JP6507001B2 - Carbon fiber reinforced resin processed sheet - Google Patents
Carbon fiber reinforced resin processed sheet Download PDFInfo
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- JP6507001B2 JP6507001B2 JP2015062600A JP2015062600A JP6507001B2 JP 6507001 B2 JP6507001 B2 JP 6507001B2 JP 2015062600 A JP2015062600 A JP 2015062600A JP 2015062600 A JP2015062600 A JP 2015062600A JP 6507001 B2 JP6507001 B2 JP 6507001B2
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 90
- 239000004917 carbon fiber Substances 0.000 title claims description 90
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 77
- 229920005989 resin Polymers 0.000 title claims description 10
- 239000011347 resin Substances 0.000 title claims description 10
- 239000004744 fabric Substances 0.000 claims description 61
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 54
- 238000000465 moulding Methods 0.000 claims description 53
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000010030 laminating Methods 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010998 test method Methods 0.000 claims description 5
- 238000003475 lamination Methods 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 2
- 238000005452 bending Methods 0.000 description 40
- 239000005060 rubber Substances 0.000 description 24
- 229920001971 elastomer Polymers 0.000 description 16
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 12
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000002759 woven fabric Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 5
- 238000009661 fatigue test Methods 0.000 description 5
- 238000009958 sewing Methods 0.000 description 5
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 241000665112 Zonitoides nitidus Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000013037 co-molding Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Description
本発明は、カバン、バック、財布、名刺入れなどの縫製品、車の内装品、衣服の部材、壁紙などに用いることのできる、炭素繊維強化樹脂加工シートに関する。さらに詳しくは、炭素繊維布帛に熱可塑性エラストマーフィルムやゴムフィルムをラミネートしてなる、縫製品の生地として優れた特性を有しており、同一組成または同一シート内であっても剛軟度の異なる箇所を適宜用途に応じて変更できる炭素繊維強化樹脂加工シートに関する。 The present invention relates to a carbon fiber reinforced resin-processed sheet that can be used for sewing products such as bags, bags, wallets, and business card holders, car interior products, members of clothes, wallpaper, and the like. More specifically, it has excellent properties as a fabric of a sewn product, which is obtained by laminating a thermoplastic elastomer film or a rubber film on a carbon fiber fabric, and the bending resistance differs even in the same composition or in the same sheet. The present invention relates to a carbon fiber reinforced resin-processed sheet which can be appropriately changed depending on the application.
炭素繊維強化プラスチック（ＣＦＲＰ）は、比強度が高いことから、金属代替材料として、航空機や車の車体などに用いられている。このような構造部材に使用されているＣＦＲＰのマトリクスとして、フェノール樹脂やエポキシ樹脂などの熱硬化性樹脂や、近年では成形サイクルの短縮の目的で熱可塑性樹脂が使用されている。このような構造部材に用いられるＣＦＲＰは剛直であるため、それ自身が屈曲することはない。 Carbon fiber reinforced plastic (CFRP) is used as a metal substitute material for car bodies of aircrafts and cars because of its high specific strength. As a CFRP matrix used for such structural members, thermosetting resins such as phenol resins and epoxy resins, and in recent years thermoplastic resins have been used for the purpose of shortening the molding cycle. Since CFRP used for such a structural member is rigid, it does not bend by itself.
炭素繊維は、高比強度や高比弾性率などの機械的特性や耐熱性に優れているが、繊維軸に対して直角方向から力が加わると繊維が切断して毛羽立ちとなる。そのため、炭素繊維布帛は擦れ合ったり、強く曲げられたりすることで破損や表面に毛羽立ちが生じるため、炭素繊維だけを使用することはできなかった。 Carbon fibers are excellent in mechanical properties such as high specific strength and high specific elastic modulus and heat resistance, but when a force is applied in a direction perpendicular to the fiber axis, the fibers are cut and fuzzed. Therefore, it was not possible to use only carbon fiber, because the carbon fiber cloth is broken or frustrated by being rubbed or strongly bent.
特許文献１では、炭素繊維布帛に柔軟性のある高分子化合物を含浸させ、樹脂量を均一にすることで縫製品や衣服の一部に使用できる樹脂加工シートを提供しているが、同一組成では炭素繊維布帛に高分子化合物が均一に含浸されることで、一定の剛軟度を有する樹脂加工シートが得られる。しかしながら、剛軟度の異なる箇所を有する樹脂加工シートを得るには、組成を変更する必要があり、同一シート内で剛軟度の異なる箇所を有する樹脂加工シートを製造するには、生産性が劣る。 Patent Document 1 provides a resin-processed sheet that can be used for a part of a sewing product or a garment by impregnating a carbon fiber cloth with a flexible polymer compound to make the resin amount uniform, but the same composition Then, the carbon fiber cloth is uniformly impregnated with the polymer compound, whereby a resin-processed sheet having a certain degree of bending resistance can be obtained. However, it is necessary to change the composition to obtain a resin-processed sheet having portions with different bending resistances, and in order to manufacture a resin-processed sheet having portions with different bending resistances in the same sheet, the productivity is It is inferior.
本発明は、カバンやバック、財布や名刺入れなどの縫製品、車などの内装品、衣服の部材、壁紙、そのほか意匠性の高い製品として使用できる特性を有し、かつ同一組成であっても、剛軟度を調整することのできる炭素繊維強化樹脂加工シートであって、同一シート内であっても適宜用途に応じて剛軟度の大きい箇所と小さい箇所の割合を変更できる炭素繊維強化樹脂加工シートを提供することにある。 The present invention has characteristics that can be used as bags and bags, sewing products such as wallets and business card holders, interior products such as cars, members of clothes, wallpaper, and other products with high designability, and even if they have the same composition A carbon fiber reinforced resin-processed sheet capable of adjusting the bending resistance, wherein the ratio of the high bending resistance portion to the high bending resistance portion can be appropriately changed according to the application even within the same sheet It is to provide a processed sheet.
本発明は、炭素繊維布帛の両面に、熱可塑性エラストマーフィルムもしくはゴムフィルムをラミネートしてなる炭素繊維強化樹脂加工シートであって、当該フィルム面において、ＪＩＳ−Ｌ０８４９−２０１３の試験方法に従い、摩擦に対する染色堅ろう度試験を行い、乾燥条件および湿潤条件のどちらにおいてもＪＩＳ−Ｌ０８０１−２０１１ １０の判定方法によって判定される外観変化が４〜５級であり、かつＪＩＳ−Ｌ１０９６−２０１０ ８．２３．１ Ｂ法に従い測定される縫目の滑りの最大孔の大きさが１．０ｍｍ以下であることを特徴とする炭素繊維強化樹脂加工シートに関する。
ここで、上記炭素繊維布帛は、好ましくは、当該布帛が織物であり、その目付けが５０〜６００ｇ／ｍ２である。
また、上記熱可塑性エラストマーとしては、ポリウレタン系熱可塑性エラストマー、ポリアクリル酸エステル系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ポリ塩化ビニル系熱可塑性エラストマー、ポリ塩化ビニリデン系熱可塑性エラストマー、およびエチレン酢酸ビニル共重合体系熱可塑性エラストマーの群から選ばれた少なくとも1種が挙げられ、上記ゴムが、シリコーンゴム、合成ゴムもしくは天然ゴムが挙げられる。
さらに、炭素繊維布帛と熱可塑性エラストマーフィルムもしくはゴムフィルムとの比率は、好ましくは質量基準で７５：２５〜３０：７０である。
さらに、本発明の炭素繊維強化樹脂加工シートは、炭素繊維布帛へ熱可塑性エラストマーフィルムもしくはゴムフィルムをラミネートするに際し、成形温度および成形圧力を調節することで、ＪＩＳ−Ｌ１０９６−２０１０ ８．２２．１ Ａ法（ガーレ法）に従い測定される曲げ反発性（剛軟度）が、同一組成であっても５〜７０ｍＮの範囲で調節でき、このときの成形温度は、使用する熱可塑性エラストマーもしくはゴムの示差走査熱量測定での吸熱ピークのトップから求められる融点よりも２０℃低い温度から当該融点よりも５０℃高い温度の範囲にすることで、同一組成であっても上記範囲の剛軟度を調節することが可能となる。また、上記範囲の成形温度で、同時成形するか、あるいは成形後にさらに再成形することで、同一シート内であっても上記範囲の剛軟度に調節することが可能であり、同一シート内で剛軟度が小さい範囲の割合が１．０〜９９％で、剛軟度が大きい範囲の値が９９〜１．０％の範囲で調整することできる。
さらに、本発明の炭素繊維強化樹脂加工シートは、成形温度を融点−２０℃≦成形温度≦融点＋１０℃として成形した炭素繊維強化樹脂加工シートは、１分間に６０回の速度で、つかみ間距離２〜７cmの間で試験片を５００回屈曲させる屈曲疲労試験により折り曲げ操作をした後、外観にひび割れや亀裂が認められない。
The present invention is a carbon fiber reinforced resin-processed sheet formed by laminating a thermoplastic elastomer film or a rubber film on both sides of a carbon fiber cloth, and the film surface is subjected to friction according to the test method of JIS-L 0849-2013. The color fastness test is conducted, and the appearance change judged by the judgment method of JIS-L 0801-2011 10 under the drying condition and the wet condition is grade 4 to 5, and JIS-L 1096-2010 8.23.1 The present invention relates to a carbon fiber reinforced resin-processed sheet characterized in that the size of the largest hole of the stitch slippage measured according to method B is 1.0 mm or less.
Here, in the carbon fiber fabric, preferably, the fabric is a fabric, and the fabric weight is 50 to 600 g / m 2 .
In addition, as the thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyacrylic acid ester-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyvinyl chloride-based thermoplastic elastomer, polyvinylidene chloride-based thermoplastic elastomer, and ethylene vinyl acetate At least one member selected from the group of copolymer-based thermoplastic elastomers may be mentioned, and the rubber may be silicone rubber, synthetic rubber or natural rubber.
Furthermore, the ratio of the carbon fiber fabric to the thermoplastic elastomer film or rubber film is preferably 75:25 to 30:70 on a mass basis.
Furthermore, when laminating a thermoplastic elastomer film or rubber film on a carbon fiber cloth, the carbon fiber reinforced resin-processed sheet of the present invention can be adjusted according to JIS-L 1096-2010 8.22.1 by adjusting molding temperature and pressure. The bending resilience (bending resistance) measured according to method A (Gare method) can be adjusted in the range of 5 to 70 mN even with the same composition, and the molding temperature at this time is the thermoplastic elastomer or rubber used. By setting the temperature from 20 ° C lower than the melting point determined from the top of the endothermic peak in differential scanning calorimetry to 50 ° C higher than the melting point, the hardness in the above range is adjusted even for the same composition. It is possible to Further, by simultaneously molding at the molding temperature in the above range, or by further remolding after molding, it is possible to adjust the bending resistance in the above range even within the same sheet, and within the same sheet The ratio of the range where the bending resistance is small is 1.0 to 99%, and the value of the range where the bending resistance is large can be adjusted within the range of 99 to 1.0%.
Furthermore, the carbon fiber reinforced resin-processed sheet of the present invention has a molding temperature of -20 ° C. ≦ molding temperature ≦ melting point + 10 ° C. The carbon fiber-reinforced resin processed sheet has a gripping distance of 60 times per minute. After the bending operation according to the bending fatigue test in which the test piece is bent 500 times between 2 and 7 cm, no cracks or cracks are observed in the appearance.
本発明の炭素繊維強化樹脂加工シートは、炭素繊維布帛を熱可塑性エラストマーフィルムまたはゴムフィルムでラミネートすることで得られ、繊維同士の接着および耐摩擦性に優れ、同一組成であっても剛軟度を調節することが可能である。さらに、同時成形または再成形により、同一シート内であっても、剛軟度を調節することが可能となる。特に、成形温度を融点−２０℃≦成形温度≦融点＋１０℃として成形した樹脂加工シートは、耐屈曲疲労性に優れており、財布や名刺入れなどの折り曲げ部位に用いることができる。 The carbon fiber-reinforced resin-processed sheet of the present invention is obtained by laminating a carbon fiber cloth with a thermoplastic elastomer film or a rubber film, and is excellent in adhesion and friction resistance between fibers, and even when the composition is the same. It is possible to adjust the Furthermore, co-molding or re-shaping makes it possible to adjust the bending resistance even within the same sheet. In particular, a resin-processed sheet molded with a molding temperature of −20 ° C. ≦ molding temperature ≦ melting point + 10 ° C. is excellent in bending fatigue resistance, and can be used for a folded portion such as a wallet or a business card holder.
本発明の炭素繊維強化樹脂加工シートは、炭素繊維布帛の両面に、熱可塑性エラストマーフィルムもしくはゴムフィルムがラミネートされているものである。 The carbon fiber reinforced resin-processed sheet of the present invention is obtained by laminating a thermoplastic elastomer film or a rubber film on both sides of a carbon fiber cloth.
本発明で使用される炭素繊維布帛は、公知の炭素繊維を常法に従い製造することで得られる。例えば、炭素繊維としては、レーヨン系炭素繊維、ポリアクリロニトリル系炭素繊維、リグニンポリビニルアルコール系炭素繊維、ピッチ系炭素繊維などが挙げられる。本発明では、常法に従い製造してもよく、また、市販品を炭素繊維として用いてもよい。なお、市販品としては、例えば「トレカ」（商品名、東レ（株））や「パイロフィル」（商品名、三菱レイヨン（株））などが挙げられる。
また、上記炭素繊維は、常法に従い繊維束とされて、それぞれの炭素繊維織物のたて糸およびよこ糸に用いられるが、引き揃えや撚り、さらには扁平化などについては特に限定されず、種々の繊維束が炭素繊維として用いることができる。
The carbon fiber fabric used in the present invention can be obtained by manufacturing known carbon fibers according to a conventional method. For example, as carbon fibers, rayon carbon fibers, polyacrylonitrile carbon fibers, lignin polyvinyl alcohol carbon fibers, pitch carbon fibers, etc. may be mentioned. In the present invention, it may be manufactured according to a usual method, and a commercial item may be used as carbon fiber. In addition, as a commercial item, "TORECA" (brand name, Toray Industries, Inc.) and "Pyrofill" (brand name, Mitsubishi Rayon Co., Ltd.) etc. are mentioned, for example.
The carbon fibers are made into fiber bundles according to a conventional method and used for the warp and weft of each carbon fiber woven fabric, but are not particularly limited with respect to alignment, twisting, and flattening, and various fibers Bundles can be used as carbon fibers.
炭素繊維布帛の形態は、織物、たて編みやよこ編みなどの編み物、フェルト、不織布、紙などであってもよい。中でも糸の繊維軸方向の曲がりが少なく、構造的に生地が伸び縮みしにくい織物が望ましい。 The form of the carbon fiber fabric may be textile, knitting such as warp knitting or weft knitting, felt, non-woven fabric, paper or the like. Among them, it is desirable to use a woven fabric in which the bending in the fiber axial direction of the yarn is small and the fabric is structurally difficult to stretch and shrink.
本発明で炭素繊維布帛として用いられる炭素繊維織物の製織方法としては、特に限定されず、公知の織機を用いて、前記炭素繊維を製織する方法が挙げられる。このようにして、炭素繊維を製織することにより、平織の他、綾織、朱子織、斜紋織およびこれらの変化組織等の所望の炭素繊維織物を製造することができる。 The method of weaving the carbon fiber fabric used as the carbon fiber fabric in the present invention is not particularly limited, and a method of weaving the carbon fibers using a known loom may be mentioned. Thus, by weaving carbon fibers, desired carbon fiber fabrics such as twill weaves, satin weaves, diagonal weaves, and their modified structures other than plain weaves can be manufactured.
上記炭素繊維織物などの炭素繊維布帛の目付けは、通常、５０〜６００ｇ／ｍ２であり、好ましくは１００〜３００ｇ／ｍ２である。５０ｇ／ｍ２未満では、生地が薄く、カバンやバッグ、衣服の部品などの用途で引張強度や摩耗強度の面で好ましくない。一方、６００ｇ／ｍ２より大きいと、樹脂加工シートが厚く、かつ重くなり、カバンやバッグ、衣服の部品などへの応用においては適さない。
なお、炭素繊維布帛の厚さは、通常、０．１〜０．５ｍｍ程度である。
The basis weight of the carbon fiber cloth such as the carbon fiber cloth is usually 50 to 600 g / m 2 , preferably 100 to 300 g / m 2 . If it is less than 50 g / m 2 , the fabric is thin, which is not preferable in terms of tensile strength and abrasion strength in applications such as bags, bags, and parts of clothes. On the other hand, if it is larger than 600 g / m 2 , the resin-processed sheet becomes thick and heavy, and it is not suitable for application to bags, bags, parts of clothes, and the like.
In addition, the thickness of a carbon fiber cloth is about 0.1-0.5 mm normally.
一方、本発明に用いられる熱可塑性エラストマーフィルムに用いられる熱可塑性エラストマーとしては、特に限定されるものではなく、例えばポリウレタン系熱可塑性エラストマー、ポリアクリル酸エステル系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ポリ塩化ビニル系熱可塑性エラストマー、ポリ塩化ビニリデン系熱可塑性エラストマー、エチレン酢酸ビニル共重合体系熱可塑性エラストマー等が挙げられる。これらの中でも、ポリウレタン系熱可塑性エラストマーを用いる場合には、夏期や冬期の温度差に関わらず得られるシートの風合いが変わらないなどの優れた効果を発揮することから、ポリウレタン系熱可塑性エラストマーが好ましい。なお、これらの熱可塑性エラストマーは、一種単独で用いてもよいし、二種以上を組み合わせて用いてもよい。 On the other hand, the thermoplastic elastomer used for the thermoplastic elastomer film used in the present invention is not particularly limited, and, for example, polyurethane thermoplastic elastomer, polyacrylic acid ester thermoplastic elastomer, polyester thermoplastic elastomer, Polyvinyl chloride thermoplastic elastomers, polyvinylidene chloride thermoplastic elastomers, ethylene vinyl acetate copolymer thermoplastic elastomers, etc. may be mentioned. Among these, when using a polyurethane-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer is preferable because it exerts an excellent effect such as the feeling of the sheet obtained does not change regardless of the temperature difference in summer or winter. . These thermoplastic elastomers may be used singly or in combination of two or more.
また、ゴムフィルムに用いられるゴムとしては、シリコーンゴムや、イソプレンゴム（ＩＲ）、シス−１，４−ポリブタジエン（ＢＲ）、シンジオタクチック−１，２−ポリブタジエン（１，２ＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）などの合成ゴム、そのほか天然ゴム（ＮＲ）が挙げられる。これらのゴムは、一種単独で用いることも、二種以上を組み合わせて用いてもよい。 Also, as the rubber used for the rubber film, silicone rubber, isoprene rubber (IR), cis-1,4-polybutadiene (BR), syndiotactic-1,2-polybutadiene (1,2 BR), styrene-butadiene Examples include synthetic rubbers (SBR), acrylonitrile-butadiene rubber (NBR), synthetic rubbers such as chloroprene rubber (CR), and natural rubber (NR). These rubbers may be used alone or in combination of two or more.
以上の炭素繊維布帛と熱可塑性エラストマーフィルムもしくはゴムフィルムとの比率は、質量基準で、７５：２５〜３０：７０が好ましい。
ここで、炭素繊維布帛の割合が７５：３０を超えると、炭素繊維布帛の割合が多くなり炭素繊維布帛表面での熱可塑性エラストマーまたはゴムの厚みが不均一な状態になるため光沢ムラができるため好ましくなく、一方３０：７０未満では、樹脂の割合が多くなって得られるシートが重くなり、強度も低下しやすい。
なお、上記フィルムの厚みは、通常、０．０５〜０．２ｍｍ程度である。
The ratio of the above carbon fiber cloth to the thermoplastic elastomer film or rubber film is preferably 75:25 to 30:70 on a mass basis.
Here, if the ratio of the carbon fiber fabric exceeds 75:30, the ratio of the carbon fiber fabric increases and the thickness of the thermoplastic elastomer or rubber on the surface of the carbon fiber fabric becomes uneven, so uneven gloss occurs. On the other hand, if the ratio is less than 30:70, the proportion of the resin increases, the sheet obtained becomes heavy, and the strength tends to decrease.
In addition, the thickness of the said film is about 0.05-0.2 mm normally.
上記炭素繊維布帛に、上記熱可塑性エラストマーフィルムまたはゴムフィルムをラミネートする方法は、本発明の目的を阻害しない限り特に限定されない。より具体的には、炭素繊維布帛を熱可塑性エラストマーフィルムまたはゴムフィルムで挟み、加熱・加圧することで熱可塑性エラストマーまたはゴムを軟化・溶融させ、織物などの布帛内部に熱可塑性エラストマーまたはゴムを浸透させて製造することができる、プレスやロールなどの製造設備が使用できる。
また、ラミネートする際に、離型紙あるいは離型フィルムなどの離型用シートに挟んで製造する、または表面をパターン加工した化粧板やロールで製造することにより、それらの表面パターンを樹脂加工シートに転写できるため、表面光沢を容易に調節できる。
The method of laminating the thermoplastic elastomer film or the rubber film on the carbon fiber fabric is not particularly limited as long as the object of the present invention is not impaired. More specifically, by sandwiching a carbon fiber fabric with a thermoplastic elastomer film or rubber film and heating and pressing it, the thermoplastic elastomer or rubber is softened and melted, and the thermoplastic elastomer or rubber is penetrated into the fabric such as a fabric. It is possible to use manufacturing equipment such as press and roll that can be manufactured.
In addition, when laminating, it is manufactured by sandwiching it in a mold release sheet such as mold release paper or mold release film, or by using a decorative plate or a roll whose surface is patterned, to make these surface patterns into a resin-processed sheet. The surface gloss can be easily adjusted because the image can be transferred.
上記炭素繊維布帛に対する前記熱可塑性エラストマーまたはゴムの比率が少ないと、炭素繊維布帛表面での熱可塑性エラストマーまたはゴムの厚みが不均一な状態になるため光沢ムラになり、一方で前記熱可塑性エラストマーまたはゴムの比率が多いと炭素繊維本来の黒色の光沢が損なわれる。このため、上記のように、上記炭素繊維布帛と上記熱可塑性エラストマーまたはゴムとの比率は、質量基準で７５：２５〜３０：７０であるのが好ましい。 When the ratio of the thermoplastic elastomer or rubber to the carbon fiber fabric is small, the thickness of the thermoplastic elastomer or rubber on the surface of the carbon fiber fabric becomes uneven, resulting in uneven gloss, while the thermoplastic elastomer or the thermoplastic elastomer or If the proportion of rubber is high, the original black gloss of carbon fibers is lost. For this reason, as described above, the ratio of the carbon fiber cloth to the thermoplastic elastomer or rubber is preferably 75:25 to 30:70 on a mass basis.
この製造設備（プレス成形あるいはロール成形）での成形温度は、使用する熱可塑性エラストマーまたはゴムの融点、あるいはその前後の温度であり、より具体的には成形温度を使用する樹脂の示差走査熱量測定での吸熱ピークのトップから求められる融点よりも２０℃低い温度から当該融点よりも５０℃高い温度の範囲にすることで、同一組成であっても５〜７０ｍＮの範囲で調節が可能となる。また、再成形または同時成形により、同一シート内であっても、上記範囲の剛軟度に調節することが可能であり、同一シート内で剛軟度が小さい範囲の割合が１．０〜９９％で、剛軟度が大きい範囲の値が９９〜１．０％の範囲で調整することできる。特に、成形温度を融点−２０℃≦成形温度≦融点＋１０℃として成形した樹脂加工シートは耐屈曲疲労性に優れており、財布や名刺入れなどの折り曲げ部位に用いることができる。
なお、この際の加熱は、成形温度でラミネートする、または、常温から成形温度まで昇温してラミネートしたのち、常温まで降温するなどの手法が可能である。
The molding temperature in this production facility (press molding or roll molding) is the melting point of the thermoplastic elastomer or rubber to be used, or a temperature around it, and more specifically, differential scanning calorimetry of the resin using the molding temperature By setting the temperature in the range of 20 ° C. lower than the melting point determined from the top of the endothermic peak to 50 ° C. higher than the melting point, adjustment can be made in the range of 5 to 70 mN even with the same composition. Moreover, even within the same sheet, it is possible to adjust to the above-mentioned range of the bending resistance by re-forming or simultaneous forming, and the ratio of the range where the bending resistance is small in the same sheet is 1.0 to 99 In%, the value of the range where the bending resistance is large can be adjusted in the range of 99 to 1.0%. In particular, a resin-processed sheet molded with a molding temperature of −20 ° C. ≦ molding temperature ≦ melting point + 10 ° C. is excellent in bending fatigue resistance, and can be used for a folded portion such as a wallet or a business card holder.
In this case, heating may be performed by laminating at the molding temperature or by raising the temperature from the normal temperature to the molding temperature and laminating, and then lowering the temperature to the normal temperature.
また、この際、ラミネート成形時の圧力は、通常、０．２５ＭＰａ以上、好ましくは１．０〜５．０ＭＰａである。本発明のラミネート成形では、比較的低い圧力の条件でよく、０．２５ＭＰａ未満では、炭素繊維布帛と樹脂フィルムの接着性が悪く、一方５．０ＭＰａを超えると、炭素繊維布帛の目ズレが起こりやすく、意匠性に劣る可能性がある。 Moreover, in this case, the pressure at the time of laminate molding is usually 0.25 MPa or more, preferably 1.0 to 5.0 MPa. In the laminate molding of the present invention, the condition of relatively low pressure is sufficient, and if less than 0.25 MPa, the adhesion between the carbon fiber cloth and the resin film is poor, while if it exceeds 5.0 MPa, the carbon fiber cloth is dislocated. It may be easy and inferior in design.
ここで、同時成形とは、炭素繊維布帛と熱可塑性エラストマーフィルムもしくはゴムフィルムとを同時に、加熱・加圧成形することをいう。また、再成形とは、炭素繊維布帛と熱可塑性エラストマーフィルムもしくはゴムフィルムとが既にラミネートされた樹脂加工シートを、再度、成形することをいう。
なお、再成形の場合、同時成形と同じ範囲を成形してもよく、同時成形とは異なる範囲を成形してもよい。
Here, simultaneous molding means that the carbon fiber cloth and the thermoplastic elastomer film or rubber film are simultaneously heat / pressure molded. In addition, the re-forming means that the resin-processed sheet in which the carbon fiber cloth and the thermoplastic elastomer film or the rubber film are already laminated is re-formed.
In the case of re-molding, the same range as in simultaneous molding may be formed, or a range different from simultaneous molding may be formed.
かくして得られる本発明の樹脂加工シートは、布や皮革と同様に縫製が可能であり、カバンやバック、財布や名刺入れなどに応用できる。また、柔軟性があるので、車の内装などに容易に貼り付けることができる。
また、本発明の樹脂加工シートは、耐摩耗性などの物性面での優れた特徴と同時に、使用されるフィルムが透明な場合には、炭素繊維本来の黒色の光沢を損なわないという特徴を有する。
The resin-processed sheet of the present invention thus obtained can be sewn in the same manner as cloth and leather, and can be applied to bags, bags, wallets and business card holders. In addition, because it is flexible, it can be easily attached to the interior of a car.
Further, the resin-processed sheet of the present invention is characterized by excellent characteristics in terms of physical properties such as abrasion resistance, and also does not impair the inherent black gloss of carbon fibers when the film to be used is transparent. .
本発明の樹脂加工シートは、フィルム面における、すれ作用による他への色移りの程度（汚染）、すなわち、ＪＩＳ−Ｌ０８４９−２０１３の試験方法に従い測定される、摩擦に対する染色堅ろう度が、乾燥条件および湿潤条件のどちらにおいてもＪＩＳ−Ｌ０８０１−２０１１ １０の判定方法によって判定される外観変化が４〜５級である。上記染色堅ろう度の級数において、他への色移りの程度は実用上問題ない。また、本発明の樹脂加工シートは、剛軟度の違いによらず、優れた摩擦に対する染色堅ろう度を有する。 In the resin-processed sheet of the present invention, the degree of color transfer (staining) to another on the film surface due to rubbing action, that is, the color fastness to rubbing, which is measured according to the test method of JIS-L 0849-2013, is a dry condition The appearance change determined by the determination method of JIS-L 080 1-2011 10 under both of the wet conditions and the wet conditions is grade 4 to 5. In the above-mentioned series of color fastnesses, the degree of color transfer to the other is practically acceptable. In addition, the resin-processed sheet of the present invention has excellent color fastness to rubbing regardless of the difference in bending resistance.
さらに、本発明の樹脂加工シートは、フィルム面における、ＪＩＳ−Ｌ１０９６−２０１０ ８．２３．１ Ｂ法に従い測定される縫目の滑りの最大孔の大きさ（縫目滑脱抵抗力）が１．０ｍｍ以下であり、カバンなどの縫製品の使用時に縫目にかかる荷重に対して十分な耐久性を持つ。また、本発明の樹脂加工シートは、剛軟度の違いによらず、縫目にかかる荷重に対して優れた耐久性を有する。 Furthermore, in the resin-processed sheet of the present invention, the size of the largest hole (seam-slip resistance force) of the seam slippage measured on the film surface according to JIS-L1096-2010 8.23.1 B method is 1. It is 0 mm or less and has sufficient durability against the load applied to the seam when using sewing products such as bags. Moreover, the resin-processed sheet | seat of this invention has the outstanding durability with respect to the load concerning a seam regardless of the difference in bending resistance.
さらに、本発明の樹脂加工シートは、ＪＩＳ−Ｌ１０９６−２０１０ ８．２２．１ Ａ法（ガーレ法）に従い測定される曲げ反発性（剛軟度）が、５〜７０ｍＮの範囲である。同一組成であっても必要に応じて、上記剛軟度の範囲で調節することができる。また、同時成形するか、あるいは成形後にさらに再成形することで、同一シート内であっても上記範囲の剛軟度に調節することが可能であり、同一シート内で剛軟度が小さい範囲の割合が１．０〜９９％で、剛軟度が大きい範囲の値が９９〜１．０％の範囲であり、適宜用途に応じて変更できるシートの製造も可能である。
このように、本発明の樹脂加工シートの剛軟度を上記の範囲にするには、成形時において、成形温度および成形圧力を調節すればよい。
Furthermore, the bending resistance (bending resistance) measured according to JIS-L1096-2010 8.22.1 A method (Gare method) of the resin-processed sheet of the present invention is in the range of 5 to 70 mN. Even if it is the same composition, it can be adjusted in the range of the above-mentioned bending resistance as needed. In addition, by simultaneously molding or by further re-forming after molding, it is possible to adjust to the above-mentioned range of bending resistance even within the same sheet, and within the same sheet, the range of small bending resistance It is also possible to produce a sheet whose ratio is 1.0 to 99% and the value of the range where the bending resistance is large is in the range of 99 to 1.0%, and which can be suitably changed according to the application.
As described above, in order to set the bending resistance of the resin-processed sheet of the present invention in the above range, the molding temperature and the molding pressure may be adjusted during molding.
特に、成形温度を融点−２０℃≦成形温度≦融点＋１０℃として成形した本発明の樹脂加工シートは、１分間に６０回の速度で、つかみ間距離２〜７cmの間で試験片を５００回屈曲させる屈曲疲労試験により、折り曲げ操作をした後、外観にひび割れや亀裂が認められないため、財布や名刺入れなどの折り曲げが必要な箇所に好適に用いることができる。
このような本発明の樹脂加工シートの屈曲疲労試験における耐屈曲疲労性は、成形時において、成形温度および成形圧力を調節することにより達成することができる。
In particular, the resin-processed sheet of the present invention molded at a molding temperature of −20 ° C. ≦ molding temperature ≦ melting point + 10 ° C. performs 500 times on a test piece at a speed of 60 times a minute and a distance between 2 to 7 cm. Since no cracks or cracks are found in the appearance after the bending operation by the bending fatigue test to be bent, it can be suitably used in places where bending such as a wallet or a business card holder is required.
Such bending fatigue resistance in the bending fatigue test of the resin-processed sheet of the present invention can be achieved by adjusting the molding temperature and the molding pressure at the time of molding.
以下、本発明の一実施態様を、図面を用いて説明する。
すなわち、図１は、本発明の炭素繊維強化樹脂加工シートのプレス成形による製造工程の概略図であり、（Ａ）は材料の構成図、（Ｂ）はプレス成形装置によるラミネート成形の概略図、（Ｃ）は得られる炭素繊維強化樹脂加工シートの斜視図である。
まず、図１（Ａ）に示すように、炭素繊維織物（炭素繊維布帛）の両面に、熱可塑性ウレタンシート（熱可塑性エラストマーフィルム）、離型用シート（離型紙または離型フィルム）、ＳＵＳ板（化粧板）を順次挟み込み、これを図１（Ｂ）のように、プレス機に載置して、圧力（１．０〜５．０ＭＰａ）、温度（熱可塑性エラストマーの示差走査熱量測定での吸熱ピークのトップから求められる融点よりも２０℃低い温度から当該融点よりも５０℃高い温度の範囲）をかけてプレス成形し、成形後、離型用シートおよびＳＵＳ板を取り除いて、図１（Ｃ）に示す本発明の炭素繊維強化樹脂加工シートが得られる。なお、図１では、離型用シートも用いているが、用いなくてもよい。
また、図１では、プレス成形の一例を示しているが、図示しないロール装置などでラミネート成形することもできる。
Hereinafter, an embodiment of the present invention will be described using the drawings.
That is, FIG. 1 is a schematic view of a manufacturing process by press molding of a carbon fiber reinforced resin-processed sheet of the present invention, (A) is a block diagram of a material, (B) is a schematic view of laminate molding by a press molding apparatus, (C) is a perspective view of the carbon fiber reinforced resin-processed sheet obtained.
First, as shown in FIG. 1 (A), thermoplastic urethane sheet (thermoplastic elastomer film), release sheet (release paper or release film), SUS plate on both sides of carbon fiber fabric (carbon fiber fabric) (Faceplate) is sequentially sandwiched, and this is placed in a press as shown in FIG. 1 (B), and the pressure (1.0 to 5.0 MPa) and the temperature (differential scanning calorimetry of thermoplastic elastomer is measured The sheet is press molded by applying a temperature 20 ° C. lower than the melting point determined from the top of the endothermic peak to a temperature 50 ° C. higher than the melting point), and after molding, the release sheet and the SUS plate are removed. The carbon fiber reinforced resin-processed sheet | seat of this invention shown to C) is obtained. In addition, although the sheet | seat for mold release is also used in FIG. 1, it is not necessary to use.
Moreover, although FIG. 1 shows an example of press molding, lamination molding can also be performed by a roll device or the like (not shown).
以下、実施例により本発明をさらに具体的に説明するが、これらの実施例だけに限定されるものではない。
ここで、実施例における測定方法は、下記のとおりである。
Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.
Here, the measuring method in an Example is as follows.
＜測定方法＞
摩擦に対する染色堅ろう度は、ＪＩＳ−Ｌ０８４９−２０１３の試験方法に従って測定した。より具体的には、約２２０×３０ｍｍの試験片を摩擦試験機ＩＩ型で用い、２Ｎの荷重で摩擦用白綿布（接触面積１００ｃｍ２）を試験片の中央部１００ｍｍの間を毎分３０往復の速度で１００回往復摩擦する。湿潤条件では、摩擦用白綿布は水で濡らし１００％の湿潤状態にする。なお、摩擦用白綿布の着色判定は、ＪＩＳ−Ｌ０８０１−２０１１の箇条１０によった。
<Measurement method>
The color fastness to rubbing was measured according to the test method of JIS-L 0849-2013. More specifically, a test piece of about 220 × 30 mm is used in friction tester type II, and a friction white cotton cloth (contact area 100 cm 2 ) is applied at a load of 2 N at a rate of 30 reciprocations per minute between the central portion 100 mm of the test piece. Reciprocate at a speed of 100 times. In wet conditions, the white rub cloth is wetted with water to a 100% wet state. In addition, the coloring determination of the white cotton cloth for friction was based on the item 10 of JIS-L0801-2011.
縫目滑脱抵抗力の測定方法は、ＪＩＳ−Ｌ１０９６−２０１０ ８．２３．１ Ｂ法を用い、縫目の滑りの最大孔の大きさを測定する。より具体的には、約１００×１７０ｍｍの試験片を切断端から１０ｍｍの箇所を縫い合わせ試験用試料とする。試料を１分間当たり３００ｍｍの速度で、１１７．７Ｎの荷重を与えた後つかみから取り外し、１時間放置後縫目付近のたるみが消える程度の荷重を縫目に直角方向に加え、縫目滑りの最大孔の大きさを０．１ｍｍの単位まで測定した。 The method of measuring the resistance to seam slippage is to measure the size of the largest hole of the stitch slip using JIS-L1096-2010 8.23.1 B method. More specifically, a test piece of about 100 × 170 mm and a point of 10 mm from the cutting end are used as a test sample for stitching. The sample was removed from the grip after applying a load of 117.7 N at a speed of 300 mm per minute, and after leaving for 1 hour, a load was applied in a direction perpendicular to the seam so that the slack near the seam disappears. The size of the largest hole was measured to the unit of 0.1 mm.
曲げ反発性（剛軟度）は、ＪＩＳ−Ｌ１０９６−２０１０ ８．２２．１ Ａ法（ガーレ法）による試験方法に従って測定した。より具体的には、ガーレ式試験機で用い、８９×２５ｍｍの試験片で測定した。
屈曲疲労試験の測定方法は、デマッチャ式繰り返し疲労試験による折り曲げ操作をした後、外観のひび割れや亀裂を判定した。より具体的には、１分間に６０回の速度で、つかみ間距離２〜７ｃｍの間で試験片を５００回屈曲させた後、外観を確認した。
The bending resilience (bending resistance) was measured according to the test method according to JIS-L1096-2010 8.22.1 A method (Gare method). More specifically, it used with a Gurley-type testing machine, and measured with a 89 x 25 mm test piece.
The measurement method of a bending fatigue test determined the crack and the crack of the appearance, after performing the bending operation by a Dematcher type | mold repeated fatigue test. More specifically, the appearance was confirmed after bending the test piece 500 times at a distance of 2 to 7 cm between the grips at a speed of 60 times per minute.
＜実施例1＞
東レ（株）製の炭素繊維織物（商品名：トレカクロス ＣＯ６３４３Ｂ）（厚み：０．２３ｍｍ、目付：１９８ｇ／ｍ２）の両面を、日本マタイ（株）製の熱可塑性ポリウレタンフィルム（厚み：０．１ｍｍ）でラミネートし、図１のプレス装置を用いて、成形圧力１ＭＰａで、４０℃から１５０℃まで昇温して、１５０℃で５分間保持し、その後、４０℃まで降温した。結果を表１に示す。
Example 1
Thermoplastic polyurethane film (thickness: 0) manufactured by Nippon Matai Co., Ltd. on both sides of a carbon fiber woven fabric (trade name: Treka Cross CO 6343 B) (thickness: 0.23 mm, basis weight: 198 g / m 2 ) manufactured by Toray Industries, Inc. 1), and the temperature was raised from 40 ° C. to 150 ° C. under a molding pressure of 1 MPa using the press apparatus of FIG. 1, held at 150 ° C. for 5 minutes, and then cooled to 40 ° C. The results are shown in Table 1.
＜実施例２＞
三菱レイヨン（株）製の炭素繊維（商品名：パイロフィル ＴＲ ３０Ｌ ３Ｓ、フィラメント数３０００本）を用いて、炭素繊維織物（厚み：０．３〜０．５ｍｍ、目付：２８０ｇ／ｍ２）を製造し、その製造した炭素繊維織物の両面を、日本マタイ（株）製の熱可塑性ポリウレタンフィルム（厚み：０．０５ｍｍ）でラミネートし、実施例１と同じ条件で成形した。結果を表１に示す。
Example 2
A carbon fiber fabric (thickness: 0.3 to 0.5 mm, fabric weight: 280 g / m 2 ) is manufactured using carbon fiber (trade name: Pyrophyll TR 30L 3S, 3000 filaments) manufactured by Mitsubishi Rayon Co., Ltd. Then, both surfaces of the carbon fiber woven fabric produced were laminated with a thermoplastic polyurethane film (thickness: 0.05 mm) manufactured by Nippon Mata Co., Ltd. and molded under the same conditions as in Example 1. The results are shown in Table 1.
＜実施例３＞
三菱レイヨン（株）製の炭素繊維（商品名：パイロフィル ＴＲ ３０Ｌ ３Ｓ、フィラメント数３０００本）を用いて、炭素繊維織物（厚み：０．３〜０．５ｍｍ、目付：２８０ｇ／ｍ２）を製造し、その製造した炭素繊維織物の両面を、日本マタイ（株）製の熱可塑性ポリウレタンフィルム（厚み：０．１ｍｍ）でラミネートし、実施例１と同じ条件で成形した。結果を表１に示す。
また、得られた加工シートの走査型電子顕微鏡（１５０倍）による断面写真を図２に示す。
図２によれば、写真の最上層および最下層が熱可塑性ポリウレタンシートで、中央の二層［（たて糸（上側）とよこ糸（下側））が炭素繊維織物を示している。成形温度が１５０℃と、熱可塑性ポリウレタンの融点（１５０℃）、すなわち成形温度が融点−２０℃≦成形温度≦融点＋１０℃の範囲であるために、熱可塑性ポリウレタンが炭素繊維織物表面に付着し、得られる樹脂加工シートは、「柔らかい」樹脂加工シートとなっている。
Example 3
A carbon fiber fabric (thickness: 0.3 to 0.5 mm, fabric weight: 280 g / m 2 ) is manufactured using carbon fiber (trade name: Pyrophyll TR 30L 3S, 3000 filaments) manufactured by Mitsubishi Rayon Co., Ltd. Then, both surfaces of the carbon fiber woven fabric produced were laminated with a thermoplastic polyurethane film (thickness: 0.1 mm) manufactured by Nippon Mata Co., Ltd. and molded under the same conditions as in Example 1. The results are shown in Table 1.
Further, a cross-sectional photograph of the obtained processed sheet by a scanning electron microscope (150 ×) is shown in FIG.
According to FIG. 2, the top and bottom layers of the photograph are thermoplastic polyurethane sheets, and the middle two layers (a warp (upper) and a weft (lower)) indicate a carbon fiber fabric. The thermoplastic polyurethane adheres to the surface of the carbon fiber fabric because the molding temperature is 150 ° C. and the melting point of the thermoplastic polyurethane (150 ° C.), ie, the molding temperature is in the range of melting point -20 ° C. ≦ molding temperature ≦ melting point + 10 ° C. The resulting resin-processed sheet is a "soft" resin-processed sheet.
＜実施例４＞
三菱レイヨン（株）製の炭素繊維（商品名：パイロフィル ＴＲ ３０Ｌ ３Ｓ、フィラメント数３０００本）を用い、実施例２と同様にして炭素繊維織物を製造し、その製造した炭素繊維織物の両面を、日本マタイ（株）製の熱可塑性ポリウレタンフィルム（厚み：０．２ｍｍ）でラミネートし、成形圧力３ＭＰａで、４０℃から２００℃まで昇温して、２００℃で１０分間保持し、その後、４０℃まで降温した。結果を表１に示す。
Example 4
A carbon fiber woven fabric is manufactured in the same manner as in Example 2 using a carbon fiber manufactured by Mitsubishi Rayon Co., Ltd. (trade name: Pyrophyll TR 30L 3S, 3000 filaments), and both sides of the manufactured carbon fiber woven fabric are Laminated with a thermoplastic polyurethane film (thickness: 0.2 mm) manufactured by Nippon Matai Co., Ltd., heated from 40 ° C. to 200 ° C. at a molding pressure of 3 MPa, held at 200 ° C. for 10 minutes, and then 40 ° C. It had cooled down. The results are shown in Table 1.
＜実施例５＞
実施例３で得られた樹脂加工シートを、成形圧力１ＭＰａで、４０℃から１７０℃まで昇温して、１７０℃で１０分間保持し、その後、４０℃まで降温した。結果を表１に示す。
また、得られた樹脂加工シートの走査型電子顕微鏡（１５０倍）による断面写真を図３に示す。
図３によれば、写真の最上層および最下層が熱可塑性ポリウレタンシートで、中央の二層[よこ糸（上側）とたて糸（下側）]が炭素繊維織物を示している。成形温度が１７０℃と、熱可塑性ポリウレタンの融点（１５０℃）を超える温度、すなわち、融点＜成形温度（融点＋２０℃＝１７０℃、融点＋１０℃＜成形温度≦融点＋５０℃の範囲）であるために、熱可塑性ポリウレタンが炭素繊維織物内部に浸透し、得られる加工シートは、「硬い」樹脂加工シートとなっている。
このように、実施例３と実施例５を対比して明らかなように、成形温度および成形圧力を調節することにより、熱可塑性ポリウレタンの炭素繊維織物への浸透度合いをコントロールすることができ、得られる樹脂加工シートの「しなやかさ（剛軟度）」を調整することができ、折り曲げることが可能な柔軟な樹脂加工シートから、硬い樹脂加工シートまで、幅広いしなやかさを有する樹脂加工シートを提供できる。
Example 5
The resin-processed sheet obtained in Example 3 was heated from 40 ° C. to 170 ° C. at a molding pressure of 1 MPa, held at 170 ° C. for 10 minutes, and then cooled to 40 ° C. The results are shown in Table 1.
Moreover, the cross-sectional photograph by a scanning electron microscope (150 times) of the obtained resin-processed sheet is shown in FIG.
According to FIG. 3, the top and bottom layers of the photograph are thermoplastic polyurethane sheets, and the middle two layers [weft (upper) and warp (lower)] show carbon fiber fabric. The molding temperature is 170 ° C., which exceeds the melting point (150 ° C.) of the thermoplastic polyurethane, that is, the melting point <the molding temperature (melting point + 20 ° C. = 170 ° C., melting point + 10 ° C. <forming temperature ≦ melting point + 50 ° C.) In addition, the thermoplastic polyurethane penetrates into the carbon fiber fabric, and the resulting processed sheet is a "hard" resin-processed sheet.
Thus, as apparent from the comparison between Example 3 and Example 5, the degree of penetration of the thermoplastic polyurethane into the carbon fiber fabric can be controlled by adjusting the molding temperature and the molding pressure. It is possible to provide a resin-processed sheet with a wide range of flexibility, from flexible resin-processed sheets that can be adjusted and flexible to flexible resin-processed sheets, which can adjust the "flexibility" of resin-processed sheets. .
＜実施例６＞
実施例２で得られた樹脂加工シートの１／３の範囲に１７０℃の温度および１ＭＰａの圧力をかけて再成形することで得られた樹脂加工シートは、２／３の範囲を実施例２で得られた樹脂加工シートの特性を、再成形した１／３の範囲は実施例３で得られた樹脂加工シートの特性を有していた。
Example 6
The resin-processed sheet obtained by re-forming by applying a temperature of 170 ° C. and a pressure of 1 MPa to the range of 1/3 of the resin-processed sheet obtained in Example 2 corresponds to the range of 2/3 of Example 2 In the properties of the resin-processed sheet obtained in the above, the remolded 1/3 range had the properties of the resin-processed sheet obtained in Example 3.
＜比較例１＞
東レ（株）製の炭素繊維織物（商品名：トレカクロス ＣＯ６３４３Ｂ）（厚みは０．２３ｍｍ、目付：１９８ｇ／ｍ２）を、エポキシ樹脂ワニスに含浸し、図１のプレス装置を用いて、成形圧力５ＭＰａで、８０℃から１６０℃まで昇温して、その後、４０℃まで降温した。結果を表１に示す。
Comparative Example 1
A carbon fiber fabric manufactured by Toray Industries, Inc. (trade name: TORAYCACROS CO 6343B) (thickness: 0.23 mm, basis weight: 198 g / m 2 ) is impregnated in epoxy resin varnish and molded using a press in FIG. The temperature was raised from 80 ° C. to 160 ° C. at a pressure of 5 MPa, and then lowered to 40 ° C. The results are shown in Table 1.
本発明の炭素繊維強化樹脂加工シートは、カバン、バック、財布、名刺入れなどの縫製品、車の内装品、衣服の部材、壁紙、壁紙などに有用である。
The carbon fiber reinforced resin-processed sheet of the present invention is useful for sewing products such as bags, bags, wallets, business card holders, car interior products, members of clothes, wallpaper, wallpaper and the like.
Claims (4)
When laminating a transparent film made of a polyurethane thermoplastic elastomer on both sides of a carbon fiber fabric, the molding temperature at the time of lamination is in the range of 20 ° C. lower than the melting point of the polyurethane thermoplastic elastomer to 50 ° C. higher than the melting point The method for producing a carbon fiber reinforced resin-processed sheet according to any one of claims 1 to 3, wherein a molding pressure at the time of laminating is 1.0 to 5.0 MPa.
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