JPH01214427A - Preparation of fiber-reinforced resin continuum - Google Patents
Preparation of fiber-reinforced resin continuumInfo
- Publication number
- JPH01214427A JPH01214427A JP63039164A JP3916488A JPH01214427A JP H01214427 A JPH01214427 A JP H01214427A JP 63039164 A JP63039164 A JP 63039164A JP 3916488 A JP3916488 A JP 3916488A JP H01214427 A JPH01214427 A JP H01214427A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- metallic
- thermosetting resin
- liquid thermosetting
- resin
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- 239000011347 resin Substances 0.000 title claims abstract description 33
- 238000000465 moulding Methods 0.000 claims abstract description 22
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000011342 resin composition Substances 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 18
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 abstract description 4
- 229920001567 vinyl ester resin Polymers 0.000 abstract description 4
- 239000003365 glass fiber Substances 0.000 abstract description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract description 3
- 239000000347 magnesium hydroxide Substances 0.000 abstract description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract description 3
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 2
- 239000004917 carbon fiber Substances 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 abstract description 2
- 239000001095 magnesium carbonate Substances 0.000 abstract description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 239000011787 zinc oxide Substances 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- -1 etc. Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000805 composite resin Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-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
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- XTVMZZBLCLWBPM-UHFFFAOYSA-N tert-butylcyclohexane Chemical compound CC(C)(C)C1CCCCC1 XTVMZZBLCLWBPM-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 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
Landscapes
- Reinforced Plastic Materials (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
繊維強化樹脂複合体は高強度・高弾性であり軽量である
ため、金属材料に変わって多用途に使用されている。本
発明はこれら繊維強化樹脂複合体のなかでも長手方向に
連続した線状繊維強化樹脂複合体に関する。[Detailed Description of the Invention] (Industrial Application Field) Fiber-reinforced resin composites have high strength, high elasticity, and are lightweight, so they are used for a variety of purposes instead of metal materials. Among these fiber-reinforced resin composites, the present invention relates to linear fiber-reinforced resin composites that are continuous in the longitudinal direction.
（従来の技Ｗ＞
長手方向に連続した繊維に熱硬化性の液状樹脂を含浸さ
せ、しかる後成形金型内部に連続的に導入し加熱硬化さ
せる成形法は一般にプルトルージョン成形法と呼ばれ、
長手方向に同一断面を有する繊維強化樹脂を連続的に成
形する場合に有効な方法である。しかし、プルトルージ
ョン成形法により連続成形を行なうと、しだいに成形物
の表面が傷ついたり肌荒れをおこすことがしばしばあり
、良好な成形物が連続的に安定して得られなかった。(Conventional Technique W> A molding method in which longitudinally continuous fibers are impregnated with a thermosetting liquid resin, and then continuously introduced into a mold and cured by heating is generally called a pultrusion molding method.
This is an effective method when continuously molding fiber-reinforced resin having the same cross section in the longitudinal direction. However, when continuous molding is carried out by the pultrusion molding method, the surface of the molded product is often damaged or roughened, and good molded products cannot be obtained continuously and stably.
この成形物表面の傷や肌荒れが生じる原因は成形金型内
部への樹脂付着であり、この成形金型内部への樹脂付着
物は、プルトルージョン成形とともに増大しながら硬化
し、この硬化物の塊りがその後の成形物表面を傷つけ肌
荒れを起こすのであり、さらには成形金型内部に付着し
た樹脂硬化物の塊りにより引き抜き抵抗が増大し、つい
にはプルトルージョン成形自体をも困難にしていた。こ
れに対し特開閉５９−１４５１１７号公報では樹脂含浸
繊維体上に荒目の繊維層を例えばガラス織テープの縦ぞ
えによって形成させ、しかる後成形金型内部で加熱硬化
させる方法が開示されている。ここで荒目の繊維層は上
記の硬化物の塊りを除く働きをしている。The cause of scratches and rough skin on the surface of the molded product is resin adhesion to the inside of the mold, and as the resin adheres to the inside of the mold, it increases and hardens with pultrusion molding, and this hardened material becomes a lump. This damages the surface of the molded product and causes rough skin, and furthermore, the clumping of the cured resin material adhering to the inside of the mold increases the pull-out resistance, ultimately making pultrusion molding itself difficult. On the other hand, JP-A No. 59-145117 discloses a method in which a coarse fiber layer is formed on a resin-impregnated fiber body by, for example, vertically rolling a glass woven tape, and then heated and cured inside a molding die. There is. Here, the coarse fiber layer functions to remove the lumps of the cured material.
（本発明が解決しようとする問題点）
しかし、前記公知の方法ではテープ縦そえ装置が必要に
なり、また工程が複雑になってしまう。かかる事情に鑑
がみ本発明者らは、熱硬化性樹脂自体の改質によって、
従来装置をそのまま用いて製造する成形物の肌荒れの解
消を検討し本発明に至った。(Problems to be Solved by the Present Invention) However, the above-mentioned known method requires a tape vertically holding device and also complicates the process. In view of these circumstances, the present inventors have achieved the following by modifying the thermosetting resin itself.
The present invention was developed after studying ways to eliminate rough skin of molded products manufactured using conventional equipment.
（問題を解決する為の手段）
すなわち本発明は、液状熱硬化性樹脂１００重量部に対
し、金属酸化物、金属水酸化物及び金属炭酸塩からなる
群から選ばれた少なくとも一種以上を成分とする添加剤
を５以上５０重量部以下混合して成る液状熱硬化性樹脂
組成物を長手方向に連続した繊維に含浸せしめ、しかる
後成形金型内部に連続的に導入し加熱硬化と同時に成形
せしめる方法を提供するものである。(Means for Solving the Problems) That is, the present invention includes at least one selected from the group consisting of metal oxides, metal hydroxides, and metal carbonates, based on 100 parts by weight of a liquid thermosetting resin. A liquid thermosetting resin composition prepared by mixing 5 to 50 parts by weight of additives is impregnated into continuous fibers in the longitudinal direction, and then continuously introduced into a molding die and molded at the same time as heating and curing. The present invention provides a method.
本発明で用いられる長手方向に連続した繊維とはガラス
繊維、カーボン繊維、アラミド繊維などでありこれらは
商業的に容易に入手できる。好ましくは強度の高い点１
価格の安価な事からガラス繊維が選ばれる。The longitudinally continuous fibers used in the present invention include glass fibers, carbon fibers, aramid fibers, etc., and these are easily available commercially. Preferably high strength point 1
Glass fiber is chosen because it is inexpensive.
また本発明で用いられる金属酸化物、金属水酸化物及び
金属炭酸塩はプルトルージョン成形時において樹脂組成
物の成形金型内部への付着を防止し成形物の表面状態を
良好に保つ役割をする。その粒度分布が１μ未満である
と成形金型内部への樹脂の付着が起こり成形物の肌を荒
らすようになる。またその粒度分布が４０μを越えると
成形物の機械的特性の低下が著しくなるとともに成形金
型内部での引き抜き抵抗が増大し成形を行なう事が困難
になる。尚、ここでいう粒度分布とは、存在する粒径に
対する分布が９０重量％以上のものをいう。Furthermore, the metal oxides, metal hydroxides, and metal carbonates used in the present invention serve to prevent the resin composition from adhering to the inside of the mold during pultrusion molding, and to maintain a good surface condition of the molded product. . If the particle size distribution is less than 1 μm, the resin will adhere to the inside of the molding die and roughen the surface of the molded product. Furthermore, if the particle size distribution exceeds 40 μm, the mechanical properties of the molded product will deteriorate significantly, and the resistance to pulling out inside the mold will increase, making it difficult to perform molding. Incidentally, the particle size distribution as used herein refers to a particle size distribution of 90% by weight or more based on the existing particle size.
ここで金属酸化物とは酸化アルミニウム、酸化マグネシ
ウム、酸化チタン、酸化カルシウム、酸化亜鉛などであ
り、金属水酸化物とは水酸化アルミニウム、水酸化マグ
ネシウム。Here, metal oxides include aluminum oxide, magnesium oxide, titanium oxide, calcium oxide, zinc oxide, etc., and metal hydroxides include aluminum hydroxide and magnesium hydroxide.
水酸化カルシウムなどであり、金属炭酸塩とは炭酸亜鉛
、炭酸カルシウム、炭酸マグネシウムなどである。高い
難燃性を付与できる点からは金属水酸化物が選ばれ、特
に好ましくは水酸化アルミニウム、水酸化マグネシウム
が用いられる。Calcium hydroxide, etc., and metal carbonates include zinc carbonate, calcium carbonate, magnesium carbonate, etc. Metal hydroxides are selected because they can provide high flame retardancy, and aluminum hydroxide and magnesium hydroxide are particularly preferably used.
本発明の液状熱硬化性樹脂とはエポキシ樹脂。The liquid thermosetting resin of the present invention is an epoxy resin.
不飽和ポリエステル樹脂、ビニルエステル樹脂などであ
り、これらは商業的に容易に入手できる。好ましくは成
形速度の点から有機過酸化物による加熱硬化が可能であ
る不飽和ポリエステル樹脂、ビニルエステル樹脂が用い
られる。These include unsaturated polyester resins and vinyl ester resins, and these are easily available commercially. Preferably, from the viewpoint of molding speed, unsaturated polyester resins and vinyl ester resins that can be heat-cured with organic peroxides are used.
ここで有機過酸化物としてはビス（４−ｔ−ブチルシク
ロヘキサン）バーオキシジカーボ〜４−
ネート、シミリスチルパーオキシジカーボネート、ｔ−
ブチルパーオキシ（２−エチルヘキサノエート）、ベン
ゾイルパーオキサイド。Here, the organic peroxides include bis(4-t-butylcyclohexane) baroxydicarbonate, cimilistyl peroxydicarbonate, t-
Butyl peroxy (2-ethylhexanoate), benzoyl peroxide.
１．１−ジ−ｔ−ブチルパーオキシ−３，３゜５−トリ
メチルシクロヘキサン、１，１−ジ−ｔ−ブチルパーオ
キシシクロヘキサンなどであり、これらは一種または二
種以上の混合物として上記の不飽和ポリエステル樹脂、
ビニルエステル樹脂に配合される。さらに本発明の効果
を高めるために脂肪族炭化水素、高級脂肪酸、脂肪族ア
ルコール、脂肪酸アミド。1.1-di-t-butylperoxy-3,3゜5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, etc., which can be used alone or as a mixture of two or more of the above-mentioned saturated polyester resin,
Compounded with vinyl ester resin. Furthermore, in order to enhance the effect of the present invention, aliphatic hydrocarbons, higher fatty acids, aliphatic alcohols, and fatty acid amides.
金属石けん、脂肪酸エステル、有機リン酸エステルなど
が外部離型剤として併用され必要に応じて着色のための
顔料を使用してもよい。Metal soaps, fatty acid esters, organic phosphate esters, etc. may be used in combination as external mold release agents, and if necessary, pigments may be used for coloring.
またベンゾキノン、ヒドロキノン、ｔ−ブチルヒドロキ
ノン、ｔ−ブチルカテコールなどを重合禁止剤として液
状熱硬化性樹脂に添加することはこの液状熱硬化性樹脂
の可使用時間を延長させるのに効果的である。Furthermore, adding benzoquinone, hydroquinone, t-butylhydroquinone, t-butylcatechol, etc. to the liquid thermosetting resin as a polymerization inhibitor is effective in extending the usable life of the liquid thermosetting resin.
（実施例） 以下、本発明を実施例により説明する。(Example) The present invention will be explained below using examples.
実施例及び比較例は表−１及び表−２に記載した配合組
成により液状熱硬化性樹脂組成物を配合せしめガラスロ
ービング＜ＲＥＲＩ １５ＲＤ ：日本板硝子（株）製
〉を７本引きそろえとしプルトルージョン成形法により
直径２．５ｍｍの繊維強化樹脂連続体を成形せしめたも
のである。この時成形金型の温度は最高温部で１４０℃
、成形速度は１．５ｍ／分であった。この直径２．５
ｍ ｍの繊維強化樹脂連続体の表面状態及び ＪＩＳ
Ｋ ６９１１ に基づく曲げ強度試験の結果を表−
１及び表−２に併記した。In the Examples and Comparative Examples, seven glass rovings <RERI 15RD manufactured by Nippon Sheet Glass Co., Ltd.> were prepared by blending liquid thermosetting resin compositions according to the compositions shown in Tables 1 and 2, and pultrusion was performed. A fiber-reinforced resin continuum with a diameter of 2.5 mm was molded using a molding method. At this time, the temperature of the molding die is 140℃ at the highest temperature part.
, the molding speed was 1.5 m/min. This diameter is 2.5
Surface condition of fiber reinforced resin continuum of mm and JIS
The results of the bending strength test based on K 6911 are shown below.
1 and Table 2.
比較例１は不飽和ポリエステル樹脂に硬化剤である有機
過酸化物、外部離型剤であるステアリン酸亜鉛９重合禁
止剤であるハイドロキノンのみを配合したものであるが
、成形開始直後より得ようとした繊維強化樹脂連続体の
表面が著しく削られ成形金型内部にて破断するに至り表
面状態の良好なる繊維強化樹脂連枕体を得る事は不可能
であり従って曲げ強度の測定も実施できなかっな。In Comparative Example 1, only an organic peroxide as a curing agent, zinc stearate as an external mold release agent, and hydroquinone as a polymerization inhibitor were blended into an unsaturated polyester resin. The surface of the fiber-reinforced resin continuum was significantly scraped and broke inside the mold, making it impossible to obtain a fiber-reinforced resin continuum with good surface condition, and therefore, it was not possible to measure the bending strength. Na.
比較例２．４，６．１１は比較例１の樹脂組成物に粒度
分布が１μ未満なる酸化アルミニウム、水酸化アルミニ
ウム、炭酸カルシウムを単独または併用したものである
が、いずれの比較例においても得られた繊維強化樹脂連
続体の表面状態は不均一で時として表面が削られ不可で
あった。In Comparative Examples 2.4 and 6.11, aluminum oxide, aluminum hydroxide, and calcium carbonate having a particle size distribution of less than 1 μm were used alone or in combination in the resin composition of Comparative Example 1. The surface condition of the fiber-reinforced resin continuum thus obtained was non-uniform and sometimes the surface was scraped.
比較例３．５．７．１２は粒度分布が４０μを越える酸
化アルミニウム、水酸化アルミニウム、炭酸カルシウム
を単独または併用したものであるが、いずれの比較例に
おいても成形金型内部での引き抜き抵抗が高くガラスロ
ービングが破断するに至り、目的とする繊維強化樹脂連
続体を成形する事はできなかった。Comparative Example 3.5.7.12 uses aluminum oxide, aluminum hydroxide, and calcium carbonate with a particle size distribution of more than 40 μ, alone or in combination, but in all of the comparative examples, the pull-out resistance inside the mold was low. The glass roving broke at a high temperature, and it was not possible to form the intended fiber-reinforced resin continuum.
比較例８，９．１０は粒度分布が１〜４０μなる酸化ア
ルミニウム、水酸化アルミニウム。Comparative Examples 8, 9, and 10 are aluminum oxide and aluminum hydroxide having a particle size distribution of 1 to 40 μm.
炭酸カルシウムを各々１００重量部配合したものである
が、比較例３．５．７と同じく成形金型内部での引き抜
き抵抗が高くガラスロービングが破断するに至り、目的
とする繊維強化樹脂連続体を成形する事はできなかった
。Although 100 parts by weight of calcium carbonate were mixed in each, as in Comparative Example 3.5.7, the pull-out resistance inside the mold was high and the glass roving broke, making it difficult to produce the desired fiber-reinforced resin continuum. It could not be molded.
比較例１３は粒度分布が４０μを越える水酸化アルミニ
ウムと粒度分布が１μ未満なる炭酸カルシウムを配合し
たものであるが、成形金型内部での引き抜き抵抗が高く
引き抜きは困難であった。Comparative Example 13 was a mixture of aluminum hydroxide with a particle size distribution of more than 40 μm and calcium carbonate with a particle size distribution of less than 1 μm, but the drawing resistance inside the mold was high and it was difficult to pull it out.
実施例１．２．３は比較例８，９．１０の樹脂組成にお
いて粒度分布１〜４０μなる酸化アルミニウム、水酸化
アルミニウム及び炭酸カルシウムを各々５重量部とした
ものであるが表面状態は著しく向上し滑かな表面を有す
る繊維強化樹脂連続体が１０００ｍ以上の長尺に渡って
得られるようになった。また得られた繊維強化樹脂連続
体の曲げ強度は１０８〜１１５ ｋ ｇ ／ ｍ ｍ
２と非常に高強度であった。Examples 1.2.3 are the resin compositions of Comparative Examples 8 and 9.10, but each contains 5 parts by weight of aluminum oxide, aluminum hydroxide, and calcium carbonate with a particle size distribution of 1 to 40μ, but the surface condition is significantly improved. A fiber-reinforced resin continuum having a smooth surface can now be obtained over a length of 1000 m or more. The bending strength of the obtained fiber reinforced resin continuum was 108 to 115 kg/mm.
2, which was extremely high strength.
実施例４．５．６及び実施例７．８．９は粒度分布１〜
４０μなる酸化アルミニウム１水酸化アルミニウム及び
炭酸カルシウムを各々１５重量部及び５０重量部とした
ものであるがなんら表面が荒れることもなく光沢のある
滑らかで良好な表面状態をもつ繊維強化樹脂連続体が１
０．０００ｍ以上の長尺に渡る連続成形において得られ
た。またこの時の繊維強化樹脂連続体の曲げ強度は８４
〜１０９ｋｇ／ｍｍ２と高、い曲げ強度を示し実用的に
十分な曲げ強度を有していることが判る。Examples 4.5.6 and 7.8.9 have a particle size distribution of 1 to 1.
The fiber-reinforced resin continuum was made by using aluminum oxide 1 with a diameter of 40μ, aluminum hydroxide, and calcium carbonate at 15 parts by weight and 50 parts by weight, respectively, and having a glossy, smooth, and good surface condition without any surface roughening. 1
It was obtained by continuous molding over a long length of 0.000 m or more. In addition, the bending strength of the fiber reinforced resin continuum at this time was 84
It shows a high bending strength of ~109 kg/mm2, indicating that it has a practically sufficient bending strength.
実施例１０，１１．１２．１３は粒度分布１〜４０μな
る酸化アルミニウム、水酸化アルミニウム、炭酸カルシ
ウムを各々１０重量部づつ２種以上混合した上で配合し
たものであるが実施例４．５．６．７．８．９と何ら変
わる事なく良好な表面状態をもつ繊維強化樹脂連続体が
１０．０００ｍ以上の長尺に渡って得られた。またこの
時の繊維強化樹脂連続体の曲げ強度は９５〜１０１ ｋ
ｇ ／ ｍ ｍ ２と高い曲げ強度を示した。In Examples 10, 11, 12, and 13, two or more types of aluminum oxide, aluminum hydroxide, and calcium carbonate each having a particle size distribution of 1 to 40 μm were mixed and blended in an amount of 10 parts by weight. A fiber-reinforced resin continuum with a good surface condition no different from that of 6.7.8.9 was obtained over a length of 10,000 m or more. In addition, the bending strength of the fiber-reinforced resin continuum at this time is 95 to 101 k.
It exhibited high bending strength of g/mm2.
（以下余白）
（発明の効果）
本発明により、従来の方法では達成できなかったつやの
ある表面状態の良好な成形物が安定して製造できるよう
になった。これにより成形不良によるロスを大幅に低減
させるとともに、長時間の連続運転が可能となり作業性
も大幅に向上した。またこのように表面状態がよく、シ
かも長尺にわたって安定しているため長尺での信頼性が
要求される用途にも用いることが可能となった。(The following is a margin) (Effects of the invention) According to the present invention, it has become possible to stably produce a molded product with a glossy and good surface condition that could not be achieved by conventional methods. This has greatly reduced losses due to molding defects, enabled continuous operation for long periods of time, and greatly improved work efficiency. In addition, since the surface condition is good and the surface is stable over a long length, it has become possible to use it in applications that require reliability over a long length.
更に本発明によるところの粒径１〜４０μの粒度分布を
もつ金属水酸化物５以上５０重量部以下混合した液状熱
硬化性樹脂組成物によりプルトルージョン成形せしめた
ところの成形物は良好なる外観に加え高い難燃性を容易
に付与することが可能となりその工業的価値は極めて大
きい。Furthermore, the molded product obtained by pultrusion molding with the liquid thermosetting resin composition containing 5 or more and 50 parts by weight or less of a metal hydroxide having a particle size distribution of 1 to 40 μm according to the present invention has a good appearance. In addition, high flame retardance can be easily imparted, and its industrial value is extremely large.
−１３＝−13=
Claims (1)
選ばれた少なくとも一種以上を成分とする添加剤を５以
上５０重量部以下混合して成る液状熱硬化性樹脂組成物
を長手方向に連続した繊維に含浸せしめ、しかる後成形
金型内部に連続的に導入し加熱硬化と同時に成形せしめ
ることを特徴とする繊維強化樹脂連続体の製造方法。[Scope of Claims] 5 to 50 parts by weight of an additive containing at least one selected from the group consisting of metal oxides, metal hydroxides, and metal carbonates per 100 parts by weight of the liquid thermosetting resin. A fiber-reinforced resin characterized by impregnating continuous fibers in the longitudinal direction with a liquid thermosetting resin composition of less than 50% of the mixture, and then continuously introducing it into a molding die and molding it simultaneously with heating and curing. Method of manufacturing continuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63039164A JP2547602B2 (en) | 1988-02-22 | 1988-02-22 | Method for producing fiber-reinforced continuous tree finger |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63039164A JP2547602B2 (en) | 1988-02-22 | 1988-02-22 | Method for producing fiber-reinforced continuous tree finger |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01214427A true JPH01214427A (en) | 1989-08-28 |
| JP2547602B2 JP2547602B2 (en) | 1996-10-23 |
Family
ID=12545482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63039164A Expired - Fee Related JP2547602B2 (en) | 1988-02-22 | 1988-02-22 | Method for producing fiber-reinforced continuous tree finger |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2547602B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5061465A (en) * | 1973-10-03 | 1975-05-27 | ||
| JPH01163045A (en) * | 1987-12-21 | 1989-06-27 | Toa Nenryo Kogyo Kk | Pultrusion product made of carbon fiber reinforced composite resin and its production |
-
1988
- 1988-02-22 JP JP63039164A patent/JP2547602B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5061465A (en) * | 1973-10-03 | 1975-05-27 | ||
| JPH01163045A (en) * | 1987-12-21 | 1989-06-27 | Toa Nenryo Kogyo Kk | Pultrusion product made of carbon fiber reinforced composite resin and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2547602B2 (en) | 1996-10-23 |
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