JP6818289B2 - Fiber-resin composite and its manufacturing method - Google Patents
Fiber-resin composite and its manufacturing method Download PDFInfo
- Publication number
- JP6818289B2 JP6818289B2 JP2016119161A JP2016119161A JP6818289B2 JP 6818289 B2 JP6818289 B2 JP 6818289B2 JP 2016119161 A JP2016119161 A JP 2016119161A JP 2016119161 A JP2016119161 A JP 2016119161A JP 6818289 B2 JP6818289 B2 JP 6818289B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- cnf
- base material
- fiber
- resin composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000805 composite resin Substances 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000463 material Substances 0.000 claims description 83
- 229920005989 resin Polymers 0.000 claims description 79
- 239000011347 resin Substances 0.000 claims description 79
- 239000007788 liquid Substances 0.000 claims description 38
- 229920002678 cellulose Polymers 0.000 claims description 21
- 239000001913 cellulose Substances 0.000 claims description 21
- 239000002121 nanofiber Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 239000004745 nonwoven fabric Substances 0.000 claims description 9
- 239000002759 woven fabric Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 50
- 239000000123 paper Substances 0.000 description 28
- 239000000835 fiber Substances 0.000 description 17
- 239000011159 matrix material Substances 0.000 description 13
- 238000011282 treatment Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920003043 Cellulose fiber Polymers 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000555745 Sciuridae Species 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 210000000050 mohair Anatomy 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Images
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、繊維−樹脂複合体及びその製造方法に関するものであり、詳しくは、セルロースナノファイバーを補強材として用いて樹脂材料の機械的特性を改善する技術に関する。 The present invention relates to a fiber-resin composite and a method for producing the same, and more particularly to a technique for improving the mechanical properties of a resin material by using cellulose nanofibers as a reinforcing material.
セルロースナノファイバー(CNF)は、軽量で高強度、かつ低熱膨張な物性を有しており、樹脂の機械的特性を改善する補強材料として注目を集めている。CNFは、繊維径が4〜100nm、長さマイクロオーダーの極細の繊維であり、これらが互いに絡み合うことで大きな構造体となり、全体としての強度を発現する。 Cellulose nanofibers (CNFs) are lightweight, have high strength, and have low thermal expansion physical properties, and are attracting attention as reinforcing materials for improving the mechanical properties of resins. CNF is an ultrafine fiber having a fiber diameter of 4 to 100 nm and a length of micro order, and when these are entangled with each other, a large structure is formed and the strength as a whole is exhibited.
セルロース繊維は側鎖に水酸基を有するため、樹脂との親和性が良好でない。そのため、セルロースナノファイバーの樹脂への分散性が悪く、また、分散性が悪いと、樹脂の機械的特性を十分に改善できないおそれがある。そこで従来、セルロース繊維が有する水酸基を酸無水物で変性することによって樹脂との親和性を高めたり、樹脂で変性した変性セルロースナノファイバーを用いたりする技術が提案されている(例えば、特許文献1及び特許文献2参照)。 Since the cellulose fiber has a hydroxyl group in the side chain, its affinity with the resin is not good. Therefore, the dispersibility of the cellulose nanofibers in the resin is poor, and if the dispersibility is poor, the mechanical properties of the resin may not be sufficiently improved. Therefore, conventionally, a technique has been proposed in which the hydroxyl group of the cellulose fiber is modified with an acid anhydride to increase the affinity with the resin, or the modified cellulose nanofiber modified with the resin is used (for example, Patent Document 1). And Patent Document 2).
しかしながら、セルロース繊維が有する水酸基の化学修飾により樹脂との親和性を高める手法では、高度な技術や複雑な処理が必要になる。そのため、CNFを用いて樹脂の機械的特性を改善しようとすると、高度かつ高価な設備が必要となったり、製品の高価格化を招いたりすることが考えられる。 However, the method of increasing the affinity with the resin by chemically modifying the hydroxyl group of the cellulose fiber requires advanced technology and complicated treatment. Therefore, if an attempt is made to improve the mechanical properties of a resin by using CNF, it is conceivable that advanced and expensive equipment will be required or the price of the product will be increased.
本発明は上記課題に鑑みなされたものであり、汎用の処理により簡便に樹脂の機械的特性を改善することができる繊維−樹脂複合体の製造方法及び繊維−樹脂複合体を提供することを一つの目的とする。 The present invention has been made in view of the above problems, and provides a method for producing a fiber-resin composite and a fiber-resin composite capable of easily improving the mechanical properties of the resin by a general-purpose treatment. For one purpose.
本開示は、上記課題を解決するために以下の手段を採用した。 The present disclosure employs the following means to solve the above problems.
第1の構成は、以下の工程(A)〜(C)を含む繊維−樹脂複合体の製造方法である。
(A)セルロースナノファイバーと溶剤とを含む液状組成物を、親水性かつ多孔性の基材に塗布する工程。
(B)前記液状組成物を塗布した後の前記基材から前記溶剤を除去する工程。
(C)前記溶剤を除去した後の前記基材と、樹脂とを複合化する工程。
The first configuration is a method for producing a fiber-resin composite, which comprises the following steps (A) to (C).
(A) A step of applying a liquid composition containing cellulose nanofibers and a solvent to a hydrophilic and porous substrate.
(B) A step of removing the solvent from the base material after applying the liquid composition.
(C) A step of compounding the base material and the resin after removing the solvent.
上記構成の製造方法では、セルロースナノファイバー(CNF)と溶剤とを含む液状組成物(以下、「CNF含有液」ともいう。)を、親水性かつ多孔性の基材に塗布した後、基材から溶剤を除去する。これにより、CNF同士が絡み合った状態で基材表面上に付着する。また、CNFが付着した基材は多孔性であるため、CNFが付着した基材と樹脂とを複合化する際に、基材が有する微細な隙間に樹脂が入り込み、樹脂とCNFとの分離を抑制しつつ一体化させることができる。これにより、優れた機械的特性を示すものとすることができる。また、上記方法によれば、機械的特性に優れた樹脂複合体を、汎用の処理を組み合わせることによって簡便な方法で得ることができる。 In the production method having the above structure, a liquid composition containing cellulose nanofibers (CNF) and a solvent (hereinafter, also referred to as “CNF-containing liquid”) is applied to a hydrophilic and porous base material, and then the base material is used. Remove the solvent from. As a result, the CNFs adhere to each other on the surface of the base material in an entangled state. Further, since the base material to which CNF is attached is porous, when the base material to which CNF is attached and the resin are composited, the resin enters into the fine gaps of the base material, and the resin and CNF are separated from each other. It can be integrated while being suppressed. As a result, it is possible to exhibit excellent mechanical properties. Further, according to the above method, a resin composite having excellent mechanical properties can be obtained by a simple method by combining general-purpose treatments.
第2の構成は、セルロースナノファイバーが樹脂マトリクスに含有された繊維−樹脂複合体であって、前記樹脂マトリクス中に、前記セルロースナノファイバーが表面に付着した多孔性の基材を備えることを特徴とする繊維−樹脂複合体である。 The second configuration is a fiber-resin composite in which cellulose nanofibers are contained in a resin matrix, and the resin matrix is provided with a porous base material to which the cellulose nanofibers are attached to a surface. It is a fiber-resin composite.
上記構成の繊維−樹脂複合体では、CNFが表面に付着した基材を樹脂マトリクスの内部に含有させる構成とすることにより、CNFの化学的変性処理等といった高度な技術を用いなくても、樹脂とCNFとの分離を抑制しつつ、CNFを樹脂マトリクスに含有させることができる。よって、機械的特性に優れた樹脂複合体を簡便な方法で得ることができる。 In the fiber-resin composite having the above structure, the base material having the CNF adhered to the surface is contained inside the resin matrix, so that the resin can be used without using advanced techniques such as chemical modification of the CNF. The CNF can be contained in the resin matrix while suppressing the separation between the CNF and the CNF. Therefore, a resin composite having excellent mechanical properties can be obtained by a simple method.
以下に、本開示の繊維−樹脂複合体及びその製造方法について詳しく説明する。当該製造方法は、以下に示す工程(A)〜(C)を含む。 The fiber-resin composite of the present disclosure and a method for producing the same will be described in detail below. The manufacturing method includes the following steps (A) to (C).
<工程(A)>
工程(A)は、CNF含有液を親水性かつ多孔性の基材に塗布する工程である。
(CNF含有液)
CNF含有液は、セルロースナノファイバー(CNF)が溶剤に分散又は溶解されてなる液状組成物である。CNFは、セルロース繊維を解繊することによって得られるものである。セルロース繊維の種類は特に限定されず、例えば、パルプ、綿、再生繊維(例えば、レーヨン、アセテート繊維等)、ホヤ、セルロース合成細菌等に由来するセルロース繊維が挙げられる。セルロース繊維を解繊してセルロースナノファイバーを得る方法としては、公知の方法を適用することができる。具体的には、例えば、セルロース繊維からリグニン及びヘミセルロースを除去した後、リファイナー、高圧ホモジナイザー、グラインダー、混練機、ビーズミル等を用いて機械的に解繊する方法;TEMPO酸化、オゾン処理、酵素処理等の化学的処理を施してセルロース結晶間の相互作用を弱めて解繊する方法、等が挙げられる。
<Process (A)>
The step (A) is a step of applying the CNF-containing liquid to a hydrophilic and porous substrate.
(CNF-containing liquid)
The CNF-containing liquid is a liquid composition in which cellulose nanofibers (CNF) are dispersed or dissolved in a solvent. CNF is obtained by defibrating cellulose fibers. The type of cellulose fiber is not particularly limited, and examples thereof include cellulose fibers derived from pulp, cotton, regenerated fibers (for example, rayon, acetate fibers, etc.), squirrels, cellulose synthetic bacteria, and the like. As a method for defibrating cellulose fibers to obtain cellulose nanofibers, a known method can be applied. Specifically, for example, a method of removing lignin and hemicellulose from cellulose fibers and then mechanically defibrating using a refiner, a high-pressure homogenizer, a grinder, a kneader, a bead mill, or the like; TEMPO oxidation, ozone treatment, enzyme treatment, etc. The method of defibrating the fiber by weakening the interaction between the cellulose crystals by performing the chemical treatment of the above can be mentioned.
なお、セルロース繊維が解繊されてセルロースナノファイバーになった状態とは、例えば、セルロースナノファイバーの平均繊維径が2〜500nmの範囲内である場合をいう。セルロースナノファイバーの平均繊維径は、好ましくは2〜200nmであり、より好ましくは4〜100nmである。セルロースナノファイバーの繊維径は電子顕微鏡で観察して測定することができる。 The state in which the cellulose fibers are defibrated into cellulose nanofibers means, for example, a case where the average fiber diameter of the cellulose nanofibers is in the range of 2 to 500 nm. The average fiber diameter of the cellulose nanofibers is preferably 2 to 200 nm, more preferably 4 to 100 nm. The fiber diameter of cellulose nanofibers can be measured by observing with an electron microscope.
CNF含有液は、溶剤としての分散媒にCNFが分散された分散液であることが好ましい。分散媒としては、CNFの凝集を抑制してCNFを均一に分散させる観点から、水系溶媒であることが好ましく、例えば水、アルコール又は水とアルコールとの混合溶媒等が挙げられる。CNF含有液としては、分散性及び入手容易性の観点から、CNFが水に分散された水分散液を用いることが好ましい。 The CNF-containing liquid is preferably a dispersion liquid in which CNF is dispersed in a dispersion medium as a solvent. The dispersion medium is preferably an aqueous solvent from the viewpoint of suppressing the aggregation of CNF and uniformly dispersing CNF, and examples thereof include water, alcohol, or a mixed solvent of water and alcohol. As the CNF-containing liquid, it is preferable to use an aqueous dispersion in which CNF is dispersed in water from the viewpoint of dispersibility and availability.
CNF含有液におけるCNF濃度は、粘性等を考慮して適宜に選択されるが、好ましくは0.1〜10質量%の範囲である。CNF濃度を0.1質量%未満とすると、CNFによる樹脂の補強効果が得られにくく、10質量%よりも高くすると、CNF含有液の粘性が高くなりすぎ扱いにくくなる。CNF濃度は、より好ましくは0.3〜5質量%であり、さらに好ましくは0.5〜3質量%である。 The CNF concentration in the CNF-containing liquid is appropriately selected in consideration of viscosity and the like, but is preferably in the range of 0.1 to 10% by mass. If the CNF concentration is less than 0.1% by mass, the effect of reinforcing the resin by CNF is difficult to obtain, and if it is higher than 10% by mass, the viscosity of the CNF-containing liquid becomes too high and it becomes difficult to handle. The CNF concentration is more preferably 0.3 to 5% by mass, still more preferably 0.5 to 3% by mass.
CNF含有液には、本開示の効果を損なわない範囲で、CNF及び溶剤以外のその他の成分が含有されていてもよい。かかるその他の成分としては、例えば各種樹脂、添加剤、有機フィラー、無機フィラー等が挙げられる。これらの含有割合は、その他の成分の種類に応じて適宜選択することができる。その他の成分の配合割合は、5質量%以下とすることが好ましく、1質量%以下とすることがより好ましい。 The CNF-containing liquid may contain other components other than CNF and the solvent as long as the effects of the present disclosure are not impaired. Examples of such other components include various resins, additives, organic fillers, inorganic fillers and the like. These content ratios can be appropriately selected according to the types of other components. The blending ratio of the other components is preferably 5% by mass or less, and more preferably 1% by mass or less.
(基材)
基材としては、親水性かつ多孔性であればその材質は特に限定されない。ここで、親水性とは、一般的には水分子との親和性が大きい性質を意味し、水を弾く撥水性に相対する性質を指す。ここでは、水を基材の厚み方向に透過可能又は保持可能であるとき、その基材は親水性であるという。基材が親水性であることにより、CNF含有液を基材に塗布した場合に、CNF含有液中の溶剤が基材に吸収されるため、これを乾燥することによってCNFが表面に付着した基材が得られる。また、CNF含有液が基材表面の全体に濡れ広がり、CNFを基材表面に均一に付着させることが可能となる。これにより、樹脂マトリクスの全体に亘って均一に、高い強度や剛性を付与することができる。「多孔性」とは、多数の微細な孔(隙間)を有することを意味する。
(Base material)
The material of the base material is not particularly limited as long as it is hydrophilic and porous. Here, hydrophilicity generally means a property having a high affinity with water molecules, and refers to a property opposite to water repellency that repels water. Here, when water can be permeated or retained in the thickness direction of the base material, the base material is said to be hydrophilic. Since the base material is hydrophilic, when the CNF-containing liquid is applied to the base material, the solvent in the CNF-containing liquid is absorbed by the base material, and the group to which the CNF adheres to the surface by drying the base material. The material is obtained. Further, the CNF-containing liquid wets and spreads over the entire surface of the base material, and the CNF can be uniformly adhered to the surface of the base material. As a result, high strength and rigidity can be imparted uniformly throughout the resin matrix. "Porosity" means having a large number of fine pores (gap).
親水性かつ多孔性の基材としては、好ましくは、紙、織物又は不織布である。これらの材料を基材として用いることにより、薄くて軽く、かつ剛性に優れた樹脂複合体を、高度な技術や施設を必要とせずに安価に製造することができる。これらはいずれも繊維からなる材料であるが、通常、CNFよりも太い繊維(例えば、1μm以上)を用いて形成されている。 The hydrophilic and porous base material is preferably paper, woven fabric or non-woven fabric. By using these materials as a base material, a thin, light, and highly rigid resin composite can be manufactured at low cost without the need for advanced technology or facilities. All of these are materials made of fibers, but are usually formed by using fibers thicker than CNF (for example, 1 μm or more).
紙は、一般に植物繊維(パルプ)を材料として、繊維を絡ませながら膠着させて製造されたシート状の薄片である。なお、紙に使用される繊維径はCNFよりも太く、例えば1〜100μmである。基材として用いる紙は、種々の用途で使用される紙を適用することができ、具体的には、例えば印刷・情報用紙、包装用紙、衛生用紙、工業用雑種紙、家庭用雑種紙、新聞紙等が挙げられる。なお、基材としての紙は、和紙及び洋紙のいずれでもよい。 Paper is generally a sheet-like flakes produced by using plant fibers (pulp) as a material and entwining the fibers while sticking them together. The fiber diameter used for paper is larger than that of CNF, for example, 1 to 100 μm. As the paper used as the base material, paper used for various purposes can be applied. Specifically, for example, printing / information paper, wrapping paper, sanitary paper, industrial mixed paper, household mixed paper, newspaper. And so on. The paper as the base material may be either Japanese paper or Western paper.
基材としての紙は、繊維を水に分散させて抄いた後、これを脱水・乾燥して製造されたものであってもよく、水を使用しない乾式で製造されたものであってもよい。前者の場合、脱水・乾燥した後の紙を基材として用いてもよく、あるいは、抄紙した後、脱水・乾燥する前の水を含んだ状態の紙を基材として用いてもよい。 The paper as a base material may be produced by dispersing fibers in water, then dehydrating and drying the paper, or may be produced by a dry method that does not use water. .. In the former case, paper after dehydration / drying may be used as a base material, or paper containing water after papermaking and before dehydration / drying may be used as a base material.
織物は、繊維(糸)を縦横に組み合わせて織ったシート状の布地である。織り方は特に限定されず、例えば平織、綾織、朱子織等が挙げられる。不織布は、繊維を織らずに、機械的又は化学的な処理によって絡み合わせたシート状の布地である。不織布はいずれの方法によって製造されたものであってもよく、例えば乾式法、湿式法、スパンボンド法等のフリース形成法;サーマルボンド法、ケミカルボンド法、ニードルパンチ法等のフリース結合法が挙げられる。織物、不織布を構成する繊維の種類は特に制限されず、例えば、木綿、絹、麻、モヘヤ、ウール、カシミア等の天然繊維;アセテート、レーヨン、キュプラ等の再生繊維;ナイロン、ポリエステル、ポリウレタン等の合成繊維、等が挙げられる。 A woven fabric is a sheet-like fabric woven by combining fibers (threads) vertically and horizontally. The weaving method is not particularly limited, and examples thereof include plain weave, twill weave, and satin weave. Nonwoven fabrics are sheet-like fabrics that are entwined by mechanical or chemical treatment without weaving fibers. The non-woven fabric may be produced by any method, and examples thereof include a fleece forming method such as a dry method, a wet method, and a spunbond method; and a fleece bonding method such as a thermal bond method, a chemical bond method, and a needle punch method. Be done. The types of fibers constituting the woven fabric and non-woven fabric are not particularly limited, and for example, natural fibers such as cotton, silk, linen, mohair, wool and cashmere; recycled fibers such as acetate, rayon and cupra; nylon, polyester, polyurethane and the like. Synthetic fibers, etc. may be mentioned.
紙、織物及び不織布の色や柄は特に限定されない。例えば、紙、織物及び不織布に印刷が施されていてもよいし、葉、花(生花、押し花、ドライフラワー等)、色紙、糸、毛糸等からなる模様が含まれていてもよい。あるいは、手書きの模様や文字等が付されていてもよい。基材として色彩や模様、文字が施された材料を使用することにより、デザイン性に優れた樹脂複合体を得ることができる。また、紙や織物、不織布には、様々なバリエーションの模様や色、文字を手軽に付すことができ、装飾性や美観性に優れた樹脂複合体を簡単な方法で製造することが可能である。 The color and pattern of paper, woven fabric and non-woven fabric are not particularly limited. For example, paper, woven fabric, and non-woven fabric may be printed, or may include a pattern composed of leaves, flowers (fresh flowers, pressed flowers, dried flowers, etc.), colored paper, threads, yarns, and the like. Alternatively, a handwritten pattern, characters, or the like may be attached. By using a material with colors, patterns, and letters as the base material, a resin composite having excellent design can be obtained. In addition, various variations of patterns, colors, and characters can be easily attached to paper, woven fabric, and non-woven fabric, and a resin composite having excellent decorativeness and aesthetics can be manufactured by a simple method. ..
基材の大きさは、樹脂複合体の使用用途等に応じて適宜に選択される。基材の形状は、シート状であることが好ましい。基材の厚みは、得られる樹脂複合体における所望の機械的特性(強度や剛性等)に応じて適宜選択されるが、基材の取り扱い性を良好にしつつ、強度や剛性が高い樹脂複合体を得る観点から、10〜1500μmの範囲とすることが好ましく、20〜500μmの範囲とすることがより好ましい。基材としては、表面に付着させたCNFに対する固定化能が高い点や、基材の厚さが薄く、より高い強度の樹脂複合体が得られる点、選択の自由度が高い点、入手が容易である点等の理由から、上記の中でも紙を特に好ましく用いることができる。 The size of the base material is appropriately selected according to the intended use of the resin composite and the like. The shape of the base material is preferably sheet-like. The thickness of the base material is appropriately selected according to the desired mechanical properties (strength, rigidity, etc.) of the obtained resin composite, but the resin composite has high strength and rigidity while improving the handleability of the base material. From the viewpoint of obtaining the above, the range is preferably in the range of 10 to 1500 μm, and more preferably in the range of 20 to 500 μm. As a base material, it has a high immobilization ability for CNF attached to the surface, a thin base material can be obtained, a resin composite having higher strength can be obtained, a high degree of freedom of selection, and availability. Among the above, paper can be particularly preferably used because of its ease of use.
CNF含有液を基材に塗布する方法は特に限定されず、例えばシャワー法、スプレー法、ディップ(浸漬)法、パドル(液盛り)法、刷毛塗り、ローラーブラシ塗布、ロールコーター法、オフセット印刷法、インクジェット印刷法等の種々の方法を適用することができる。このとき、CNF含有液の塗布量を多くするために、例えば基材へのCNF含有液の塗布を複数回行うことも有効である。基材に塗布されるCNF含有液の厚みは、適宜選択されるが、液垂れ防止とCNFによる補強効果とを両立させる観点から、0.5〜10mmの範囲とすることが好ましく、1〜8mmの範囲とすることがより好ましい。CNF含有液は基材の一面のみに塗布してもよいし、両面に塗布してもよい。 The method of applying the CNF-containing liquid to the substrate is not particularly limited, and for example, a shower method, a spray method, a dip (immersion) method, a paddle (liquid filling) method, a brush coating, a roller brush coating, a roll coater method, and an offset printing method. , Various methods such as an inkjet printing method can be applied. At this time, in order to increase the amount of the CNF-containing liquid applied, it is also effective to apply the CNF-containing liquid to the base material a plurality of times, for example. The thickness of the CNF-containing liquid applied to the base material is appropriately selected, but is preferably in the range of 0.5 to 10 mm, preferably 1 to 8 mm, from the viewpoint of achieving both prevention of dripping and the reinforcing effect of CNF. It is more preferable to set it in the range of. The CNF-containing liquid may be applied to only one surface of the base material or to both surfaces.
<工程(B)>
工程(B)は、CNF含有液を塗布した後の基材から溶剤を除去する工程である。本工程により基材が乾燥され、CNFが基材表面で絡み合うことにより基材表面に固定化された基材を得ることができる。溶剤を除去する方法としては、特に限定されるものではなく、例えば自然乾燥、送風乾燥、加熱乾燥、減圧乾燥等による方法が挙げられる。好ましくは、温風、恒温槽、ホットプレート等による加熱乾燥である。このときの加熱温度は、溶剤や基材の種類、加熱方法等に応じて適宜選択できるが、好ましくは20〜150℃、より好ましくは30〜100℃である。加熱時間は、好ましくは3〜60分であり、より好ましくは5〜30分である。
<Process (B)>
The step (B) is a step of removing the solvent from the base material after applying the CNF-containing liquid. By this step, the base material is dried, and the CNF is entangled on the surface of the base material to obtain a base material immobilized on the surface of the base material. The method for removing the solvent is not particularly limited, and examples thereof include methods such as natural drying, blast drying, heat drying, and vacuum drying. Preferably, it is heated and dried by warm air, a constant temperature bath, a hot plate or the like. The heating temperature at this time can be appropriately selected depending on the type of solvent, the base material, the heating method, and the like, but is preferably 20 to 150 ° C, more preferably 30 to 100 ° C. The heating time is preferably 3 to 60 minutes, more preferably 5 to 30 minutes.
なお、得られる複合体の機械的強度を更に高めるために、溶剤除去した後に延伸工程や加圧工程等の補強のための工程を追加してもよい。 In addition, in order to further increase the mechanical strength of the obtained composite, a step for reinforcement such as a stretching step and a pressurizing step may be added after removing the solvent.
<工程(C)>
工程(C)は、溶剤を除去した後の基材と樹脂とを複合化する工程である。
(樹脂)
CNFとの複合化に用いる樹脂としては、熱可塑性樹脂、熱硬化性樹脂が挙げられる。熱可塑性樹脂は、冷却と加熱を繰り返した場合に塑性が可逆的に保たれる樹脂である。したがって、加熱により軟化して塑性を示し成形することが可能であり、冷却すると固化する。熱可塑性樹脂の具体例としては、例えばポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリ酢酸ビニル、ポリテトラフルオロエチレン、アクリロニトリル−ブタジエン−スチレン(ABS)樹脂、アクリロニトリル−スチレン(AS)樹脂、アクリル樹脂、ポリアミド、ポリアセタール、ポリエステル、変性ポリフェニレンエーテル等が挙げられる。樹脂は、透明及び不透明のいずれでもよいが、基材に付した色彩や模様、文字等を視認可能にできる観点で、透明樹脂とすることが好ましい。
<Process (C)>
The step (C) is a step of synthesizing the base material and the resin after removing the solvent.
(resin)
Examples of the resin used for compounding with CNF include a thermoplastic resin and a thermosetting resin. The thermoplastic resin is a resin whose plasticity is reversibly maintained when cooling and heating are repeated. Therefore, it can be softened by heating to show plasticity and can be molded, and solidified by cooling. Specific examples of the thermoplastic resin include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, acrylic resin, and the like. Examples thereof include polyamide, polyacetal, polyester, and modified polyphenylene ether. The resin may be transparent or opaque, but it is preferable to use a transparent resin from the viewpoint of making the colors, patterns, characters and the like attached to the base material visible.
熱硬化性樹脂は、低分子量の固体又は液体の化合物を加熱することによって反応が起こり、不可逆的に硬化する樹脂である。熱硬化性樹脂の具体例としては、例えばエポキシ樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂、ウレタン樹脂、シリコーン樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、熱硬化性ポリイミド、アルキド樹脂等が挙げられる。なお、樹脂は、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。 Thermosetting resins are resins that react irreversibly by heating a low molecular weight solid or liquid compound. Specific examples of the thermosetting resin include epoxy resin, phenol resin, melamine resin, urea resin, urethane resin, silicone resin, unsaturated polyester resin, diallyl phthalate resin, thermosetting polyimide, alkyd resin and the like. As the resin, one type may be used alone, or two or more types may be used in combination.
複合化に用いる樹脂としては、熱硬化性樹脂を好ましく使用でき、不飽和ポリエステル樹脂、エポキシ樹脂、ポリアミド樹脂、フェノール樹脂又はアクリル樹脂が好ましく、エポキシ樹脂が特に好ましい。繊維−樹脂複合体におけるマトリクスには、樹脂とともに従来公知の添加剤が含有されていてもよい。このような添加剤としては、例えば硬化剤、着色剤、酸化防止剤、重合開始剤、難燃剤、帯電防止剤、消泡剤、レベリング剤、無機フィラー等が挙げられる。添加剤の配合割合は、本開示の効果を損なわない範囲で適宜に選択することができる。 As the resin used for the composite, a thermosetting resin can be preferably used, and an unsaturated polyester resin, an epoxy resin, a polyamide resin, a phenol resin or an acrylic resin is preferable, and an epoxy resin is particularly preferable. The matrix in the fiber-resin composite may contain a conventionally known additive together with the resin. Examples of such additives include curing agents, coloring agents, antioxidants, polymerization initiators, flame retardants, antistatic agents, defoaming agents, leveling agents, inorganic fillers and the like. The blending ratio of the additive can be appropriately selected as long as the effect of the present disclosure is not impaired.
CNFが付着した基材(以下「CNF付着基材」ともいう。)と樹脂とを複合化する方法は特に限定されないが、例えば、CNF付着基材の一部又は全体に液体状の樹脂を含浸させることにより、樹脂マトリクス中にCNF付着基材を有する複合体を形成し、その後、樹脂を硬化する方法が挙げられる。 The method for synthesizing the CNF-attached base material (hereinafter, also referred to as “CNF-attached base material”) and the resin is not particularly limited, but for example, a part or the whole of the CNF-attached base material is impregnated with a liquid resin. A method of forming a composite having a CNF-adhered base material in the resin matrix and then curing the resin can be mentioned.
樹脂との複合化に使用するCNF付着基材は、1のみであってもよいが、得られる繊維−樹脂複合体の強度や剛性を更に高くする観点から、CNF付着基材を複数用い、これを積層した積層体を樹脂により一体化することが好ましい。本開示の製造方法では、基材が有する微細な隙間に樹脂が入り込むことで、CNFが表面に付着した複数の基材同士を樹脂によって一体化することができる。 The number of CNF-attached base materials used for the composite with the resin may be only one, but from the viewpoint of further increasing the strength and rigidity of the obtained fiber-resin composite, a plurality of CNF-attached base materials are used. It is preferable to integrate the laminated body obtained by laminating the above with a resin. In the manufacturing method of the present disclosure, a plurality of base materials having CNF attached to the surface can be integrated with each other by the resin by entering the fine gaps of the base material.
積層体を樹脂によって一体化する方法としては、例えば、CNF含有液を塗布・乾燥した後の1の基材に液体状の樹脂を含浸させたものを複数準備し、これらを重ね合わせることにより2以上の基材を積層する方法;CNF付着基材を複数重ね合わせて積層体を形成した後、樹脂を積層体に含浸させる方法;これらの組み合わせ等が挙げられる。 As a method of integrating the laminate with the resin, for example, a plurality of base materials 1 impregnated with a liquid resin after the CNF-containing liquid is applied and dried are prepared, and these are overlapped with each other. A method of laminating the above base materials; a method of laminating a plurality of CNF-adhered base materials to form a laminated body and then impregnating the laminated body with a resin; a combination of these can be mentioned.
樹脂の硬化の際には、得られる複合体の強度や剛性を更に高めるために、積層した複数のCNF付着基材を圧縮しながら硬化処理を行うとよい。圧縮の操作を行うことにより、基材が有する微細な隙間に樹脂が万遍なく流入しやすくなり、成形体内部における空隙の形成を抑制することが可能となる。繊維−樹脂複合体が成形体である場合、樹脂を硬化する際に目的とする形状に成形する。成形方法としては、通常使用される方法を適用でき、例えば圧縮成形、射出成形、中空成形、真空成形等が挙げられる。なお、熱可塑性樹脂を用いる場合には、熱硬化性樹脂の場合と同じく、液体状の樹脂をCNF付着基材に含浸させたものを所望の型に合わせて圧縮等しながら冷却し硬化させることにより、最終製品となる繊維−樹脂複合体を製造してもよい。あるいは、液体状の樹脂をCNF付着基材に含浸させて一旦冷却、硬化することにより、繊維−樹脂複合体としての中間物を作成し、この中間物を所望の型に合わせて加熱し軟化させ、これを圧縮等しながら冷却し硬化させることにより、最終製品となる繊維−樹脂複合体を製造してもよい。 When the resin is cured, in order to further increase the strength and rigidity of the obtained composite, it is preferable to perform the curing treatment while compressing the plurality of laminated CNF-adhered substrates. By performing the compression operation, the resin can easily flow into the fine gaps of the base material evenly, and the formation of voids inside the molded product can be suppressed. When the fiber-resin composite is a molded product, it is molded into a desired shape when the resin is cured. As the molding method, a commonly used method can be applied, and examples thereof include compression molding, injection molding, hollow molding, vacuum forming and the like. When a thermoplastic resin is used, as in the case of a thermosetting resin, a CNF-adhered base material impregnated with a liquid resin is cooled and cured while being compressed according to a desired mold. May produce a fiber-resin composite as a final product. Alternatively, the CNF-adhered base material is impregnated with a liquid resin, cooled and cured once to prepare an intermediate as a fiber-resin composite, and the intermediate is heated and softened according to a desired mold. , This may be cooled and cured while being compressed or the like to produce a fiber-resin composite as a final product.
上記方法によれば、CNFが付着した基材の厚みを薄くして積層数を増やす、といった簡単な操作によって、強度や剛性により優れた樹脂複合体を得ることができる。また、基材の厚みや積層数によって、得られる樹脂複合体が所望の機械的特性になるように微調整しやすく、用途に合わせた強化樹脂を設計しやすいといった利点もある。 According to the above method, a resin composite having higher strength and rigidity can be obtained by a simple operation such as reducing the thickness of the base material to which the CNF is attached and increasing the number of layers. Further, there is an advantage that the obtained resin composite can be easily finely adjusted so as to have desired mechanical properties depending on the thickness of the base material and the number of layers, and it is easy to design a reinforced resin according to the application.
図1に、本開示の繊維−樹脂複合体の製造方法の一実施形態を示す。この実施形態では、親水性かつ多孔性の基材として紙、織物又は不織布を用いる。まず、ステップS11の処理では、基材シートの表面上にCNF含有液を塗布する。ここでは、基材シートの片面のみにCNF含有液を塗布する。ただし、シート両面にCNF含有液を塗布してもよい。続くステップS12の処理では、CNF含有液を塗布した基材シートから溶剤を完全に除去し、基材シートを乾燥させる。本実施形態では、このシート(以下、「CNF付着シート」ともいう。)を複数枚作製する。 FIG. 1 shows an embodiment of the method for producing a fiber-resin composite of the present disclosure. In this embodiment, paper, woven fabric or non-woven fabric is used as the hydrophilic and porous base material. First, in the treatment of step S11, the CNF-containing liquid is applied on the surface of the base material sheet. Here, the CNF-containing liquid is applied only to one side of the base sheet. However, the CNF-containing liquid may be applied to both sides of the sheet. In the subsequent treatment of step S12, the solvent is completely removed from the base sheet coated with the CNF-containing liquid, and the base sheet is dried. In this embodiment, a plurality of sheets (hereinafter, also referred to as "CNF adhering sheets") are produced.
続くステップS13の処理では、CNF付着シートを複数積層した積層体を樹脂により一体化する。ここでは、CNF付着シートのCNF付着面及びCNF非付着面の少なくとも一方から液体状の樹脂を含浸させたものを複数準備し、それらを積層する。基材の孔に樹脂を隙間なく充填できる点で、CNF付着シートにおけるCNF非付着面から樹脂を含浸させることが好ましい。その後、ステップS14の処理では、CNF付着シートの積層体を圧縮しながら樹脂を硬化させる。これにより、積層された複数のCNF付着シートが、硬い樹脂マトリクスによってシート全体を覆うようにして一体化された繊維−樹脂複合体が得られる。 In the subsequent process of step S13, the laminated body in which a plurality of CNF adhering sheets are laminated is integrated with the resin. Here, a plurality of CNF-attached sheets impregnated with a liquid resin from at least one of the CNF-attached surface and the CNF-non-attached surface are prepared and laminated. It is preferable to impregnate the resin from the non-CNF-attached surface of the CNF-attached sheet because the holes of the base material can be filled with the resin without gaps. After that, in the process of step S14, the resin is cured while compressing the laminated body of the CNF adhering sheets. As a result, a fiber-resin composite is obtained in which a plurality of laminated CNF-attached sheets are integrated so as to cover the entire sheet with a hard resin matrix.
図2に、上記図1の製造方法により得られる繊維−樹脂複合体10の模式図を示す。繊維−樹脂複合体10は、樹脂マトリクス13と、セルロースナノファイバー12が表面に付着した多孔性の基材11と、を備える。樹脂マトリクス13の内部には、積層された複数(図2では3枚)の基材11が含まれており、樹脂マトリクス13にCNFが含有された状態となっている。
FIG. 2 shows a schematic view of the fiber-
本開示の繊維−樹脂複合体は、種々の用途に適用することができる。具体的には、例えば自動車用部材(例えば、ボディやバンパー等の外装品、ダッシュボードやパネル等の内装品等)、鉄道用部材、船舶用部材(例えば、船体等)、航空関連部材、家電用部材(例えば、筐体等)、建材(例えば、壁材、床材、建具、ダクト、制振・免震構造材等)、家具材、住宅設備機器(例えば、ユニットバスや浄化槽等)、生活用品、生活雑貨(例えば、スマートフォンカバーやステーショナリー等)、スポーツ・レジャー用品、医療用部材、容器・包装部材等が挙げられる。 The fiber-resin composite of the present disclosure can be applied to various uses. Specifically, for example, automobile parts (for example, exterior parts such as bodies and bumpers, interior parts such as dashboards and panels), railway parts, ship parts (for example, hulls), aviation-related parts, home appliances, etc. Materials (for example, housings), building materials (for example, wall materials, floor materials, fittings, ducts, vibration damping / seismic isolation structural materials, etc.), furniture materials, housing equipment (for example, unit baths, septic tanks, etc.), Examples include daily necessities, household goods (for example, smartphone covers and stationery), sports / leisure products, medical materials, containers / packaging materials, and the like.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
[実施例1]
10cm×5cmの和紙の一方の表面に、1質量%セルロースナノファイバー水懸濁液を4〜5mmの厚さとなるようにヘラで塗布した。続いて、セルロースナノファイバー水懸濁液を塗布した和紙を、60℃前後に温めたホットプレート上に置いて水分を除去することによって乾燥させ、和紙表面にCNFが付着したCNF付着シートを得た。上記と同様の操作を繰り返し、CNF付着シートを2枚準備した。2枚のCNF付着シートそれぞれに、CNF付着側の裏面(CNF非付着側の面)からエポキシ樹脂(プレポリマー)と硬化剤との混合物を含浸させた。樹脂を含浸させたCNF付着シートを2枚重ね合わせ、金型にはめた状態で、30℃、面圧0.1MPaで加熱・圧縮して樹脂を硬化した。これにより、樹脂成形体として、2枚のCNF付着シートを樹脂マトリクス内部に有する厚さ1〜2mm程度の繊維−樹脂複合体が得られた。
[Example 1]
A 1% by mass cellulose nanofiber aqueous suspension was applied with a spatula to a thickness of 4 to 5 mm on one surface of 10 cm × 5 cm Japanese paper. Subsequently, the Japanese paper coated with the cellulose nanofiber aqueous suspension was placed on a hot plate heated to about 60 ° C. and dried by removing water to obtain a CNF-attached sheet having CNF attached to the surface of the Japanese paper. .. The same operation as above was repeated to prepare two CNF adhering sheets. Each of the two CNF-attached sheets was impregnated with a mixture of an epoxy resin (prepolymer) and a curing agent from the back surface on the CNF-attached side (the surface on the non-CNF-attached side). Two CNF-adhering sheets impregnated with the resin were superposed, and the resin was cured by heating and compressing at 30 ° C. and a surface pressure of 0.1 MPa in a state of being fitted in a mold. As a result, a fiber-resin composite having a thickness of about 1 to 2 mm having two CNF-attached sheets inside the resin matrix was obtained as the resin molded body.
[比較例1]
CNF含有液を和紙に塗布しなかった点及び和紙の乾燥処理を行わなかった点以外は、実施例1と同様の操作により樹脂成形体を作製した。
[Comparative Example 1]
A resin molded product was produced by the same operation as in Example 1 except that the CNF-containing liquid was not applied to the Japanese paper and the Japanese paper was not dried.
実施例1及び比較例1の樹脂成形体につき、樹脂成形体を上下方向に素手で曲げることにより両者の曲げ強度(剛性)を比較した。その結果、実施例1のものは比較例1のものに比べて曲がりにくく、剛性に優れていることが分かった。 The bending strength (rigidity) of the resin molded bodies of Example 1 and Comparative Example 1 was compared by bending the resin molded bodies in the vertical direction with bare hands. As a result, it was found that the one of Example 1 was harder to bend and had excellent rigidity as compared with that of Comparative Example 1.
[実施例2、3]
CNF付着シートの積層枚数を5枚、10枚にそれぞれ変更した点以外は、実施例1と同様の操作により樹脂成形体を製造し、上記と同様の方法により剛性を比較した。その結果、CNF付着シートの積層枚数が多いほど、樹脂成形体の剛性が高かった。以上から、上記工程(A)〜(C)を含む製造方法によれば、汎用の処理を用いた簡便な方法で樹脂の機械的特性を改善できることが分かった。
[Examples 2 and 3]
A resin molded product was produced by the same operation as in Example 1 except that the number of laminated CNF-attached sheets was changed to 5 and 10 respectively, and the rigidity was compared by the same method as described above. As a result, the larger the number of laminated CNF-attached sheets, the higher the rigidity of the resin molded product. From the above, it was found that according to the production method including the above steps (A) to (C), the mechanical properties of the resin can be improved by a simple method using a general-purpose treatment.
10…繊維−樹脂複合体、11…基材、12…セルロースナノファイバー、13…樹脂マトリクス。 10 ... Fiber-resin composite, 11 ... Base material, 12 ... Cellulose nanofiber, 13 ... Resin matrix.
Claims (3)
(A)セルロースナノファイバーと溶剤とを含む液状組成物を、親水性かつ多孔性の基材に塗布する工程、
(B)前記液状組成物を塗布した後の前記基材から前記溶剤を除去する工程、
(C)前記溶剤を除去した後の前記基材と、樹脂とを複合化する工程、
を含む、繊維−樹脂複合体の製造方法であって、
前記工程(C)は、前記溶剤を除去した後の前記基材が複数積層された積層体を前記樹脂により一体化することにより複合化する工程である、繊維−樹脂複合体の製造方法。 The following steps (A) to (C )
(A) A step of applying a liquid composition containing cellulose nanofibers and a solvent to a hydrophilic and porous substrate .
(B) A step of removing the solvent from the base material after applying the liquid composition .
(C) A step of compounding the base material and the resin after removing the solvent .
A method for producing a fiber-resin composite, which comprises.
The step (C) is a step of compositing a laminate in which a plurality of the base materials are laminated after removing the solvent by integrating them with the resin, which is a method for producing a fiber-resin composite.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016119161A JP6818289B2 (en) | 2016-06-15 | 2016-06-15 | Fiber-resin composite and its manufacturing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016119161A JP6818289B2 (en) | 2016-06-15 | 2016-06-15 | Fiber-resin composite and its manufacturing method |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2017222786A JP2017222786A (en) | 2017-12-21 |
JP6818289B2 true JP6818289B2 (en) | 2021-01-20 |
Family
ID=60687846
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016119161A Active JP6818289B2 (en) | 2016-06-15 | 2016-06-15 | Fiber-resin composite and its manufacturing method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6818289B2 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7032204B2 (en) * | 2018-03-29 | 2022-03-08 | 株式会社熊谷組 | Floors, walls, and structures |
JP2019206153A (en) * | 2018-05-30 | 2019-12-05 | 旭化成株式会社 | Resin-containing multilayer structure |
JP7527618B2 (en) | 2019-04-25 | 2024-08-05 | 国立大学法人富山大学 | Cellulose nanofiber reinforced aluminum matrix composite material and aluminum matrix composite extrusion material, and methods for producing the same |
KR102153308B1 (en) * | 2019-12-24 | 2020-09-08 | 재단법인 한국섬유기계융합연구원 | Nanocellulose complex sheets and method for preparing the same |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI615530B (en) * | 2014-09-26 | 2018-02-21 | Asahi Kasei Fibers Corp | Film sheet comprising cellulose microfiber layer |
JP6872763B2 (en) * | 2016-06-03 | 2021-05-19 | 学校法人立教学院 | Cellulose nanofiber composite membrane and its manufacturing method |
-
2016
- 2016-06-15 JP JP2016119161A patent/JP6818289B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2017222786A (en) | 2017-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102243567B1 (en) | A molded object and a manufacturing method thereof | |
JP6818289B2 (en) | Fiber-resin composite and its manufacturing method | |
FI73900C (en) | Process for producing a flocked textile surface structure and a flexible textile surface structure | |
JP4233560B2 (en) | Manufacturing method of prepreg | |
EP0238014B2 (en) | Thermoplastic membrane, process for its manufacture and apparatus for performing the same | |
KR101677099B1 (en) | multi-layered composite using nanofibrillated cellulose and thermoplastic matrix polymer | |
JP2014095049A (en) | Cellulose fiber reinforced thermoplastic resin composite molded article | |
JPWO2017006993A1 (en) | Skin material sheet, method for producing the same, and sound absorbing material | |
KR101234044B1 (en) | Ultraviolet-curable type fabric for waterproof and breathable and preparing the same | |
EP2925517A1 (en) | Sandwich material | |
JP6112989B2 (en) | Laminated nonwoven fabric with printing | |
KR100937804B1 (en) | Breathable laminate with a high abrasion resistance and method of manufacturing the same | |
KR20090063199A (en) | The foam coating method of textile of function characteristic | |
KR20160047636A (en) | Method manufacture of glass fiber mat reinforced thermoplastics and housing with an external method of fiberglass composite material | |
KR101246736B1 (en) | Foamed vinyl wallpaper and methods for manufacturing a foamed vinyl wallpaper | |
KR101630413B1 (en) | Manufacturing method of coating agent treated fiber wallpaper for prevent release formaldehyde | |
KR101479747B1 (en) | The method for promoting abrasion-durability of surface of nano fiber membrane using paper coated with silicon | |
JP2016150569A (en) | Decorative resin molding | |
JP7462748B2 (en) | Composite sound absorbing material | |
KR102308469B1 (en) | Multi-layer Interior Materials For Noise Absorption-Insulation | |
EP3993998B1 (en) | Artificial leather product and process for producing same | |
JP2011090060A (en) | Sound absorbing material and sound insulating panel | |
EP1868807B1 (en) | Hydrophobic insulation material | |
US11773299B2 (en) | Sticky adhesive mesh and method for manufacturing sticky adhesive mesh | |
KR101479750B1 (en) | The method for promoting abrasion-durability of surface of nano fiber membrane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190531 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200630 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200721 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200918 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201208 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20201217 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6818289 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |