JP3048911B2 - Carbon fiber for resin reinforcement and reinforced thermoplastic resin molding - Google Patents
Carbon fiber for resin reinforcement and reinforced thermoplastic resin moldingInfo
- Publication number
- JP3048911B2 JP3048911B2 JP8012737A JP1273796A JP3048911B2 JP 3048911 B2 JP3048911 B2 JP 3048911B2 JP 8012737 A JP8012737 A JP 8012737A JP 1273796 A JP1273796 A JP 1273796A JP 3048911 B2 JP3048911 B2 JP 3048911B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- carbon fiber
- thermoplastic resin
- reinforcement
- molded article
- 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.)
- Expired - Lifetime
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 66
- 239000004917 carbon fiber Substances 0.000 title claims description 66
- 229920005989 resin Polymers 0.000 title claims description 59
- 239000011347 resin Substances 0.000 title claims description 59
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 48
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 44
- 230000002787 reinforcement Effects 0.000 title claims description 35
- 238000000465 moulding Methods 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims description 17
- 230000003014 reinforcing effect Effects 0.000 claims description 11
- 229920005668 polycarbonate resin Polymers 0.000 claims description 5
- 239000004431 polycarbonate resin Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000003856 thermoforming Methods 0.000 description 6
- 238000005187 foaming Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Moulding By Coating Moulds (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、樹脂強化用炭素繊
維およびその樹脂強化用炭素繊維を用いて強化された強
化熱可塑性樹脂成形体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon fiber for resin reinforcement and a reinforced thermoplastic resin molded article reinforced with the carbon fiber for resin reinforcement.
【０００２】[0002]
【従来の技術】従来、炭素繊維は、コンクリート等の補
強用としてまたは熱硬化性樹脂成形体を強化する目的で
用いられており、その多くの場合、炭素繊維はその表面
がマトリックス材料の種類別に選択された処理剤により
処理を施されておらず、むしろ表面を処理されていない
炭素繊維が最適であるとされている。2. Description of the Related Art Conventionally, carbon fibers have been used for reinforcing concrete or the like or for the purpose of reinforcing thermosetting resin molded articles. In many cases, the surface of carbon fibers is classified according to the type of matrix material. Carbon fibers that have not been treated with the treatment agent selected, but rather have not been treated on the surface, are considered optimal.
【０００３】近年になって、熱可塑性樹脂成形体を炭素
繊維で強化することが検討され、炭素繊維と熱可塑性樹
脂との接着性を向上させるために、炭素繊維の表面処理
が研究されている。この場合の処理剤としては、例え
ば、イソシアネート架橋剤、ポリビニルピロリドン、ポ
リウレタン樹脂、ビスマレイミド等のイミド系樹脂など
が検討されており、その組成は母材樹脂としての熱可塑
性樹脂との接着性やそれ自体の熱安定性などを考慮して
決定されている。In recent years, studies have been made on reinforcing a thermoplastic resin molded body with carbon fibers, and surface treatment of carbon fibers has been studied in order to improve the adhesion between the carbon fibers and the thermoplastic resin. . As the treating agent in this case, for example, an isocyanate crosslinking agent, polyvinylpyrrolidone, a polyurethane resin, an imide-based resin such as bismaleimide, and the like have been studied. It is determined in consideration of its own thermal stability.
【０００４】しかしながら、上記の処理剤で表面処理さ
れた炭素繊維では、強化しようとする熱可塑性樹脂の融
点以上の温度をかけないと、熱可塑性樹脂と炭素繊維と
の接着性が十分でなく、強化した熱可塑性樹脂成形体の
曲げ強度、曲げ弾性率などの機械的特性がなお満足する
までには至っていない。また、処理剤によっては熱可塑
性樹脂成形体の熱成形時の加熱により変色を起こすな
ど、熱安定性にも問題があった。とりわけ、熱変形温度
が高く、加熱時の粘性の比較的低い樹脂、例えばポリカ
ーボネート樹脂を炭素繊維で強化した樹脂成形体などの
場合では、前記の接着性や熱安定性に起因して、強化さ
れた熱可塑性樹脂成形体が熱成形時に変色したり発泡す
るという問題がある。[0004] However, in the case of carbon fibers surface-treated with the above-mentioned treating agent, the adhesiveness between the thermoplastic resin and the carbon fibers is not sufficient unless a temperature higher than the melting point of the thermoplastic resin to be reinforced is applied. Mechanical properties such as flexural strength and flexural modulus of the reinforced thermoplastic resin molding have not yet been satisfied. In addition, depending on the treatment agent, there is a problem in thermal stability, such as discoloration due to heating during thermoforming of the thermoplastic resin molded article. In particular, in the case of a resin having a high heat deformation temperature and a resin having a relatively low viscosity at the time of heating, for example, a resin molded body in which a polycarbonate resin is reinforced with carbon fibers, the resin is reinforced due to the aforementioned adhesiveness and thermal stability. In addition, there is a problem in that the molded thermoplastic resin discolors or foams during thermoforming.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記のよう
な従来技術を背景にしてなされたもので、その主たる目
的は、熱可塑性樹脂の融点以下の低温下で熱可塑性樹脂
との接着性が高く、強化熱可塑性樹脂成形体の機械的強
度を高める樹脂強化用炭素繊維と、これを用いた強化熱
可塑性樹脂成形体を提供することである。DISCLOSURE OF THE INVENTION The present invention has been made on the basis of the above-mentioned prior art, and its main object is to provide an adhesive with a thermoplastic resin at a low temperature below the melting point of the thermoplastic resin. It is an object of the present invention to provide a carbon fiber for resin reinforcement which enhances the mechanical strength of a reinforced thermoplastic resin molded article and a reinforced thermoplastic resin molded article using the same.
【０００６】[0006]
【発明を解決するための手段】本発明は、上記目的を達
成するために、樹脂強化用炭素繊維を熱可塑性ポリエス
テル樹脂で表面処理すれば、樹脂強化用炭素繊維の熱可
塑性樹脂との接着性を高めることができ、また熱可塑性
ポリエステル樹脂として特定の軟化点のものを選べば、
熱可塑性樹脂と処理剤の接着性がさらに向上し、処理剤
の熱安定性を高めることができ、かかる処理剤で表面処
理された樹脂強化用炭素繊維を用いて強化熱可塑性樹脂
成形体とすれば、機械特性に優れ、かつ熱成形性にも優
れた熱可塑性樹脂成形体を得ることができることを見出
し完成したものである。According to the present invention, in order to attain the above object, the surface of a carbon fiber for resin reinforcement is treated with a thermoplastic polyester resin, and the adhesiveness of the carbon fiber for resin reinforcement with the thermoplastic resin is improved. If you choose a specific softening point as the thermoplastic polyester resin,
The adhesiveness between the thermoplastic resin and the treating agent is further improved, and the thermal stability of the treating agent can be increased. For example, they have found that a thermoplastic resin molded article having excellent mechanical properties and excellent thermoformability can be obtained.
【０００７】すなわち、本発明の第１の発明は、熱可塑
性ポリエステル樹脂からなる処理剤で表面処理されたこ
とを特徴とする樹脂強化用炭素繊維を要旨とするもので
ある。That is, a first aspect of the present invention is to provide a carbon fiber for resin reinforcement characterized by being surface-treated with a treating agent comprising a thermoplastic polyester resin.
【０００８】また、第１の発明の具体的な態様は、処理
剤が軟化点１５０℃以上の熱可塑性ポリエステル樹脂か
らなる処理剤で表面処理された前記樹脂強化用炭素繊維
である。[0008] A specific embodiment of the first invention is the carbon fiber for resin reinforcement, wherein the surface of the carbon fiber is treated with a treating agent comprising a thermoplastic polyester resin having a softening point of 150 ° C or higher.
【０００９】さらにまた、第１の発明の別の具体的な態
様は、処理剤の付着量が強化用炭素繊維に対して１２〜
３０重量％である前記樹脂強化用炭素繊維である。Further, in another specific embodiment of the first invention, the amount of the treatment agent attached to the reinforcing carbon fiber is 12 to 10%.
30% by weight of the carbon fiber for resin reinforcement.
【００１０】つぎに、本発明の第２の発明は、前記樹脂
強化用炭素繊維により強化された強化熱可塑性樹脂成形
体である。Next, a second aspect of the present invention is a reinforced thermoplastic resin molded article reinforced by the carbon fiber for resin reinforcement.
【００１１】また、第２の発明の具体的な態様は、前記
樹脂強化用炭素繊維と熱可塑性樹脂成形体とが交互に積
層された形態の強化熱可塑性樹脂成形体である。Further, a specific aspect of the second invention is a reinforced thermoplastic resin molded article in which the carbon fibers for resin reinforcement and the thermoplastic resin molded article are alternately laminated.
【００１２】さらにまた、第２の発明の別の具体的な態
様は、前記樹脂強化用炭素繊維とポリカーボネート樹脂
成形体とが交互に積層された形態の強化熱可塑性樹脂成
形体である。Further, another specific embodiment of the second invention is a reinforced thermoplastic resin molded article in which the carbon fibers for resin reinforcement and the polycarbonate resin molded article are alternately laminated.
【００１３】まず、本発明の第１の発明の樹脂強化用炭
素繊維に用いられる炭素繊維について説明すると、炭素
繊維の形態として、それ自体がシート状を呈し、強化の
対象となる母材樹脂としての熱可塑性樹脂と積層一体化
する際に、成層可能な形態のものが好適に用いられる。
例えば、ストランドから織成された平織、朱子織、綾織
等のクロス、あるいは編物などの織布状のもの、またチ
ョップドストランドマット、サーフェーシングマット等
の短繊維マットやあるいはダイヤモンドマット、スワー
ルマット等の長繊維マットなどの不織布状のものが適用
され、一般市販品が適用される。First, the carbon fiber used for the carbon fiber for resin reinforcement according to the first invention of the present invention will be described. As a form of the carbon fiber, the carbon fiber itself has a sheet shape and is used as a base material resin to be reinforced. When laminating and integrating with a thermoplastic resin of the above, a layer capable of forming a layer is preferably used.
For example, cloths such as plain weave, satin weave, twill weave or the like woven from strands, or woven fabrics such as knitted fabrics, chopped strand mats, short fiber mats such as surfacing mats or diamond mats, swirl mats etc. A nonwoven fabric such as a long fiber mat is applied, and a general commercial product is applied.
【００１４】つぎに、第１発明において用いられる樹脂
強化用炭素繊維の処理について以下に説明する。Next, the treatment of the carbon fiber for resin reinforcement used in the first invention will be described below.
【００１５】樹脂強化用炭素繊維の処理剤の主成分とし
ての熱可塑性ポリエステル樹脂は、２種以上の二塩基酸
成分と一種以上のグリコール成分とを共重合させること
により得られるものである。ここで、二塩基酸成分と
は、例えばテレフタール酸、オルソフタール酸等の芳香
族ジカルボン酸、およびコハク酸、アジピン酸、セバシ
ン酸等の脂肪族ジカルボン酸などが挙げられる。また、
グリコール成分とは、例えばエチレングリコール、プロ
ピレングリコール、１，４−ブタンジオール等が挙げら
れる。なお、二塩基酸成分とグリコール成分は、上記で
例示したものに限定されるものではない。The thermoplastic polyester resin as a main component of the treating agent for the carbon fiber for resin reinforcement is obtained by copolymerizing two or more dibasic acid components and one or more glycol components. Here, the dibasic acid component includes, for example, aromatic dicarboxylic acids such as terephthalic acid and orthophthalic acid, and aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid. Also,
The glycol component includes, for example, ethylene glycol, propylene glycol, 1,4-butanediol and the like. In addition, the dibasic acid component and the glycol component are not limited to those exemplified above.
【００１６】第１発明の具体的な態様において、樹脂強
化用炭素繊維の処理剤の主成分として用いられる軟化点
が１５０℃以上の熱可塑性ポリエステル樹脂について
は、これを用いることによって樹脂との接着性の向上の
みならず、処理剤の熱安定性を向上することができる。
ここで、熱可塑性ポリエステル樹脂が１５０℃未満の軟
化点のものであるときは、強化熱可塑性樹脂成形体の爾
後の熱成形において、１８０℃以上の加熱温度を要する
場合に、熱安定性が低下して、処理剤の変色を起こした
り、樹脂との接着性をも低下せしめる結果となる。な
お、熱可塑性ポリエステル樹脂の軟化点は、強化しよう
とする樹脂成形体の母材樹脂の種類、熱成形温度等を考
慮して、前記二塩基酸成分とグリコール成分との組み合
わせ、組成比を適宜変化させて得るものとする。In a specific embodiment of the first invention, a thermoplastic polyester resin having a softening point of 150 ° C. or higher, which is used as a main component of a treatment agent for carbon fibers for resin reinforcement, is used to bond the resin with the resin. In addition to improving the properties, the thermal stability of the treating agent can be improved.
Here, when the thermoplastic polyester resin has a softening point of less than 150 ° C., in the subsequent thermoforming of the reinforced thermoplastic resin molded body, when a heating temperature of 180 ° C. or more is required, the thermal stability is reduced. As a result, the discoloration of the treatment agent is caused and the adhesion to the resin is also reduced. In addition, the softening point of the thermoplastic polyester resin, the type of the base resin of the resin molded body to be reinforced, considering the thermoforming temperature and the like, the combination of the dibasic acid component and the glycol component, the composition ratio appropriately. It shall be obtained by changing.
【００１７】なお、処理剤の成分として上記のほか、フ
ィルム形成剤、潤滑剤、帯電防止剤、熱安定剤等その他
の添加物を、本発明の目的を逸脱せずその効果を妨げな
い限り添加することができる。In addition to the above components, other additives such as a film forming agent, a lubricant, an antistatic agent and a heat stabilizer are added as components of the treating agent as long as they do not deviate from the object of the present invention and do not hinder the effects thereof. can do.
【００１８】ここで、樹脂強化用炭素繊維の処理方法
と、処理によって炭素繊維に付着する処理剤の付着量に
ついて述べる。まず処理方法は、前記処理剤をエマルジ
ョン状態または有機溶液状態とした処理液を、常法によ
り強化用炭素繊維に含浸させる方法、または前記処理剤
を溶融状態にして強化用炭素繊維にコーティングする方
法等を採用できるが、とくにこれらの方法に限定される
ものではない。また、処理剤の付着量については、強化
用炭素繊維に対して、処理剤の成分を１２〜３０重量％
とするが、１２重量％未満では母材としての熱可塑性樹
脂との十分な接着性が得られず、また３０重量％を超え
ると付着量の増加に見合うより以上の効果はもはや得ら
れないので、好ましくは１５〜２５重量％とする。ここ
でいう付着量は、繊維質量含有率（ＪＩＳ Ｋ７０７
５）による方法で測定したときの量を示すものとする。Here, a method of treating the carbon fiber for resin reinforcement and the amount of the treatment agent adhered to the carbon fiber by the treatment will be described. First, the processing method is a method of impregnating the reinforcing carbon fiber with a processing liquid in which the processing agent is in an emulsion state or an organic solution state, or a method of coating the reinforcing agent in a molten state with the processing agent. Etc. can be adopted, but it is not particularly limited to these methods. Regarding the amount of the treatment agent attached, the content of the treatment agent is 12 to 30% by weight based on the reinforcing carbon fiber.
However, if it is less than 12% by weight, sufficient adhesiveness to the thermoplastic resin as the base material cannot be obtained, and if it exceeds 30% by weight, no more effect than the increase in the amount of adhesion can be obtained. , Preferably 15 to 25% by weight. The adhesion amount referred to here is the fiber mass content rate (JIS K707).
The amount measured by the method according to 5) shall be indicated.
【００１９】つぎに、樹脂強化用炭素繊維を用いて強化
する本発明の第２の発明である熱可塑性樹脂成形体につ
いて説明すると、熱可塑性樹脂成形体の母材樹脂として
は、例えば塩化ビニル樹脂、熱可塑性ポリエステル樹
脂、ポリカーボネート樹脂などが挙げられ、その形態は
樹脂強化用炭素繊維と共に積層一体化される際に成層可
能な例えばシート状またはフィルム状のものが好適に適
用されるが、そのほかに母材樹脂を樹脂強化用炭素繊維
に溶融含浸させた、いわゆるプリプレグの形態とするこ
ともできる。Next, a thermoplastic resin molded article according to the second invention of the present invention, which is reinforced by using carbon fibers for resin reinforcement, will be described. As a base resin of the thermoplastic resin molded article, for example, vinyl chloride resin , Thermoplastic polyester resin, polycarbonate resin and the like, the form of which is preferably applied in the form of a sheet or film, for example, which can be layered when laminated and integrated with resin-reinforced carbon fibers. A so-called prepreg form in which the base resin is melt-impregnated into the carbon fiber for resin reinforcement can also be used.
【００２０】本発明の樹脂強化用炭素繊維と熱可塑性樹
脂成形体との積層方法については、通常最外層に熱可塑
性樹脂層が形成されるようにこれらを交互に積み重ね、
熱盤、熱ロール、オートクレーブ等を用いる方法により
加熱一体化する。また母材樹脂が前記プリプレグの形態
をとる場合にも、プリプレグ単独またはプリプレグと熱
可塑性樹脂成形体とを前記と同様にして積層し、加熱一
体化する。In the method of laminating the carbon fiber for resin reinforcement of the present invention and the thermoplastic resin molded article, these are usually stacked alternately so that the thermoplastic resin layer is formed on the outermost layer.
The heating is integrated by a method using a hot plate, a hot roll, an autoclave or the like. Also in the case where the base resin takes the form of the prepreg, the prepreg alone or the prepreg and the thermoplastic resin molded body are laminated and heat-integrated in the same manner as described above.
【００２１】ここで、本発明の強化熱可塑性樹脂成形体
全体に占める樹脂強化用炭素繊維の含有量について述べ
ると、樹脂強化用炭素繊維はその表面処理前の炭素繊維
に換算して、５〜８０重量％とする。含有量が５重量％
未満であると、曲げ強度、曲げ弾性率などの機械的強度
が得られず、８０重量％を超えると、相対的に母材樹脂
である熱可塑性樹脂の絶対量が不足する結果、熱可塑性
樹脂層にボイドが発生し、熱可塑性樹脂と炭素繊維との
接着性が著しく低下して、強化熱可塑性樹脂成形体とし
て実用に耐えないものとなる。したがって、樹脂強化用
炭素繊維の含有量は、５〜８０重量％とし、好ましくは
１０〜７０重量％とする。Here, the content of the carbon fiber for resin reinforcement in the entire reinforced thermoplastic resin molded article of the present invention will be described. The carbon fiber for resin reinforcement is 5 to 5% in terms of the carbon fiber before the surface treatment. 80% by weight. Content is 5% by weight
If the amount is less than the above, mechanical strength such as bending strength and flexural modulus cannot be obtained. If the amount exceeds 80% by weight, the absolute amount of the thermoplastic resin as the base material resin is relatively insufficient. Voids are generated in the layer, and the adhesiveness between the thermoplastic resin and the carbon fibers is significantly reduced, making it unsuitable for practical use as a reinforced thermoplastic resin molded article. Therefore, the content of the carbon fiber for resin reinforcement is 5 to 80 % by weight, preferably 10 to 70% by weight.
【００２２】このようにして得られる本発明の第２の発
明である強化熱可塑性樹脂成形体は、そのままの状態す
なわち多くの場合は板状体で実用に供されるほか、折曲
げ成形やマッチドモールド成形またはこれらに類似する
各種の熱成形法により所望の成形体に成形されたのち、
実用に供される。The thus obtained reinforced thermoplastic resin molded article according to the second invention of the present invention is practically used as it is, that is, in many cases, in a plate-like form. After being molded into the desired molded body by molding or various similar thermoforming methods,
Provided for practical use.
【００２３】[0023]
【発明の実施の形態】本発明の実施の形態は、熱可塑性
樹脂成形体を強化するための樹脂強化用炭素繊維とし
て、熱可塑性ポリエステル樹脂からなる処理剤で表面を
処理された成層可能な樹脂強化用炭素繊維であり、つい
で前記樹脂強化用炭素繊維と熱可塑性樹脂成形体とが加
熱加圧され積層一体化された強化熱可塑性樹脂成形体で
ある。BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention relates to a layerable resin whose surface has been treated with a treating agent comprising a thermoplastic polyester resin as a carbon fiber for reinforcing a thermoplastic resin molded article. The reinforcing carbon fiber is a reinforced thermoplastic resin molded body in which the resin-reinforced carbon fiber and the thermoplastic resin molded body are heated and pressed to be laminated and integrated.
【００２４】[0024]
実施例１〜６ 強化用炭素繊維の処理剤である熱可塑性ポリエステル樹
脂の炭素繊維に対する付着量を、表１に示すように変化
させるよう処理剤を用意した。ついで、質量２００ｇ／
ｍ2 、織り密度１２．５×１２．５本／２５mmの平織り
カーボンクロス（鐘紡（株）社製 品番ＣＦ３１０１）
を処理剤に浸漬し、１２０℃、３分間乾燥した。ここ
で、実施例１〜５の処理剤の主成分としては、テレフタ
ール酸（６５モル％）、イソフタール酸（１０モル％）
およびセバシン酸（２５モル％）の二塩基酸成分と、
１，４−ブタンジオールのグリコール成分とのモル比が
１：１からなる、軟化点１７０℃の熱可塑性ポリエステ
ル樹脂を、また実施例６ではテレフタール酸（６２モル
％）、イソフタール酸（２３モル％）およびアジピン酸
（１５モル％）の二塩基酸成分と、１，４−ブタンジオ
ール（９０モル％）、エチレングリコール（１０モル
％）のグリコール成分とのモル比が１：１からなる、軟
化点１５５℃の熱可塑性ポリエステル樹脂をそれぞれに
おいて用いた。Examples 1 to 6 Treatment agents were prepared so as to change the amount of the thermoplastic polyester resin, which is a treatment agent for reinforcing carbon fibers, attached to carbon fibers as shown in Table 1. Then, the mass 200g /
m 2 , plain weave carbon cloth with a weave density of 12.5 × 12.5 strands / 25 mm (manufactured by Kanebo Co., Ltd., product number CF3101)
Was immersed in a treating agent and dried at 120 ° C. for 3 minutes. Here, as the main components of the treating agents of Examples 1 to 5, terephthalic acid (65 mol%) and isophthalic acid (10 mol%)
And a dibasic acid component of sebacic acid (25 mol%);
A thermoplastic polyester resin having a softening point of 170 ° C. and a molar ratio of 1,4-butanediol to a glycol component of 1: 1 was used. In Example 6, terephthalic acid (62 mol%) and isophthalic acid (23 mol%) were used. ) And adipic acid (15 mol%), and a softening ratio of the glycol components of 1,4-butanediol (90 mol%) and ethylene glycol (10 mol%) of 1: 1. A thermoplastic polyester resin at a point of 155 ° C. was used in each case.
【００２５】ついで、上記各樹脂強化用炭素繊維と、表
１に示す種類の母材樹脂とを、母材樹脂が表裏両面に位
置するように交互に積層し、ホットプレスにより、母材
樹脂がポリ塩化ビニルの場合は１８０℃×１０分、１０
ｋｇｆ／ｃｍ2 の加熱加圧条件で、またポリカーボネー
ト樹脂の場合は２２０℃×１０分、１０ｋｇｆ／ｃｍ2
の加熱加圧条件で積層一体化し、厚さ３mmの板状の強化
熱可塑性樹脂成形体を得た。ここで、母材樹脂の形態は
いずれも押出成形法による厚さ０．１〜０．３mmのフィ
ルム状のものを用い、強化熱可塑性樹脂成形体としての
炭素繊維含有量が表１に示す含有量に見合うように、厚
さと枚数を適宜選択した。Next, the carbon fibers for resin reinforcement and the matrix resin of the type shown in Table 1 are alternately laminated so that the matrix resin is located on both front and back surfaces, and the matrix resin is hot-pressed. 180 ° C x 10 minutes for polyvinyl chloride, 10
kgf / cm 2 under heating and pressing conditions, and in the case of polycarbonate resin, 220 ° C. × 10 minutes, 10 kgf / cm 2
Under heat and pressure conditions to obtain a plate-shaped reinforced thermoplastic resin molded article having a thickness of 3 mm. Here, the base resin is in the form of a film having a thickness of 0.1 to 0.3 mm by extrusion molding, and the carbon fiber content of the reinforced thermoplastic resin molded product is as shown in Table 1. The thickness and the number of sheets were appropriately selected so as to match the amount.
【００２６】比較例１〜７ 比較例３において、強化用炭素繊維の処理剤の成分とし
て、テレフタール酸（４４モル％）、イソフタール酸
（３１モル％）およびアジピン酸（２５モル％）の二塩
基酸成分と、１，４−ブタンジオールのグリコール成分
とのモル比が１：１からなる、軟化点１３０℃の熱可塑
性ポリエステル樹脂を用いるほかは、実施例と同様にし
て、表１に示す各成分との組み合わせにおいて、炭素繊
維に対する各成分の付着量を変化させるべく、それぞれ
の処理剤を用意した。そして、それぞれの処理剤によ
り、実施例と同様の炭素繊維を用いてこれを表面処理し
た。なお、比較例２の処理剤成分である塩化ビニルラテ
ックスは、固形分４０重量％のものを、比較例５〜７の
処理剤成分であるポリエステル系ウレタン樹脂は、固形
成分２０重量％のものを用いたほかは、実施例と同様の
ものを用いた。Comparative Examples 1 to 7 In Comparative Example 3, dibasic terephthalic acid (44 mol%), isophthalic acid (31 mol%) and adipic acid (25 mol%) were used as the components of the treating agent for reinforcing carbon fibers. Except for using a thermoplastic polyester resin having a softening point of 130 ° C. and a molar ratio of an acid component to a glycol component of 1,4-butanediol of 1: 1, each of the components shown in Table 1 was used in the same manner as in Examples. In the combination with the components, respective treatment agents were prepared in order to change the amount of each component attached to the carbon fiber. Then, each of the treating agents was subjected to a surface treatment using the same carbon fiber as in the example. In addition, the vinyl chloride latex which is a treating agent component of Comparative Example 2 has a solid content of 40% by weight, and the polyester-based urethane resin which is a treating agent component of Comparative Examples 5 to 7 has a solid component of 20% by weight. Other than that used, the same one as in the example was used.
【００２７】ついで、得られた炭素繊維を用い、実施例
と同様にして、表１に示す母材樹脂と積層し、ホットプ
レスにより加熱加圧一体化して、厚さ３mmの板状成形体
を得た。Next, the obtained carbon fiber was laminated with the matrix resin shown in Table 1 in the same manner as in the Example, and was heated and pressed by a hot press to form a plate-shaped molded product having a thickness of 3 mm. Obtained.
【００２８】[0028]
【表１】 上記実施例と比較例によって得た各成形体について曲げ
強度、曲げ弾性率を測定し比較評価し、また熱成形時の
熱安定性を、処理剤の熱劣化による成形体の変色、発泡
について目視検査することにより評価した。その結果を
表１に併記する。なお、上記各測定と評価は、以下のと
おりとした。[Table 1] The flexural strength and flexural modulus of each molded article obtained in the above Examples and Comparative Examples were measured and comparatively evaluated, and the thermal stability at the time of thermoforming was visually examined for discoloration and foaming of the molded article due to thermal deterioration of the treating agent. It was evaluated by inspection. The results are also shown in Table 1. In addition, each said measurement and evaluation were as follows.
【００２９】［曲げ強度および曲げ弾性率］：ＪＩＳ
Ｋ７０５５に準拠して行い、各測定値の評価基準を、曲
げ強度については、１５００ｋｇｆ／ｃｍ2 を超えるも
のを良とし、曲げ弾性率については、１２００００ｋｇ
ｆ／ｃｍ2 を超えるものを良とした。[Bending strength and flexural modulus]: JIS
Performed in accordance with K7055 and evaluated the evaluation criteria of each measured value. The flexural strength was determined to be higher than 1500 kgf / cm 2 , and the flexural modulus was determined to be 120,000 kg.
Those exceeding f / cm 2 were regarded as good.
【００３０】［変色、発泡状態］：成形体の表面から、
樹脂強化用炭素繊維を透視し、変色が目立たず発泡のな
いものを○、変色が目立ち発泡したものを×とした。[Discoloration, foaming state]: From the surface of the molded body,
The carbon fibers for resin reinforcement were seen through, and those with no noticeable discoloration and no foaming were evaluated as ○, and those with noticeable discoloration and foamed were evaluated as ×.
【００３１】上記表１に示したとおり、本発明の実施例
による樹脂強化用炭素繊維を用いて得た強化熱可塑性樹
脂成形体は、いずれも曲げ強度、曲げ弾性率で示す機械
的強度の高いものであった。これに対し、比較例による
積層体は、比較例４、６および７の曲げ強度を除き、機
械的強度の低いものであった。また、本発明の実施例に
よる樹脂強化用炭素繊維は、これ自体熱による変色がな
く、これを用いて得たた強化熱可塑性樹脂成形体は、変
色や発泡が目立たなかった。これに対し、比較例は、比
較例１及び４を除き、いずれも樹脂強化用炭素繊維の変
色により積層体が変色するとともに発泡を生じ熱安定性
の劣るものであった。As shown in Table 1, the reinforced thermoplastic resin molded articles obtained by using the carbon fibers for resin reinforcement according to the examples of the present invention have high mechanical strengths represented by flexural strength and flexural modulus. Was something. On the other hand, the laminate according to the comparative example had low mechanical strength except for the flexural strengths of comparative examples 4, 6, and 7. Further, the carbon fiber for resin reinforcement according to the example of the present invention itself did not undergo discoloration due to heat, and in the reinforced thermoplastic resin molded article obtained by using the same, discoloration and foaming were not conspicuous. On the other hand, in Comparative Examples, except for Comparative Examples 1 and 4, the laminate was discolored due to the discoloration of the carbon fiber for resin reinforcement and foaming occurred, resulting in poor thermal stability.
【００３２】[0032]
【発明の効果】以上のように、本発明による樹脂強化用
炭素繊維は、表面処理に用いられる処理剤の成分とし
て、熱可塑性ポリエステル樹脂を主成分とするものとし
たから、自体の熱安定性が高く、しかもこれを用いた強
化熱可塑性樹脂成形体の母材樹脂としての熱可塑性樹脂
との接着性が高く、機械的強度が一段と高い強化熱可塑
性樹脂成形体を得ることができる。As described above, the carbon fiber for resin reinforcement according to the present invention is mainly composed of a thermoplastic polyester resin as a component of the treating agent used for the surface treatment. Thus, it is possible to obtain a reinforced thermoplastic resin molded article having high adhesiveness to a thermoplastic resin as a base resin of the reinforced thermoplastic resin molded article using the same, and having further higher mechanical strength.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ // Ｂ２９Ｋ 67:00 105:08 307:04 (56)参考文献 特開 昭62−33861（ＪＰ，Ａ) 特開 昭58−149383（ＪＰ，Ａ) 特開 平６−192436（ＪＰ，Ａ) 特開 平５−311069（ＪＰ，Ａ) 特開 平５−263363（ＪＰ，Ａ) 特開 平５−106163（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 5/06 ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 7 Identification symbol FI // B29K 67:00 105: 08 307: 04 (56) References JP-A-62-33861 (JP, A) JP-A-58 JP-149383 (JP, A) JP-A-6-192436 (JP, A) JP-A-5-311069 (JP, A) JP-A-5-263363 (JP, A) JP-A-5-106163 (JP, A) (58) Fields surveyed (Int. Cl. 7 , DB name) C08J 5/06
Claims (6)
で表面処理されたことを特徴とする樹脂強化用炭素繊
維。1. A carbon fiber for resin reinforcement, which has been surface-treated with a treatment agent comprising a thermoplastic polyester resin.
リエステル樹脂からなる請求項１記載の樹脂強化用炭素
繊維。2. The carbon fiber for reinforcing a resin according to claim 1, wherein the treating agent comprises a thermoplastic polyester resin having a softening point of 150 ° C. or higher.
１２〜３０重量％である請求項１または２記載の樹脂強
化用炭素繊維。3. The carbon fiber for resin reinforcement according to claim 1, wherein the amount of the treatment agent attached is 12 to 30% by weight based on the carbon fiber for reinforcement.
脂強化用炭素繊維により強化されてなる強化熱可塑性樹
脂成形体。4. A reinforced thermoplastic resin molded article reinforced by the carbon fiber for resin reinforcement according to any one of claims 1 to 3.
脂強化用炭素繊維により強化されてなる熱可塑性樹脂成
形体がポリカーボネ−ト樹脂成形体である強化熱可塑性
樹脂成形体。5. A reinforced thermoplastic resin molded article, wherein the thermoplastic resin molded article reinforced by the carbon fiber for resin reinforcement according to claim 1 is a polycarbonate resin molded article.
とが交互に積層されてなる請求項４または５記載の強化
熱可塑性樹脂成形体。6. The reinforced thermoplastic resin molded article according to claim 4, wherein the carbon fibers for resin reinforcement and the thermoplastic resin molded article are alternately laminated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8012737A JP3048911B2 (en) | 1996-01-29 | 1996-01-29 | Carbon fiber for resin reinforcement and reinforced thermoplastic resin molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8012737A JP3048911B2 (en) | 1996-01-29 | 1996-01-29 | Carbon fiber for resin reinforcement and reinforced thermoplastic resin molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09208713A JPH09208713A (en) | 1997-08-12 |
| JP3048911B2 true JP3048911B2 (en) | 2000-06-05 |
Family
ID=11813752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8012737A Expired - Lifetime JP3048911B2 (en) | 1996-01-29 | 1996-01-29 | Carbon fiber for resin reinforcement and reinforced thermoplastic resin molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3048911B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6853555B2 (en) * | 2018-06-05 | 2021-03-31 | エステック株式会社 | Method of manufacturing a laminate |
-
1996
- 1996-01-29 JP JP8012737A patent/JP3048911B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09208713A (en) | 1997-08-12 |
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