JPH0343216Y2 - - Google Patents
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- Publication number
- JPH0343216Y2 JPH0343216Y2 JP230585U JP230585U JPH0343216Y2 JP H0343216 Y2 JPH0343216 Y2 JP H0343216Y2 JP 230585 U JP230585 U JP 230585U JP 230585 U JP230585 U JP 230585U JP H0343216 Y2 JPH0343216 Y2 JP H0343216Y2
- Authority
- JP
- Japan
- Prior art keywords
- strength
- fiber
- fibers
- acrylic
- present
- 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
Links
- 229920002972 Acrylic fiber Polymers 0.000 claims description 25
- 239000012779 reinforcing material Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- 229920002430 Fibre-reinforced plastic Polymers 0.000 claims description 4
- 239000011151 fibre-reinforced plastic Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 17
- 238000010526 radical polymerization reaction Methods 0.000 description 13
- 239000000835 fiber Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 230000015271 coagulation Effects 0.000 description 9
- 238000005345 coagulation Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000001891 gel spinning Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004412 Bulk moulding compound Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 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
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Description
〔考案の技術分野〕
本考案は、高強力アクリル系繊維を補強材とす
る繊維強化プラスチツクスに関する。 〔従来技
術〕
繊維強化プラスチツクス（以下、FRPと略記
する）における補強材としては、補強効果が大き
いガラス繊維が主流であり、近年では耐熱性、高
弾性率、あるいは高強度繊維として炭素繊維や芳
香族ポリアミド等が使用されつつある。
また、耐衝撃性が要求されるFRPでは補強材
として合成繊維が使用されており、ナイロン、ポ
リエステル、ビニロン、ポリプロピレン等が単独
で、またはガラス繊維と併用で使用されている。
しかしながら補強材としてのアクリル繊維は、
工業的に高強力、高弾性率の糸が従来得られてお
らず、従来の湿式紡糸による糸は耐侯性が良好で
あるにもかかわらず、強力、弾性率が低いために
FRP用補強材としては殆ど使用されていなかつ
た。
一方、改良された性質を有する高強力アクリル
系繊維またはその製造方法については、従来から
多くの提案がなされており、例えば(イ)特開昭51−
75119号公報、(ロ)特開昭57−51810号公報や(ハ)特開
昭57−161117号公報等を挙げることができる。
しかしながら、(イ)では得られる繊維が失透して
内部に多数のボイドを発生させためFRPとして
必ずしも高強度化をもたらすものではなく、ま
た、(ロ)，(ハ)で得られる繊維は、弾性率は高い値を
示すものの、引張強度は9.3g／ｄにすぎず、FRP
用補強材として使用されるには至らなかつた。
そこで本考案者らは、改良された性質を有する
アクリル系繊維を補強材とするFRPについて鋭
意検討を行い、本考案を完成した。
〔考案の目的〕
本考案は、高強力アクリル系繊維を補強材とす
る、高強力、高弾性率で耐衝撃性、耐水性等に優
れたFRPを提供することにある。
〔考案の構成〕
上記目的を達成する本考案は、極限粘度が少な
くとも2.5であるアクリルニトリル系重合体を乾
湿式紡糸することによつて得られた、引張強度が
10g／ｄ以上、結節強度が2.2g／ｄ以上のアクリ
ル系繊維を補強材とし、熱硬化性樹脂をマトリツ
クスとするものである。
以下、本考案を詳細に説明する。
本考案に係る繊維強化プラスチツクスの特徴の
一つは、引張強度が10g／ｄ以上、結節強度が
2.2g／ｄ以上であるアクリル系繊維を補強材とす
ることである。
また、本考案の他の特徴は、上記アクリル系繊
維が、極限粘度が少なくとも2.5のアクリルニト
リル（以下、ANと略記する）系重合体を乾湿式
紡糸することによつて得られたものである。
まず、極限粘度が少なくとも2.5のAN系重合体
は、公知の懸濁方法、乳化重合および溶液重合な
どによつて製造され、好ましくは溶液重合法が採
用され、得られる重合体の分子量は通常15〜30万
の範囲が紡糸の安定性から望ましい。
溶媒としては、例えばDMSO、DMA、DMF、
ロダンソーダ、塩化亜鉛水溶液、硝酸等がある
が、DMSO、DMA、DMFが好ましく、DMSO
が特に好ましい。
また、重合体濃度は、極限粘度や溶媒の種類に
もよるが、45℃における溶液粘度が少なくとも
2000ポイズ、好ましくは3000〜10000ポイズの範
囲内で、高濃度、好ましくは重合体濃度約５〜15
％とするのが良い。
ここで、本考案における極限粘度は、次のよう
にして測定される値である。
即ち、約75mgの乾燥したサンプル重合体をフラ
スコに入れ、0.1Nチオシアン酸ソーダを含むジ
メチルホルムアミド25mlを加えて完全に溶解す
る。
得られた溶液をオストワルド粘度計を用いて20
℃で比粘度を測定し、次式に従つて極限粘度を算
出する。
極限粘度＝√１＋1.32×（比粘度）−１／0.198
次に、このような極限粘度を有する重合体の紡
糸原液を乾湿式紡糸する。
乾湿式紡糸法とは、紡糸原液を直接凝固液体浴
に吐出しないで、一旦、空気等の不活性雰囲気の
微小空間に吐出し、ついでこの吐出糸条を凝固浴
に導いて糸条を形成させる紡糸法である。
即ち、凝固浴面上に設置された紡糸口金を通し
て吐出させ、吐出糸条は一定の不活性雰囲気中、
例えば空気中を走行した後、凝固浴に導かれる。
ここで吐出糸条が不活性雰囲気中を走行する距
離（口金面から凝固浴面までの距離）は、紡糸原
液の溶媒、粘度等により異なるが、通常では１〜
200mm、好ましくは３〜20mmに設定される。
凝固浴としては、湿式紡糸法と同様に、AN重
合体の溶媒と共通の溶剤水溶液が用いられ、ここ
で凝固した糸条は、熱水中および／または蒸熱下
で洗浄、脱溶剤されながら２〜10倍に延伸され
る。
更に乾燥緻密化を行つた後、乾熱で少なくとも
1.1倍、好ましくは1.5倍の延伸を行い、全延伸倍
率を10倍、好ましくは12倍以上とする。
乾熱延伸温度は、150〜270℃、好ましくは200
〜270℃である。
かくして得られた本考案におけるアクリル系繊
維は、引張強度が10g／ｄ以上であり、結節強度
が2.2g／ｄ以上である。
かかるアクリル系繊維は、従来のアクリル繊維
に比較して、アクリル繊維が有する特性を有して
いて高強力、高結節強力であり、かつ例えば
200g／ｄの弾性率を有していて高弾性率である。
また、耐摩耗性、耐疲労性にも優れており、表
面平滑性が良好なので、FRP用補強材とし使用
したときに、耐衝撃性を増大せしめる利点があ
る。
かつ、ポリエステルやナイロン等の産業用繊維
に比べて、耐候性、耐水性、湿潤安定性が良好で
あり、耐薬品（酸・アルカリ）性に優れ、軽量で
ある等のアクリル繊維一般の特性を有している。
本考案においては、かかる高強力アクリル系繊
維の織物、ロービングクロス、短繊維不織布、ロ
ービング、チヨツプストランド等がFRPの補強
材として使用される。
第１図に本考案ににおける高強力アクリル系繊
維のチヨツプドストランド１とガラス繊維２を併
用し、熱硬化性樹脂３とからなるバルクモウルデ
イングコンパウンド成形板４を示し、まか第２図
には本考案における高強力アクリル系繊維のロー
ビングクロス５と熱硬化性樹脂３とからなる積層
板６を示す。
なお、本考案におけるマトリツクス樹脂は、特
に限定されるものではなく、通常のFRP製造に
おけるように、熱硬化性樹脂、例えば不飽和ポリ
エステル樹脂、エポキシ樹脂、フエノール樹脂等
が使用される。
〔考案の効果〕
以上述べたように本考案によるFRPは、極限
粘度が少なくとも2.5であるアクリルニトリル系
重合体を乾湿式紡糸することによつて得られた、
引張強度が10g／ｄ以上、結節強度が2.2g／ｄ以
上であるアクリル系繊維を補強材とし、熱硬化性
樹脂をマトリツクスとするものである。
従つて本考案のFRPは、補強材として高強力
のアクリル系繊維を使用するので、従来のAN系
繊維補強材では達成されなかつた高強力、高弾性
率を保持することができる。
かつ、高強力アクリル系繊維が乾湿式紡糸され
表面平滑性であるので、耐衝撃性に優れ、また耐
水性、電気絶縁性にも優れている。
かかる特性を有する本考案のFRPは、電気部
品、住宅関連部品、保護具、機械部品用のバルク
モウルデイングコンパウンド成型品や、ヘルメツ
ト、保護具、緩衝材、自動車部品用の積層板とし
て広く使用することできる。
以下、本考案を実施例により具体的に説明す
る。
〔実施例〕
実施例１〜３、比較例１〜２
アクリルニトリル100％をジメチルスルホキシ
ド中で溶液重合させて、各種極限粘度〔η〕のア
クリル系重合体を製造した。
これらの重合体をDMSOに溶解し、45℃の溶
液粘度が約3000ポイズになるように重合体濃度を
調整して紡糸原液を作成した後、湿式および乾湿
式紡糸を行つた。
凝固浴は20℃の55％DMSO水溶液を用いた。
乾湿式紡糸の場合、口金と凝固浴液面の空間部
分の長さは５mm、凝固浴液面から集束ガイドまで
の距離は400mmとした。
次に未延伸糸を熱水中で５倍延伸後、水洗し、
油剤を付与した後に130℃で乾燥、緻密化を行い、
180〜200℃の乾熱チユーブ中で最高延伸倍率の90
％で延伸した。
得られたアクリル系繊維Ａ〜Ｅの単繊維は、約
2.0デニールｄであり、その他の性質を下記第１
表に示す。
[Technical Field of the Invention] The present invention relates to fiber-reinforced plastics using high-strength acrylic fibers as a reinforcing material. [Prior art] Glass fiber, which has a large reinforcing effect, is the mainstream as a reinforcing material for fiber-reinforced plastics (hereinafter abbreviated as FRP).In recent years, carbon fiber and other materials have been used as heat resistant, high modulus, or high strength fibers. Aromatic polyamides and the like are being used. In addition, synthetic fibers are used as reinforcing materials in FRP, which requires impact resistance, and nylon, polyester, vinylon, polypropylene, etc. are used alone or in combination with glass fiber. However, acrylic fibers as reinforcing materials
Yarns with high strength and high elastic modulus have not been obtained industrially, and although yarns produced by conventional wet spinning have good weather resistance, they have low strength and low elastic modulus.
It was hardly used as a reinforcing material for FRP. On the other hand, many proposals have been made regarding high-strength acrylic fibers with improved properties and methods for producing the same.
75119, (b) JP-A-57-51810, and (c) JP-A-57-161117. However, since the fibers obtained in (a) devitrify and generate many voids inside, they do not necessarily provide high strength as FRP, and the fibers obtained in (b) and (c) Although the elastic modulus shows a high value, the tensile strength is only 9.3 g/d, and FRP
It was not possible to use it as a reinforcing material. Therefore, the present inventors conducted extensive research on FRP that uses acrylic fibers with improved properties as a reinforcing material, and completed the present invention. [Purpose of the invention] The purpose of the invention is to provide an FRP that uses high-strength acrylic fiber as a reinforcing material and has high strength, high modulus of elasticity, and excellent impact resistance, water resistance, etc. [Structure of the invention] The present invention achieves the above object by dry-wet spinning an acrylonitrile polymer having an intrinsic viscosity of at least 2.5, and which has a high tensile strength.
The reinforcing material is acrylic fiber with a knot strength of 10 g/d or more and a knot strength of 2.2 g/d or more, and a thermosetting resin is used as the matrix. The present invention will be explained in detail below. One of the characteristics of the fiber-reinforced plastics according to the present invention is that the tensile strength is 10 g/d or more and the knot strength is
The purpose is to use acrylic fibers with a density of 2.2 g/d or more as the reinforcing material. Another feature of the present invention is that the acrylic fiber is obtained by dry-wet spinning an acrylonitrile (hereinafter abbreviated as AN) polymer having an intrinsic viscosity of at least 2.5. . First, an AN-based polymer having an intrinsic viscosity of at least 2.5 is produced by a known suspension method, emulsion polymerization, solution polymerization, etc., preferably a solution polymerization method is adopted, and the molecular weight of the obtained polymer is usually 15. A range of ~300,000 is desirable from the viewpoint of spinning stability. Examples of solvents include DMSO, DMA, DMF,
Rodan soda, zinc chloride aqueous solution, nitric acid, etc. are available, but DMSO, DMA, DMF are preferable, and DMSO
is particularly preferred. In addition, the polymer concentration depends on the intrinsic viscosity and the type of solvent, but the solution viscosity at 45℃ is at least
2000 poise, preferably within the range of 3000 to 10000 poise, with a high concentration, preferably a polymer concentration of about 5 to 15
It is better to use %. Here, the intrinsic viscosity in the present invention is a value measured as follows. That is, about 75 mg of dried sample polymer is placed in a flask, and 25 ml of dimethylformamide containing 0.1N sodium thiocyanate is added to completely dissolve it. The resulting solution was measured using an Ostwald viscometer for 20
Measure the specific viscosity at °C and calculate the intrinsic viscosity according to the following formula. Intrinsic viscosity=√1+1.32×(specific viscosity)−1/0.198 Next, the spinning stock solution of the polymer having such an intrinsic viscosity is subjected to dry-wet spinning. In the dry-wet spinning method, the spinning stock solution is not directly discharged into a coagulation liquid bath, but is first discharged into a microscopic space in an inert atmosphere such as air, and then this discharged thread is introduced into a coagulation bath to form a thread. This is a spinning method. That is, the yarn is discharged through a spinneret placed above the surface of the coagulation bath, and the discharged yarn is placed in a constant inert atmosphere.
For example, after traveling through air, it is introduced into a coagulation bath. Here, the distance that the discharged yarn travels in the inert atmosphere (distance from the spinneret surface to the coagulation bath surface) varies depending on the solvent and viscosity of the spinning dope, but is usually 1 to 1.
It is set to 200 mm, preferably 3 to 20 mm. As in the wet spinning method, an aqueous solution of the same solvent as that of the AN polymer is used as the coagulation bath, and the coagulated thread is washed and desolventized in hot water and/or steam, and Stretched ~10 times. After further drying and densification, at least
Stretching is performed by 1.1 times, preferably 1.5 times, and the total stretching ratio is 10 times, preferably 12 times or more. Dry heat stretching temperature is 150~270℃, preferably 200℃
~270℃. The thus obtained acrylic fiber of the present invention has a tensile strength of 10 g/d or more and a knot strength of 2.2 g/d or more. Compared to conventional acrylic fibers, such acrylic fibers have the characteristics of acrylic fibers, such as high strength and high knot strength, and, for example,
It has a high elastic modulus of 200 g/d. It also has excellent wear resistance and fatigue resistance, and has good surface smoothness, so it has the advantage of increasing impact resistance when used as a reinforcing material for FRP. In addition, compared to industrial fibers such as polyester and nylon, it has the characteristics of general acrylic fibers, such as better weather resistance, water resistance, and wet stability, excellent chemical resistance (acid and alkali), and light weight. have. In the present invention, such high-strength acrylic fiber woven fabrics, roving cloths, short fiber nonwoven fabrics, rovings, tip strands, etc. are used as reinforcing materials for FRP. FIG. 1 shows a bulk molding compound molded plate 4 made of a thermosetting resin 3 in combination with chopped strands 1 of high-strength acrylic fibers and glass fibers 2 according to the present invention. The figure shows a laminate 6 made of a roving cloth 5 made of high-strength acrylic fibers and a thermosetting resin 3 according to the present invention. Note that the matrix resin in the present invention is not particularly limited, and thermosetting resins such as unsaturated polyester resins, epoxy resins, phenol resins, etc. are used as in normal FRP manufacturing. [Effects of the invention] As described above, the FRP according to the invention is obtained by dry-wet spinning an acrylonitrile polymer having an intrinsic viscosity of at least 2.5.
The reinforcing material is acrylic fiber with a tensile strength of 10 g/d or more and a knot strength of 2.2 g/d or more, and a thermosetting resin is used as the matrix. Therefore, since the FRP of the present invention uses high-strength acrylic fibers as a reinforcing material, it can maintain high strength and high elastic modulus, which were not achieved with conventional AN-based fiber reinforcing materials. In addition, since the high-strength acrylic fibers are dry-wet-spun and have a smooth surface, they have excellent impact resistance, water resistance, and electrical insulation. The FRP of the present invention, which has such characteristics, can be widely used as bulk molding compounds for electrical parts, housing-related parts, protective equipment, and mechanical parts, as well as laminates for helmets, protective equipment, cushioning materials, and automobile parts. I can do that. Hereinafter, the present invention will be specifically explained with reference to Examples. [Example] Examples 1 to 3, Comparative Examples 1 to 2 Acrylic polymers having various intrinsic viscosities [η] were produced by solution polymerizing 100% acrylonitrile in dimethyl sulfoxide. These polymers were dissolved in DMSO and the polymer concentration was adjusted so that the solution viscosity at 45° C. was approximately 3000 poise to prepare a spinning stock solution, and then wet and dry-wet spinning was performed. A 55% DMSO aqueous solution at 20°C was used as the coagulation bath. In the case of dry-wet spinning, the length of the space between the die and the coagulation bath surface was 5 mm, and the distance from the coagulation bath surface to the focusing guide was 400 mm. Next, the undrawn yarn was stretched 5 times in hot water, washed with water,
After applying the oil agent, dry and densify at 130℃,
Maximum stretching ratio of 90 in a dry heat tube at 180-200℃
%. The obtained single fibers of acrylic fibers A to E are approximately
2.0 denier d, and the other properties are as follows.
Shown in the table.
【表】
次いで上記第１表の繊維Ａ〜Ｅを繊維長６mmに
切断して補強用繊維とした。
一方、不飽和ポリエステル樹脂30部、CaCO3
57部、ベンゾイルペーオキシド0.3部、MgOO.3
部、ステアリン酸亜鉛１部からなる樹脂混合物を
ニーダーに入れ、次いで補強用繊維１部を加えて
15分間、混練した。
続いて、繊維長６mmのガラス繊維（日東紡績、
CB6E）10部を加えて更に５分間混練してプリミ
ツクスを製造した。
このプリミツクスを120℃、100Kg／cm2、３分間
圧縮成形して厚さ約３mmの成形板を得た。
得られた成形板をJIS−Ｋ−6911に準じ、曲げ
強さ、および衝撃強さを測定した。
下記第２表に測定結果を示す。
この表から、本考案の乾湿式紡糸された高重合
体のアクリル系繊維からなる成形板は、曲げ強さ
が高く、耐衝撃性に優れていることが明らかであ
る。[Table] Next, the fibers A to E shown in Table 1 were cut into fiber lengths of 6 mm to obtain reinforcing fibers. Meanwhile, 30 parts of unsaturated polyester resin, CaCO 3
57 parts, benzoyl peroxide 0.3 parts, MgOO.3
1 part of zinc stearate was placed in a kneader, and then 1 part of reinforcing fiber was added.
Kneaded for 15 minutes. Next, glass fiber with a fiber length of 6 mm (Nitto Boseki,
CB6E) was added and kneaded for an additional 5 minutes to produce Primics. This Primics was compression molded at 120° C., 100 kg/cm 2 for 3 minutes to obtain a molded plate with a thickness of about 3 mm. The bending strength and impact strength of the obtained molded plate were measured according to JIS-K-6911. The measurement results are shown in Table 2 below. From this table, it is clear that the molded plate made of the dry-wet spun high polymer acrylic fiber of the present invention has high bending strength and excellent impact resistance.
【表】
実施例４〜６、比較例３〜４
前記第１表に示した繊維Ａ〜Ｅからなる繊度
1000デニールＤのフイラメントを５本合糸してロ
ービングとし、ついで織密度縦36本／インチ、平
織で製織し、重量460g／m2の補強用ロービング
クロスを製造した。
次に、不飽和ポリエステル樹脂100部、パーブ
チルＺ（日本油脂製硬化剤）１部を配合した樹脂
を補強用ロービングクロスに含浸し、室温で24時
間熟成した。
この樹脂を含浸したロービングクロスを金型に
10枚積層した後、145℃で５分間加熱プレスして
厚さ約５mm、繊維含有量75重量％の積層板を得
た。
得られた積層板をJIS−Ｋ−6911に準じて曲げ
強さを、ASTM−Ｄ−256に準じて衝撃強さを測
定した。
第３表に測定結果を示す。
この第３表から明らかなように、本考案の乾湿
式紡糸された高重合体のアクリル系繊維からなる
積層板は、曲げ強さが高く、耐衝撃性に優れてい
る。[Table] Examples 4 to 6, Comparative Examples 3 to 4 Fineness of fibers A to E shown in Table 1 above
Five filaments of 1000 denier D were spun together to form a roving, and then woven in a plain weave with a weave density of 36 filaments/inch lengthwise to produce a reinforcing roving cloth weighing 460 g/m 2 . Next, a reinforcing roving cloth was impregnated with a resin containing 100 parts of unsaturated polyester resin and 1 part of Perbutyl Z (hardening agent manufactured by NOF Corporation), and aged at room temperature for 24 hours. The roving cloth impregnated with this resin is used as a mold.
After laminating 10 sheets, they were heated and pressed at 145° C. for 5 minutes to obtain a laminate with a thickness of about 5 mm and a fiber content of 75% by weight. The bending strength of the obtained laminate was measured according to JIS-K-6911, and the impact strength was measured according to ASTM-D-256. Table 3 shows the measurement results. As is clear from Table 3, the laminate made of the dry-wet spun high polymer acrylic fiber of the present invention has high bending strength and excellent impact resistance.
第１図は本考案にかかるバルクモウルデイング
成形板の斜視図、第２図は積層板の斜視図であ
る。
１……高強力アクリル系繊維のチヨツプドスト
ランド、２……ガラス繊維、３……熱硬化性樹
脂、４……バルクモウルデイングコンパウンド、
５……高強力アクリル系繊維のロービングクロ
ス、６……積層板。
FIG. 1 is a perspective view of a bulk molding plate according to the present invention, and FIG. 2 is a perspective view of a laminate. 1... Chopped strand of high-strength acrylic fiber, 2... Glass fiber, 3... Thermosetting resin, 4... Bulk molding compound,
5... Roving cloth made of high-strength acrylic fiber, 6... Laminated board.
Claims (1)
リル系重合体を乾湿式紡糸することによつて得ら
れた、引張強度が10g／ｄ以上、結節強度が
2.2g／ｄ以上であるアクリル系繊維を補強材と
し、熱硬化性樹脂をマトリツクスとする繊維強化
プラスチツクス。 A material with a tensile strength of 10 g/d or more and a knot strength of
Fiber-reinforced plastics with acrylic fibers of 2.2 g/d or more as reinforcing materials and thermosetting resin as a matrix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP230585U JPH0343216Y2 (en) | 1985-01-14 | 1985-01-14 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP230585U JPH0343216Y2 (en) | 1985-01-14 | 1985-01-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61120731U JPS61120731U (en) | 1986-07-30 |
| JPH0343216Y2 true JPH0343216Y2 (en) | 1991-09-10 |
Family
ID=30475855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP230585U Expired JPH0343216Y2 (en) | 1985-01-14 | 1985-01-14 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0343216Y2 (en) |
-
1985
- 1985-01-14 JP JP230585U patent/JPH0343216Y2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61120731U (en) | 1986-07-30 |
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