3% by mass.
サイジング剤０を、前記と同じ原料サイジング剤で希釈し、フラーレン含有量がそれぞれ、０．０５質量％のサイジング剤１（実施例１）、０．１質量％のサイジング剤２（実施例２）、０．２質量％のサイジング剤３（実施例３）を得た。
Sizing agent 0 was diluted with the same raw material sizing agent as described above, and the content of each of the fullerenes was 0.05% by mass Sizing agent 1 (Example 1), 0.1% by mass Sizing agent 2 (Example 2) And 0.2% by mass of sizing agent 3 (Example 3).
なお、サイジング剤０～３を得た上記全工程は２０℃で行った。
＜繊維へのサイジング処理＞
得られた各サイジング剤について、東レ製の６６ナイロン糸（４７０Ｔ－７２－１７８１）を２０℃で１０秒間浸漬し、サイジング処理を行い、滑り性対金属高温低速摩擦係数の測定を行い摩擦係数を求めた。結果を表１に示す。
（比較例１）
サイジング剤１の代わりに、原料サイジング剤（フラーレンを含まないサイジング剤）を用いた以外は、実施例１と同様に操作及び測定を行った。 The above whole process of obtaining sizing agents 0 to 3 was performed at 20.degree.
<Sizing processing to fiber>
For each sizing agent obtained, immersing Toray's 66 nylon yarn (470T-72-1781) at 20 ° C for 10 seconds, sizing is performed, and the coefficient of friction is measured by measuring the slipperiness vs. metal high-temperature low-speed friction coefficient I asked. The results are shown in Table 1.
(Comparative example 1)
The operation and measurement were performed in the same manner as in Example 1 except that a raw material sizing agent (a sizing agent containing no fullerene) was used instead of the sizing agent 1.
＜繊維へのサイジング処理＞
得られた各サイジング剤について、東レ製の６６ナイロン糸（４７０Ｔ－７２－１７８１）を２０℃で１０秒間浸漬し、サイジング処理を行い、滑り性対金属高温低速摩擦係数の測定を行い摩擦係数を求めた。結果を表１に示す。
（比較例１）
サイジング剤１の代わりに、原料サイジング剤（フラーレンを含まないサイジング剤）を用いた以外は、実施例１と同様に操作及び測定を行った。 The above whole process of obtaining sizing agents 0 to 3 was performed at 20.degree.
<Sizing processing to fiber>
For each sizing agent obtained, immersing Toray's 66 nylon yarn (470T-72-1781) at 20 ° C for 10 seconds, sizing is performed, and the coefficient of friction is measured by measuring the slipperiness vs. metal high-temperature low-speed friction coefficient I asked. The results are shown in Table 1.
(Comparative example 1)
The operation and measurement were performed in the same manner as in Example 1 except that a raw material sizing agent (a sizing agent containing no fullerene) was used instead of the sizing agent 1.
Claims (12)
- フラーレンが溶解している繊維のサイジング剤。 Fiber sizing agent in which fullerene is dissolved.
- 前記フラーレンが、前記サイジング剤中に０．００１～１質量％含まれる請求項１に記載のサイジング剤。 The sizing agent according to claim 1, wherein the fullerene is contained in an amount of 0.001 to 1% by mass in the sizing agent.
- 前記のフラーレンが、Ｃ６０、Ｃ７０及びＣ７０より高次フラーレンを含む混合物である請求項１または２に記載のサイジング剤。 Wherein the fullerene, the sizing agent according to claim 1 or 2 which is a mixture containing higher fullerenes from C 60, C 70 and C 70.
- 前記サイジング剤は、樹脂を含む請求項１～３のいずれかに記載のサイジング剤。 The sizing agent according to any one of claims 1 to 3, wherein the sizing agent comprises a resin.
- 前記樹脂が、ウレタン樹脂、アクリル樹脂、エポキシ樹脂、アミド樹脂、エステル樹脂およびエーテル樹脂から選ばれる少なくとも一種である請求項４に記載のサイジング剤。 The sizing agent according to claim 4, wherein the resin is at least one selected from urethane resin, acrylic resin, epoxy resin, amide resin, ester resin and ether resin.
- 請求項１～５のいずれかに記載のサイジング剤の製造方法であって、フラーレンを含まない原料サイジング剤とフラーレンとを混合し混合液を得る工程と、前記混合液から不溶成分を除去する工程とを有するサイジング剤の製造方法。 The method for producing a sizing agent according to any one of claims 1 to 5, wherein a raw material sizing agent containing no fullerene and a fullerene are mixed to obtain a mixed solution, and a step of removing an insoluble component from the mixed solution. And a method of producing a sizing agent.
- 前記不溶成分の除去が、前記混合液をろ過することにより行われる請求項６に記載のサイジング剤の製造方法。 The manufacturing method of the sizing agent of Claim 6 which removal of the said insoluble component is performed by filtering the said liquid mixture.
- さらに、不溶成分を除去後の溶液を、原料サイジング剤で希釈する工程を有する請求項６または７に記載のサイジング剤の製造方法。 Furthermore, the manufacturing method of the sizing agent of Claim 6 or 7 which has the process of diluting the solution after removing an insoluble component with a raw material sizing agent.
- 請求項１～５のいずれかに記載のサイジング剤で被覆された繊維。 A fiber coated with the sizing agent according to any one of claims 1 to 5.
- 前記繊維が、ガラス繊維、合成繊維または炭素繊維である請求項９に記載の繊維。 The fiber according to claim 9, wherein the fiber is glass fiber, synthetic fiber or carbon fiber.
- 請求項１～５のいずれかに記載のサイジング剤を含む繊維トウ。 A fiber tow comprising the sizing agent according to any one of claims 1 to 5.
- 前記繊維トウを構成する繊維が、ガラス繊維、合成繊維または炭素繊維である請求項１１に記載の繊維トウ。 The fiber tow according to claim 11, wherein the fiber constituting the fiber tow is glass fiber, synthetic fiber or carbon fiber.
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| JP2019527741A JP6814882B2 (en) | 2017-07-06 | 2018-07-04 | Sizing agent and its manufacturing method, and fiber and fiber tow |
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| JP2017-132953 | 2017-07-06 | ||
| JP2017132953 | 2017-07-06 |
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| JP (1) | JP6814882B2 (en) |
| WO (1) | WO2019009325A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100215948A1 (en) * | 2009-02-20 | 2010-08-26 | University Of Delaware | Rubbery-block containing polymers, fiber sizings thereof and composites thereof |
| JP5559868B2 (en) * | 2009-04-10 | 2014-07-23 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー | Fiber sizing agent composed of nanoparticles |
| WO2016063809A1 (en) * | 2014-10-23 | 2016-04-28 | ニッタ株式会社 | Composite material and reinforcing fiber |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6621970B2 (en) * | 2001-03-28 | 2003-09-16 | Alcatel | UV-curable optical fiber coating composition including fullerenes |
| JP4872112B2 (en) * | 2004-05-13 | 2012-02-08 | 国立大学法人北海道大学 | Fine carbon dispersion |
| KR100745467B1 (en) * | 2006-05-12 | 2007-08-02 | 주식회사 비 에스 지 | Functional fiber having antibacterial and antistatic effect |
| JP6744106B2 (en) * | 2016-02-16 | 2020-08-19 | 昭和電工株式会社 | Water-soluble complex of fullerene and γ-cyclodextrin and method for producing the same |
-
2018
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- 2018-07-04 JP JP2019527741A patent/JP6814882B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100215948A1 (en) * | 2009-02-20 | 2010-08-26 | University Of Delaware | Rubbery-block containing polymers, fiber sizings thereof and composites thereof |
| JP5559868B2 (en) * | 2009-04-10 | 2014-07-23 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー | Fiber sizing agent composed of nanoparticles |
| WO2016063809A1 (en) * | 2014-10-23 | 2016-04-28 | ニッタ株式会社 | Composite material and reinforcing fiber |
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| URVANOV, SERGEY ALEKSEYEVICH ET AL.: "Carbon Fiber Modified with Carbon Nanotubes and Fullerenes for Fibrous Composite Application", JOURNAL OF MATERIALS SCIENCE AND ENGINEERING A, vol. 11, 10 November 2013 (2013-11-10), pages 725 - 731 * |
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| JPWO2019009325A1 (en) | 2019-12-12 |
| JP6814882B2 (en) | 2021-01-20 |
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