WO2022260131A1 - 無機繊維用サイジング剤、無機繊維、その製造方法、及び複合材料 - Google Patents
無機繊維用サイジング剤、無機繊維、その製造方法、及び複合材料 Download PDFInfo
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- WO2022260131A1 WO2022260131A1 PCT/JP2022/023294 JP2022023294W WO2022260131A1 WO 2022260131 A1 WO2022260131 A1 WO 2022260131A1 JP 2022023294 W JP2022023294 W JP 2022023294W WO 2022260131 A1 WO2022260131 A1 WO 2022260131A1
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Images
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Definitions
- the present invention relates to an inorganic fiber sizing agent containing cellulose nanofibers, an inorganic fiber, a method for producing the same, and a composite material.
- thermoplastic resin composite materials are known as materials containing inorganic fibers such as carbon fibers and matrix resins such as thermoplastic resins as base materials, and are widely used in various fields such as building materials and transportation equipment.
- inorganic fibers such as carbon fibers and matrix resins such as thermoplastic resins as base materials
- base materials such as thermoplastic resins
- a treatment of adhering a sizing agent to the inorganic fibers is performed.
- Patent Document 1 discloses a sizing agent-coated carbon fiber obtained by coating a carbon fiber with a sizing agent containing nanocellulose having a number average fiber diameter of 1 to 1000 nm and an epoxy group-containing compound. It is described that the nanocellulose in the sizing agent is contained in an amount of 5% by mass or more with respect to the total amount of the sizing agent.
- Patent Document 1 does not sufficiently improve the adhesion of the inorganic fibers to the base material, and also has problems of insufficient prevention of falling off from the inorganic fibers and insufficient handling.
- an inorganic fiber sizing agent containing a predetermined amount of cellulose nanofibers and a resin is suitable.
- an inorganic fiber sizing agent of one aspect of the present invention contains a resin and cellulose nanofibers, and the content of the cellulose nanofibers in the nonvolatile matter of the sizing agent is 10 ppm or more and 50000 ppm.
- the gist is that it is less than
- the cellulose nanofibers may have a fiber diameter of 1 nm or more and 1000 nm or less. That is, at least part of the cellulose nanofibers may have a fiber diameter of 1 nm or more and 1000 nm or less.
- the resin contains at least one selected from epoxy resins, vinyl ester resins, polyamide resins, polyolefin resins, polyurethane resins, polyester resins, phenoxy resins, polyimide resins, and polyimide resin precursors. It may be something to do.
- the inorganic fiber sizing agent may further contain a surfactant.
- the inorganic fiber sizing agent may be applied to glass fibers or carbon fibers.
- the resin in the inorganic fiber sizing agent may contain at least one selected from an epoxy resin and a polyester resin, in which case the inorganic fiber sizing agent is a composite material in which the matrix resin is an epoxy resin, For example, it may be applied to the inorganic fibers forming part of such composite materials.
- the resin in the inorganic fiber sizing agent may contain at least one selected from polyamide resins, polyurethane resins, polyimide resins, and polyimide resin precursors, in which case the inorganic fiber sizing agent is a matrix resin is a polyamide resin, and even inorganic fibers forming part of such a composite.
- the resin in the inorganic fiber sizing agent may comprise a vinyl ester resin, in which case the inorganic fiber sizing agent is a composite material in which the matrix resin is a vinyl ester resin, and more particularly a composite material of such a composite material. It may be applied to the inorganic fibers that make up a part.
- the resin in the inorganic fiber sizing agent may contain at least one selected from a polyolefin resin and a phenoxy resin, in which case the inorganic fiber sizing agent is a composite material in which the matrix resin is a polyolefin resin, Furthermore, it may be applied to the inorganic fibers forming part of such composite materials.
- another aspect of the present invention provides an inorganic fiber to which the sizing agent for inorganic fiber is adhered.
- another aspect of the present invention provides a method for producing inorganic fibers, comprising the step of adhering the sizing agent for inorganic fibers to inorganic fibers.
- a composite material of another aspect of the present invention is a composite material containing the inorganic fiber and a matrix resin, wherein the resin in the inorganic fiber sizing agent is an epoxy resin and a polyester resin. and the matrix resin is an epoxy resin.
- a composite material of another aspect of the present invention is a composite material containing the inorganic fiber and a matrix resin, wherein the resin in the inorganic fiber sizing agent is a polyamide resin, a polyurethane resin, At least one selected from polyimide resins and polyimide resin precursors is included, and the matrix resin is a polyamide resin.
- a composite material of another aspect of the present invention is a composite material containing the inorganic fiber and a matrix resin, wherein the resin in the inorganic fiber sizing agent contains a vinyl ester resin,
- the gist is that the matrix resin is a vinyl ester resin.
- a composite material according to another aspect of the present invention is a composite material containing the inorganic fiber and a matrix resin, wherein the resin in the inorganic fiber sizing agent is a polyolefin resin and a phenoxy resin.
- the gist is that the matrix resin is a polyolefin resin, including at least one selected.
- the present invention it is possible to improve the adhesion of the inorganic fibers to the base material of the composite material, the prevention of falling off from the inorganic fibers, and the handling of the sizing agent.
- a sizing agent for inorganic fibers (hereinafter also referred to as a sizing agent) according to the present invention will be described.
- the sizing agent contains a predetermined amount of cellulose nanofibers and a resin.
- Cellulose nanofibers can improve the adhesion between the inorganic fibers and the matrix resin.
- Cellulose nanofibers include cellulose microfibrils (single cellulose nanofibers) with a width of 3 to 4 nm as a basic fiber diameter, and cellulose microfibrils with a width of 10 to 20 nm, which are bundles of several cellulose nanofibers.
- Microfibrillated cellulose forming a web-like network with a width of several tens to several hundreds of nanometers in which microfibril bundles are further aggregated into bundles, and the like, and any of them may be used.
- Cellulose nanofibers may be obtained by using a plant fiber material such as wood pulp as a raw material and defibrating and refining it by a known manufacturing method, or a commercially available product may be used.
- a plant fiber material such as wood pulp
- a commercially available product may be used.
- the known production method include, but are not limited to, a mechanical pulverization method such as a high-pressure homogenizer method and an ultrasonic fibrillation method, an underwater counter-collision method, a TEMPO oxidation method, and a method of miniaturization using an enzyme such as cellulase. mentioned.
- the lower limit of the fiber diameter of cellulose nanofibers is preferably 1 nm or more, more preferably 3 nm or more.
- the upper limit of the fiber diameter of cellulose nanofibers is preferably 1000 nm or less, preferably 800 nm or less.
- cellulose nanofibers Twenty non-overlapping cellulose nanofibers were randomly selected, and their fiber diameters were determined. The obtained maximum and minimum fiber diameters are referred to as the “fiber diameter (minimum-maximum)" of the measured cellulose nanofibers. In addition, the average value of the determined fiber diameters is referred to as the “fiber diameter (average value)” of the measured cellulose nanofibers.
- fiber diameter minimum-maximum
- the average value of the determined fiber diameters is referred to as the “fiber diameter (average value)” of the measured cellulose nanofibers.
- the sizing agent preferably contains cellulose nanofibers with a fiber diameter of 1 nm or more and 1000 nm or less, more preferably 50% by mass or more, more preferably 80% by mass or more of the total cellulose nanofibers. It is more preferable that
- the cellulose nanofibers may be used singly or in combination of two or more.
- the lower limit of the content of cellulose nanofibers in the non-volatile content of the sizing agent is 10 ppm or more, preferably 15 ppm or more. When the content is 10 ppm or more, the adhesion between the matrix resin and the inorganic fibers can be further improved.
- the upper limit of the content ratio is less than 50000 ppm, preferably 46000 ppm or less. If the content is less than 50,000 ppm, the handleability can be improved.
- the non-volatile matter refers to the residue after the object is heat-treated at 105° C. for 2 hours to sufficiently remove volatile substances, that is, the absolute dry matter.
- the resin is appropriately selected from known resins according to the use of the inorganic fiber to which the sizing agent is applied.
- resins include epoxy resins, vinyl ester resins, polyamide resins, polyolefin resins, polyurethane resins, polycarbonate resins, polyester resins, PEEK resins, fluorine resins, phenoxy resins, phenol resins, BMI resins, polyimide resins, and polyimide resins.
- Precursors, polyethersulfone resins, and the like are included.
- epoxy resins, vinyl ester resins, polyamide resins, polyolefin resins, polyurethane resins, polyester resins, phenoxy resins, polyimide resins, and polyimide resin precursors are preferred.
- the resin examples include epoxy resins (manufactured by Mitsubishi Chemical Corporation: trade names jER828 and jER1002), epoxy resins (manufactured by Nagase ChemteX Corporation: trade names Denacol EX-521), polyurethane resins (manufactured by Daiichi Kogyo Seiyaku Co., Ltd. : Product name Superflex 500M), modified polypropylene resin (manufactured by Maruyoshi Chemical Co., Ltd.: product name MGP-1650), modified polypropylene resin (manufactured by Toho Chemical Industry Co., Ltd.: product name Hitec P-9018), modified polyester resin (manufactured by Toyobo Co., Ltd.
- epoxy resins manufactured by Mitsubishi Chemical Corporation: trade names jER828 and jER1002
- epoxy resins manufactured by Nagase ChemteX Corporation: trade names Denacol EX-521
- polyurethane resins manufactured by Daiichi Kog
- the type of resin blended in the sizing agent will improve the adhesion of the inorganic fibers to the matrix resin.
- the type of the matrix resin it is preferable to consider the type of the matrix resin and make a selection.
- the matrix resin is an epoxy resin
- the resin in the sizing agent is preferably at least one selected from epoxy resins and polyester resins.
- the matrix resin is a polyamide resin
- the resin in the sizing agent is preferably at least one selected from polyamide resins, polyurethane resins, polyimide resins, and polyimide resin precursors.
- the resin in the sizing agent is preferably vinyl ester resin.
- the resin in the sizing agent is preferably at least one selected from polyolefin resins and phenoxy resins.
- the sizing agent may further contain a surfactant.
- a surfactant By blending the surfactant with the sizing agent, the cellulose nanofibers are less likely to fall off easily from the inorganic fibers to which the sizing agent has been applied, that is, the ability to prevent the cellulose nanofibers from falling off can be improved.
- surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. These surfactants may be used alone or in combination of two or more.
- nonionic surfactant a known one can be appropriately adopted.
- specific examples of nonionic surfactants include (1) compounds obtained by adding alkylene oxides having 2 to 4 carbon atoms to organic acids, organic alcohols, organic amines and/or organic amides, such as polyoxyethylene dilauric acid esters.
- anionic surfactant a known one can be appropriately adopted.
- anionic surfactants include (1) fatty alcohol phosphates such as lauryl phosphate, cetyl phosphate, octyl phosphate, oleyl phosphate, and stearyl phosphate.
- aliphatic alcohols such as polyoxyethylene lauryl ether phosphate, polyoxyethylene oleyl ether phosphate, and polyoxyethylene stearyl ether phosphate
- aliphatic alcohols such as ethylene oxide and (6) castor oil fatty acid sulfate, sesame oil fatty acid sulfate, tall oil fatty acid sulfate, soybean oil fatty acid sulfate, rapeseed oil fatty acid sulfate Fatty acid sulfates such as ester salts, palm oil fatty acid sulfates, lard fatty acid sulfates, beef tallow fatty acid sulfates, and whale oil fatty acid sulfates, (7) castor oil sulfates, sesame oil sulfates , tall oil sulfate, soybean oil sulfate, rapeseed oil sulfate, palm oil sulfate, lard sulfate, beef tallow sulfate, whale oil sulfate, etc.
- fatty acid salts such as laurate, oleate and stearate
- fatty alcohol sulfosuccinate salts such as dioctylsulfosuccinate.
- the counter ion of the anionic surfactant include alkali metal salts such as potassium salts and sodium salts, ammonium salts, alkanolamine salts such as triethanolamine, and the like.
- cationic surfactant As the cationic surfactant, a known one can be appropriately adopted. Specific examples of cationic surfactants include lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, didecyldimethylammonium chloride, 1,2-dimethylimidazole, and triethanolamine. be done.
- amphoteric surfactants can be appropriately employed.
- Specific examples of amphoteric surfactants include, for example, betaine type amphoteric surfactants.
- the lower limit of the surfactant content in the non-volatile content of the sizing agent is preferably 1% by mass or more, more preferably 2% by mass or more. When the content is 1% by mass or more, the anti-dropping property can be further improved.
- the upper limit of the surfactant content is preferably 50% by mass or less, more preferably 40% by mass or less. When the content is 50% by mass or less, the adhesiveness can be further improved.
- the action and effect of the sizing agent of this embodiment will be described.
- the sizing agent of the present embodiment contains a predetermined amount of cellulose nanofibers and a resin.
- this sizing agent is attached to the inorganic fibers, the adhesion of the inorganic fibers to the base material of the composite material and the ability to prevent the cellulose nanofibers from falling off from the inorganic fibers can be improved.
- the sizing agent is directly applied to the surface of the inorganic fiber, irregularities derived from cellulose nanofibers are formed on the surface of the fiber, and the anchor effect improves the adhesiveness.
- the content of cellulose nanofibers in the non-volatile content of the sizing agent is configured to be less than 50000 ppm. Therefore, the fluidity of the sizing agent solution can be improved or a decrease in fluidity can be suppressed. In addition, when diluting the sizing agent with a solvent or when preparing the sizing agent, it can be easily mixed with the solvent. Therefore, the handleability of the sizing agent can be improved.
- the method for manufacturing inorganic fibers of the present embodiment includes a step of adhering the sizing agent of the first embodiment to carbon fibers.
- the amount of the sizing agent (not including the solvent) attached is no particular limitation on the amount of the sizing agent (not including the solvent) attached, but it is preferable to attach the sizing agent to the inorganic fibers in an amount of 0.01% by mass or more and 10% by mass or less. By defining such a numerical range, the effects such as bundling properties of the inorganic fibers can be further improved.
- inorganic fibers applied in the present embodiment are not particularly limited, and examples thereof include glass fibers, carbon fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, slag fibers, and the like. Among these, glass fiber and carbon fiber are preferable from the viewpoint of more effectively exhibiting the effects of the present invention.
- Types of carbon fibers include, for example, PAN-based carbon fibers obtained using acrylic fibers as a raw material, pitch-based carbon fibers obtained using pitch as a raw material, recycled carbon fibers, polyester fibers, polyethylene resins, phenolic resins, cellulose resins, lignin. Examples thereof include carbon fibers obtained using resin or the like as a raw material.
- a method generally used industrially can be used.
- a roller dipping method, a roller contact method, a spray method, a papermaking method and the like can be mentioned.
- the inorganic fibers with the sizing agent attached thereto may then be dried using known methods.
- the method for producing inorganic fibers of the present embodiment includes a step of adhering a sizing agent containing cellulose nanofibers and a resin to carbon fibers. Therefore, it is possible to improve the drop-off prevention properties of the cellulose nanofibers from the inorganic fibers. In addition, since the application of the sizing agent to the inorganic fibers is completed in a single step, it is efficient, that is, the process efficiency can be improved.
- a composite material is obtained by impregnating the inorganic fibers to which the sizing agent is attached according to the second embodiment into the matrix resin as the base material.
- the form of the inorganic fibers in producing the composite material is not particularly limited, and may be, for example, long fibers, short fibers, non-woven fabrics, or the like.
- matrix resin The matrix resin is appropriately selected from known ones depending on the purpose, application, etc. of the composite material.
- matrix resins include epoxy resins, vinyl ester resins, polyamide resins, polyolefin resins, polyurethane resins, polycarbonate resins, polyester resins, PEEK resins, fluorine resins, phenoxy resins, phenol resins, BMI resins, polyimide resins, and polyimides.
- examples include resin precursors, polyethersulfone resins, and the like.
- the matrix resin may be selected in consideration of the type of resin contained in the sizing agent from the viewpoint of improving adhesion with inorganic fibers and improving recyclability.
- the resin in the sizing agent is preferably at least one selected from epoxy resins and polyester resins.
- the resin in the sizing agent is preferably at least one selected from polyamide resins, polyurethane resins, polyimide resins, and polyimide resin precursors.
- the matrix resin in the sizing agent is preferably vinyl ester resin.
- the resin in the sizing agent is preferably at least one selected from polyolefin resins and phenoxy resins.
- a sizing agent containing a predetermined amount of cellulose nanofibers and a resin is adhered in advance to the inorganic fibers contained in the composite material of the present embodiment. Therefore, due to the excellent adhesion between the inorganic fibers and the matrix resin, it is possible to obtain a fiber-reinforced resin composite material that is particularly excellent in various properties such as mechanical properties.
- the above embodiment may be modified as follows.
- the above embodiments and the following modifications can be combined with each other within a technically consistent range.
- the sizing agent of the above embodiment contains water or an organic solvent, This does not preclude the addition of smoothing agents, antioxidants, preservatives, and the like.
- the field to which the sizing agent of the above embodiment is applied is not particularly limited.
- it may be applied to carbon fiber composite materials (CFRP) impregnated with a matrix resin such as polyimide resin, as well as fibers for reinforcing concrete.
- CFRP carbon fiber composite materials
- Test category 1 preparation of sizing agent
- cellulose nanofibers (A-1) having a fiber diameter (minimum-maximum) of 20 to 300 nm and a fiber diameter (average) of 180 nm shown in Table 1, and resin (B) shown in Table 2
- Epoxy resin (B-1) shown and a random adduct (C-1) of 30 mol of ethylene oxide and 5 mol of propylene oxide of tristyrenated phenol shown in Table 3 as a surfactant (C) were used as raw materials. .
- A A mixture of raw materials was heated to 100°C and homogenized, then cooled to 70°C or less and water was gradually added to obtain an aqueous solution of a sizing agent.
- B An aqueous liquid of a sizing agent was obtained by mixing a pre-prepared resin emulsion containing a surfactant and a pre-prepared aqueous dispersion of cellulose nanofibers.
- An aqueous liquid of a sizing agent was obtained by mixing a previously prepared resin emulsion, a previously prepared aqueous dispersion of cellulose nanofibers, and a surfactant.
- An aqueous liquid of a sizing agent was obtained by mixing a previously prepared resin emulsion and a previously prepared aqueous dispersion of cellulose nanofibers.
- An aqueous liquid of a sizing agent was obtained using a previously prepared resin emulsion.
- the type and content of cellulose nanofibers (A) contained in the aqueous liquid of the sizing agent thus obtained, the type and content of resin (B) as non-volatile matter, and the type of surfactant (C) and content, and the preparation method of the sizing agent are shown in Table 4, "Cellulose nanofiber (A)” column, "Resin (B)” column, “Surfactant (C)” column, and "Mixing method during manufacturing” column. are shown respectively.
- the non-volatile content of the resin (B) was obtained as the mass of the absolute dry product obtained by heat-treating the object at 105° C. for 2 hours to sufficiently remove volatile substances.
- Polypropylene resin 2% by mass maleic anhydride-modified polypropylene *1): Non-volatile content basis *2): Parts by mass relative to a total of 100 parts by mass of the non-volatile content of resin (B) and surfactant (C) *3): Sizing agent Content ratio in non-volatile matter (ppm) Test category 2 (evaluation) - Evaluation of Adhesiveness Adhesiveness was evaluated by stress measured by a microdroplet method using a commercially available composite material interfacial property evaluation device.
- FIG. 1 shows a schematic diagram of a composite material interface property evaluation apparatus 10 .
- the aqueous liquid of each example prepared as described above was further diluted with water to prepare an aqueous liquid having a solid content of 2% by mass.
- Strand-like carbon fibers or glass to which the sizing agent of each example is applied by oiling (supplying) this aqueous liquid by an immersion method so that 2% by mass as a solid content is applied to the strand-like carbon fibers or glass fibers.
- a fiber was prepared.
- one carbon fiber or glass fiber is taken out from this strand-like carbon fiber or glass fiber, and both ends of the fiber 12 are fixed with an adhesive 14 in a state of tension to a plate-like square frame-like holder 11. .
- the matrix resin of each example shown in Table 4 was adhered to the fiber 12 so as to form a resin droplet 13 having a diameter of approximately 70 ⁇ m and was fixed.
- Two plate-like blades 17 and 18 tapered on one side in a vertical cross section are attached to the device main body (not shown) with their tips 17a and 18a facing each other. .
- the holder 11 was attached to the substrate 16 fixed to the device body at a position where the fiber 12 to which the resin droplet 13 was fixed was sandwiched between the tips 17a and 18a of the two blades 17 and 18.
- a load cell 15 is connected to the substrate 16 to measure the stress applied to the substrate 16 .
- the load cell 15 measures the maximum stress F generated when the resin droplet 13 is separated from the fiber 12 by the tips 17a and 18a of the blades 17 and 18. Measured.
- the interfacial shear strength ⁇ was calculated by the following formula 1. The same operation was repeated 20 times, and the average interfacial shear strength obtained was determined. Furthermore, for the obtained average values, the rate of increase with respect to the reference values of the matrix resin used was determined and evaluated according to the following criteria. The results are shown in Table 4, "Adhesion". The type of inorganic fiber and the type of matrix resin used are shown in the columns “inorganic fiber used for adhesion evaluation” and “matrix resin used for adhesion evaluation” in Table 4, respectively.
- Equation 1 F is the maximum stress (N) generated when the resin droplet 13 is separated from the fiber 12; D is the diameter (m) of the fiber 12; L is the diameter (m) of the resin droplet 13 in the drawing direction.
- ⁇ When used as a one-liquid sizing agent in the manufacturing process of inorganic fibers, the sizing agent maintained fluidity and was easy to weigh and pump into the process.
- x Improveper: When used as a one-liquid sizing agent in the manufacturing process of inorganic fibers, the sizing agent did not maintain fluidity, and it was difficult to measure the weight and pump it into the process.
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Abstract
Description
前記無機繊維用サイジング剤は、ガラス繊維又は炭素繊維に適用されてもよい。
前記無機繊維用サイジング剤中の前記樹脂は、エポキシ樹脂及びポリエステル樹脂から選ばれる少なくとも1つを含んでもよく、その場合、前記無機繊維用サイジング剤は、マトリックス樹脂がエポキシ樹脂である複合材料、さらに言えばそのような複合材料の一部を構成する無機繊維に適用されてもよい。
上記課題を解決するために、本発明の別の態様の無機繊維の製造方法は、前記無機繊維用サイジング剤を無機繊維に付着させる工程を含むことを要旨とする。
先ず、本発明に係る無機繊維用サイジング剤(以下、サイジング剤ともいう)を具体化した第1実施形態について説明する。サイジング剤は、所定量のセルロースナノファイバーと、樹脂とを含有する。
セルロースナノファイバーにより、無機繊維とマトリックス樹脂との接着性を向上できる。セルロースナノファイバーとしては、大きさにより、基本となる繊維径としての幅が3~4nmのセルロースミクロフィブリル(シングルセルロースナノファイバー)、それが数本の束となった幅10~20nmのセルロースミクロフィブリル束、ミクロフィブリル束がさらに集まって束となった幅数十~数百nmのクモの巣状のネットワークを形成しているミクロフィブリル化セルロース等に分けられるが、いずれを使用してもよい。セルロースナノファイバーは、木材パルプ等の植物系繊維材料を原料として、公知の製造方法により解繊、微細化することにより得てもよく、市販品を使用してもよい。公知の製造方法としては、特に限定されないが、例えば高圧ホモジナイザー法、超音波解繊法等の機械により粉砕する方法、水中カウンターコリジョン法、TEMPO酸化法、セルラーゼ等の酵素で微細化する方法等が挙げられる。
サイジング剤の不揮発分中におけるセルロースナノファイバーの含有割合の下限は、10ppm以上、好ましくは15ppm以上である。かかる含有割合が10ppm以上の場合、マトリックス樹脂と無機繊維との接着性をより向上できる。また、かかる含有割合の上限は、50000ppm未満、好ましくは46000ppm以下である。かかる含有割合が50000ppm未満の場合、ハンドリング性を向上できる。なお、本明細書において不揮発分とは、対象物を105℃で2時間熱処理して揮発性物質を十分に除去した後の残渣、すなわち絶乾物をいう。
樹脂は、サイジング剤が付与される無機繊維の用途等に応じて適宜公知のものから選択される。樹脂の具体例としては、例えばエポキシ樹脂、ビニルエステル樹脂、ポリアミド樹脂、ポリオレフィン樹脂、ポリウレタン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、PEEK樹脂、フッ素樹脂、フェノキシ樹脂、フェノール樹脂、BMI樹脂、ポリイミド樹脂、ポリイミド樹脂前駆体、ポリエーテルスルホン樹脂等が挙げられる。これらの中でエポキシ樹脂、ビニルエステル樹脂、ポリアミド樹脂、ポリオレフィン樹脂、ポリウレタン樹脂、ポリエステル樹脂、フェノキシ樹脂、ポリイミド樹脂、ポリイミド樹脂前駆体が好ましい。
サイジング剤は、さらに界面活性剤を含有してもよい。界面活性剤をサイジング剤に配合することにより、サイジング剤を付与した後の無機繊維からセルロースナノファイバーが容易に脱落しにくくなり、すなわちセルロースナノファイバーの脱落防止性を向上できる。界面活性剤としては、例えばアニオン界面活性剤、カチオン界面活性剤、非イオン界面活性剤、両性界面活性剤が挙げられる。これらの界面活性剤は、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。
サイジング剤の不揮発分中における界面活性剤の含有割合の下限は、好ましくは1質量%以上、より好ましくは2質量%以上である。かかる含有割合が1質量%以上の場合、脱落防止性をより向上できる。界面活性剤の含有割合の上限は、好ましくは50質量%以下、より好ましくは40質量%以下である。かかる含有割合が50質量%以下の場合、接着性をより向上できる。
(1-1)本実施形態のサイジング剤は、所定量のセルロースナノファイバーと、樹脂とを含有する。このサイジング剤を無機繊維に付着させた場合、複合材料の母材に対する無機繊維の接着性及び無機繊維からのセルロースナノファイバーの脱落防止性を向上できる。特に、サイジング剤が無機繊維表面に直接塗布されることにより、繊維表面上にセルロースナノファイバー由来の凹凸が形成されるため、アンカー効果により接着性が向上される。また、サイジング剤を付着させた無機繊維をマトリックス樹脂に含浸させて複合材料を形成した場合、無機繊維とマトリックス樹脂との界面におけるクラックの拡大が抑制されるため、複合材料の強度を向上できる。
次に本発明に係る無機繊維の製造方法を具体化した第2実施形態について説明する。第2実施形態について以下に記載する以外の事項は、第1実施形態と同様である。
本実施形態において適用される無機繊維の種類としては、特に限定されず、例えばガラス繊維、炭素繊維、セラミック繊維、金属繊維、鉱物繊維、岩石繊維、スラッグ繊維等が挙げられる。これらの中でも本発明の効果をより有効に発現できる観点からガラス繊維、炭素繊維が好ましい。炭素繊維の種類としては、例えばアクリル繊維を原料として得られたPAN系炭素繊維、ピッチを原料として得られたピッチ系炭素繊維、リサイクル炭素繊維、ポリエステル繊維、ポリエチレン樹脂、フェノール樹脂、セルロース樹脂、リグニン樹脂等を原料として得られる炭素繊維が挙げられる。
(2-1)本実施形態の無機繊維の製造方法は、セルロースナノファイバーと樹脂とを含むサイジング剤を炭素繊維に付着させる工程を含んでいる。したがって、特に無機繊維からのセルロースナノファイバーの脱落防止性を向上できる。また、単一の工程で無機繊維に対するサイジング剤の付与が完了するために効率的であり、すなわち工程効率性も向上できる。
次に、本発明に係る複合材料を具体化した第3実施形態について説明する。第3実施形態について以下に記載する以外の事項は、第1,2実施形態と同様である。
マトリックス樹脂は、複合材料の目的、用途等に応じて公知のものから適宜選択される。マトリックス樹脂の具体例としては、例えばエポキシ樹脂、ビニルエステル樹脂、ポリアミド樹脂、ポリオレフィン樹脂、ポリウレタン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、PEEK樹脂、フッ素樹脂、フェノキシ樹脂、フェノール樹脂、BMI樹脂、ポリイミド樹脂、ポリイミド樹脂前駆体、ポリエーテルスルホン樹脂等が挙げられる。
(3-1)本実施形態の複合材料中に含まれる無機繊維には、所定量のセルロースナノファイバーと、樹脂とを含有するサイジング剤を予め付着させている。したがって、無機繊維とマトリックス樹脂との優れた接着性により、特に機械特性等の各種特性に優れる繊維強化樹脂複合材料が得られる。
・上記実施形態のサイジング剤は、本発明の効果を阻害しない範囲内において、サイジング剤の性能を維持する観点、無機繊維に対する付与性向上等の観点から、その他の成分として、水又は有機溶媒、平滑剤、酸化防止剤、防腐剤等を配合することを妨げるものではない。
試験区分1(サイジング剤の調製)
実施例1のサイジング剤の調製に際し、表1に示される繊維径(最小-最大)20-300nm、繊維径(平均)180nmのセルロースナノファイバー(A-1)、樹脂(B)として表2に示されるエポキシ樹脂(B-1)、界面活性剤(C)として表3に示されるトリスチレン化フェノールのエチレンオキサイド30モルとプロピレンオキサイド5モルのランダム付加物(C-1)を原料として使用した。そして、予め調製した樹脂乳化物と、予め調製したセルロースナノファイバーの水分散物と、界面活性剤とを混合することで、表4に示される含有割合からなる実施例1のサイジング剤の水性液を得た。
B:予め調製した界面活性剤を含む樹脂乳化物と、予め調製したセルロースナノファイバーの水分散物を混合することでサイジング剤の水性液を得た。
D:予め調製した樹脂乳化物と、予め調製したセルロースナノファイバーの水分散物を混合することでサイジング剤の水性液を得た。
このようにして得られたサイジング剤の水性液中に含まれるセルロースナノファイバー(A)の種類と含有量、樹脂(B)の種類と不揮発分としての含有量、界面活性剤(C)の種類と含有量、サイジング剤の調製方法を、表4の「セルロースナノファイバー(A)」欄、「樹脂(B)」欄、「界面活性剤(C)」欄、「製造時の混合方法」欄にそれぞれ示す。樹脂(B)の不揮発分は、対象物を105℃で2時間熱処理して揮発性物質を十分に除去した絶乾物の質量として求めた。
(接着性評価に使用したマトリックス樹脂)
エポキシ樹脂:三菱ケミカル社製の商品名jER828+トリエチレンテトラミン
ビニルエステル樹脂:昭和電工社製の商品名リポキシR-804B(同社製のメチルエチルケトンパーオキシド硬化剤を使用)
ポリアミド樹脂:宇部興産社製のUBEナイロン 1011FB
ポリプロピレン樹脂:2質量%無水マレイン酸変性ポリプロピレン
*1):不揮発分基準
*2):樹脂(B)の不揮発分と界面活性剤(C)の合計100質量部に対する質量部
*3):サイジング剤の不揮発分中における含有割合(ppm)
試験区分2(評価)
・接着性の評価
接着性は、市販の複合材界面特性評価装置を用いてマイクロドロップレット法によって測定される応力により評価した。図1に複合材界面特性評価装置10の概略図を示す。
Fは、繊維12から樹脂滴13が剥離する際に生じる最大応力(N)、
Dは、繊維12の直径(m)、
Lは、樹脂滴13の引き抜き方向の直径(m)である。
エポキシ樹脂:60MPa
ビニルエステル樹脂:40MPa
ポリアミド樹脂:50MPa
ポリプロピレン樹脂:22MPa
接着性の評価基準
○(可):増加率が5%以上
×(不可):増加率が5%未満
・脱落防止性の評価
無機繊維にサイジング剤を付与するサイジング浴を通過させた後の無機繊維からのセルロースナノファイバーの脱落の有無を、乾燥工程を経たのちの金属ローラー部分で確認し、以下の基準で脱落防止性を評価した。結果を表4の「脱落防止性」欄に示す。
○(可):金属ローラーにセルロースナノファイバーの脱落がわずかに見られるが、2週間以上連続しての操業が可能であった場合
×(不可):金属ローラーにセルロースナノファイバーの脱落が多くみられ2週間未満で製造を止めて清掃する必要があった場合
・ハンドリング性
各例のサイジング剤のハンドリング性を以下の基準で評価した。結果を表4の「ハンドリング性」欄に示す。
×(不可):1液のサイジング剤として無機繊維の製造工程で使用する際に、サイジング剤が流動性を保っておらず、重量の計測、工程へのポンプによる投入が困難であった。
各例のサイジング剤について工程効率性を以下の基準で評価した。結果を表4の「工程効率性」欄に示す。
×(不可):セルロースナノファイバーを繊維に付与する工程と、その後に樹脂を含むサイジング剤を繊維に付与する工程という2段階の工程がある場合
以上表4の結果からも明らかなように、各実施例のサイジング剤は、接着性、脱落防止性、ハンドリング性、工程効率性の評価がいずれも可以上であった。本発明によれば、接着性、脱落防止性、ハンドリング性、工程効率性を向上できるという効果が生じる。
11…ホルダー
12…繊維
13…樹脂滴
14…接着剤
15…ロードセル
16…基板
17,18…ブレード
Claims (15)
- 樹脂及びセルロースナノファイバーを含有する無機繊維用サイジング剤であって、前記無機繊維用サイジング剤の不揮発分中における前記セルロースナノファイバーの含有割合が、10ppm以上50000ppm未満であることを特徴とする無機繊維用サイジング剤。
- 前記セルロースナノファイバーは、繊維径が1nm以上1000nm以下のものを含む請求項1に記載の無機繊維用サイジング剤。
- 前記樹脂が、エポキシ樹脂、ビニルエステル樹脂、ポリアミド樹脂、ポリオレフィン樹脂、ポリウレタン樹脂、ポリエステル樹脂、フェノキシ樹脂、ポリイミド樹脂、及びポリイミド樹脂前駆体から選ばれる少なくとも1つを含有するものである請求項1又は2に記載の無機繊維用サイジング剤。
- 更に、界面活性剤を含有する請求項1~3のいずれか一項に記載の無機繊維用サイジング剤。
- ガラス繊維又は炭素繊維に適用される請求項1~4のいずれか一項に記載の無機繊維用サイジング剤。
- 前記樹脂が、エポキシ樹脂及びポリエステル樹脂から選ばれる少なくとも1つを含み、マトリックス樹脂がエポキシ樹脂である複合材料に適用される請求項1~5のいずれか一項に記載の無機繊維用サイジング剤。
- 前記樹脂が、ポリアミド樹脂、ポリウレタン樹脂、ポリイミド樹脂、及びポリイミド樹脂前駆体から選ばれる少なくとも1つを含み、マトリックス樹脂がポリアミド樹脂である複合材料に適用される請求項1~5のいずれか一項に記載の無機繊維用サイジング剤。
- 前記樹脂が、ビニルエステル樹脂を含み、マトリックス樹脂がビニルエステル樹脂である複合材料に適用される請求項1~5のいずれか一項に記載の無機繊維用サイジング剤。
- 前記樹脂が、ポリオレフィン樹脂及びフェノキシ樹脂から選ばれる少なくとも1つを含み、マトリックス樹脂がポリオレフィン樹脂である複合材料に適用される請求項1~5のいずれか一項に記載の無機繊維用サイジング剤。
- 請求項1~5のいずれか一項に記載の無機繊維用サイジング剤が付着していることを特徴とする無機繊維。
- 請求項1~9のいずれか一項に記載の無機繊維用サイジング剤を無機繊維に付着させる工程を含むことを特徴とする無機繊維の製造方法。
- 請求項10に記載の無機繊維とマトリックス樹脂とを含む複合材料であって、前記無機繊維用サイジング剤中の樹脂が、エポキシ樹脂及びポリエステル樹脂から選ばれる少なくとも1つを含み、前記マトリックス樹脂がエポキシ樹脂であることを特徴とする複合材料。
- 請求項10に記載の無機繊維とマトリックス樹脂とを含む複合材料であって、前記無機繊維用サイジング剤中の樹脂がポリアミド樹脂、ポリウレタン樹脂、ポリイミド樹脂、及びポリイミド樹脂前駆体から選ばれる少なくとも1つを含み、前記マトリックス樹脂がポリアミド樹脂であることを特徴とする複合材料。
- 請求項10に記載の無機繊維とマトリックス樹脂とを含む複合材料であって、前記無機繊維用サイジング剤中の樹脂がビニルエステル樹脂を含み、前記マトリックス樹脂がビニルエステル樹脂であることを特徴とする複合材料。
- 請求項10に記載の無機繊維とマトリックス樹脂とを含む複合材料であって、前記無機繊維用サイジング剤中の樹脂がポリオレフィン樹脂及びフェノキシ樹脂から選ばれる少なくとも1つを含み、前記マトリックス樹脂がポリオレフィン樹脂であることを特徴とする複合材料。
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JP2016079507A (ja) * | 2014-10-09 | 2016-05-16 | Dic株式会社 | 繊維集束剤 |
JP2017119936A (ja) * | 2015-12-24 | 2017-07-06 | 東レ株式会社 | サイジング剤塗布炭素繊維、サイジング剤塗布炭素繊維の製造方法、プリプレグおよび炭素繊維強化複合材料 |
WO2019159733A1 (ja) * | 2018-02-15 | 2019-08-22 | 日本板硝子株式会社 | ゴム補強用コード及びそれを用いたゴム製品 |
CN113481717A (zh) * | 2021-07-18 | 2021-10-08 | 陕西科技大学 | 一种基于一维纳米材料改性碳纤维的制备方法 |
CN113846488A (zh) * | 2021-08-20 | 2021-12-28 | 北京化工大学 | 碳纤维用上浆剂和复合材料 |
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- 2022-06-09 KR KR1020237045052A patent/KR20240014074A/ko unknown
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JP2016079507A (ja) * | 2014-10-09 | 2016-05-16 | Dic株式会社 | 繊維集束剤 |
JP2017119936A (ja) * | 2015-12-24 | 2017-07-06 | 東レ株式会社 | サイジング剤塗布炭素繊維、サイジング剤塗布炭素繊維の製造方法、プリプレグおよび炭素繊維強化複合材料 |
WO2019159733A1 (ja) * | 2018-02-15 | 2019-08-22 | 日本板硝子株式会社 | ゴム補強用コード及びそれを用いたゴム製品 |
CN113481717A (zh) * | 2021-07-18 | 2021-10-08 | 陕西科技大学 | 一种基于一维纳米材料改性碳纤维的制备方法 |
CN113846488A (zh) * | 2021-08-20 | 2021-12-28 | 北京化工大学 | 碳纤维用上浆剂和复合材料 |
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