JPH02235726A - Draw molding process for fiber-reinforced phenol formaldehyde resin - Google Patents
Draw molding process for fiber-reinforced phenol formaldehyde resinInfo
- Publication number
- JPH02235726A JPH02235726A JP1032561A JP3256189A JPH02235726A JP H02235726 A JPH02235726 A JP H02235726A JP 1032561 A JP1032561 A JP 1032561A JP 3256189 A JP3256189 A JP 3256189A JP H02235726 A JPH02235726 A JP H02235726A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- formaldehyde resin
- temperature
- fiber
- phenol
- 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
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 34
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000465 moulding Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 33
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 229920005989 resin Polymers 0.000 abstract description 53
- 239000011347 resin Substances 0.000 abstract description 53
- 239000000835 fiber Substances 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000003733 fiber-reinforced composite Substances 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 55
- 239000000047 product Substances 0.000 description 24
- 229960004279 formaldehyde Drugs 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 5
- 229920003987 resole Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 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 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- -1 silane compound Chemical class 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 101000685083 Centruroides infamatus Beta-toxin Cii1 Proteins 0.000 description 1
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229960003531 phenolsulfonphthalein Drugs 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、繊維強化フェノール会ホルムアルデヒド樹脂
引抜成形（Ｐｕｌｔｒｕｓｉｏｎ Ｍｏｌｄｉｎｇ）複
合材料の製法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing a fiber-reinforced phenolic-formaldehyde resin pultrusion molding composite material.
（従来の技術）
引抜成形法は、種々の繊維と樹脂を混合する加工作業を
示す。しかしながら、一般的にこの加工方法には、主と
して不飽和ポリエステル樹脂およびエポキシ樹脂が使わ
れている。フェノール番ホルムアルデヒド樹脂は、エポ
キシ樹脂および不飽和ポリエステル樹脂が持つ利点を有
するばかりでなく、コストの面、耐熱性、耐摩耗性、耐
燃焼性及び電気特性などにも優れている。しかし、フェ
ノール・ホルムアルデヒド樹脂はその反応速度が遅く、
樹脂と繊維との間の結合状態が好ましくないので、一般
的に繊維強化フェノール・ホルムアルデヒドの加工方法
にはプレプレッグ、コンパウンドあるいは反応射出成形
などが採用されている。BACKGROUND OF THE INVENTION Pultrusion refers to a processing operation that mixes various fibers and resins. However, this processing method generally uses primarily unsaturated polyester resins and epoxy resins. Phenol formaldehyde resin not only has the advantages of epoxy resins and unsaturated polyester resins, but also has excellent cost, heat resistance, abrasion resistance, combustion resistance, and electrical properties. However, the reaction rate of phenol formaldehyde resin is slow,
Because the bond between the resin and the fibers is unfavorable, prepreg, compound, or reaction injection molding is generally used as a processing method for fiber-reinforced phenol/formaldehyde.
英国特許第１．３６３．２２７号に記載されているよう
に、二価アルコール類で変性したフェノール嘲ホルムア
ルデヒド樹脂を使用し、一種の有機酸を硬化触媒として
用いると、比較的低温低圧下でも速い反応速度で優れた
物性を持つ樹脂を製造することもできる。この場合、二
価アルコール類の含有量は１２〜３５重量％である。As described in British Patent No. 1.363.227, using a phenol-formaldehyde resin modified with dihydric alcohols and using a type of organic acid as a curing catalyst, the curing process is fast even at relatively low temperature and low pressure. It is also possible to produce resins with excellent physical properties due to the reaction rate. In this case, the content of dihydric alcohols is 12 to 35% by weight.
米国特許第４．４１９．４４０号には、一種の繊維強化
フェノール・ホルムアルデヒド樹脂引抜成形製品が記載
されている。この場合、フェノール赤ホルムアルデヒド
は、５００〜４０００ｃｐｓの粘度をＨし、さらに少量
の揮発性物質を含有する。最も好ましい粘度は８００〜
３０００ｃｐｓである。US Pat. No. 4,419,440 describes a type of fiber reinforced phenol-formaldehyde resin pultrusion product. In this case, phenol red formaldehyde has a viscosity of 500-4000 cps and also contains small amounts of volatile substances. The most preferable viscosity is 800~
It is 3000cps.
該米国特許に述べられた技術思想は、明細書第４カラム
、第４行口に「液体フェノールφホルムアルデヒド樹脂
が持つ低粘度は本発明の繊維強化製品の作業過程を円滑
に進めることに役立つ。該樹脂が含んでいる揮発性物質
がきわめて少ないので硬化工程で発生する気泡の現象を
避けることができる。」と記栽されている。従って、該
特許に記載された方法によれば、液体フェノールΦホル
ムアルデヒド樹脂はその架橋程度が低くて、繊維が樹脂
と接触する前に、プレーヒー夕を選択的に使用して繊維
を予備加熱することによって金型での硬化速度を上げる
ことができる。同時に、金型の温度も比較的に高いレベ
ルを保持しなければならない。フェノール・ホルムアル
デヒドが縮合反応を行って水を副生ずるので、金型の温
度、特に末端の温度が高く、加えて繊維の通過速度が速
くて、樹脂中の水は急速に膨張して、引抜成形製品の内
部に気泡を発生させることは避けられない。該特許には
繊維の通過速度が約１〜２０メートル／分と記載されて
いても、実際には、通過速度を１メートル／分から３メ
ートル／分まで上げることはない。The technical idea stated in the US patent is stated in the fourth column, fourth line of the specification: ``The low viscosity of the liquid phenol φ formaldehyde resin helps to smoothly proceed with the working process of the fiber-reinforced product of the present invention. Since the resin contains very few volatile substances, the phenomenon of bubbles generated during the curing process can be avoided. Therefore, according to the method described in the patent, the liquid phenolic formaldehyde resin has a low degree of crosslinking, and a preheater is selectively used to preheat the fibers before the fibers come into contact with the resin. This can increase the curing speed in the mold. At the same time, the mold temperature must also be maintained at a relatively high level. Phenol/formaldehyde undergoes a condensation reaction and water is produced as a by-product, so the temperature of the mold, especially at the ends, is high, and in addition, the speed of fiber passage is fast, and the water in the resin expands rapidly, resulting in pultrusion molding. The generation of air bubbles inside the product is unavoidable. Although the patent describes a fiber passage speed of approximately 1 to 20 meters/min, in practice the passage speed is not increased to 1 meter/min to 3 meters/min.
（発明が解決しようとする課題）
本発明の目的は、上記欠点を有しない一種の繊維強化フ
ェノール・ホルム，アルデヒド樹脂引抜成形方法を提供
することにある。(Problems to be Solved by the Invention) An object of the present invention is to provide a type of fiber-reinforced phenol-form-aldehyde resin pultrusion method that does not have the above-mentioned drawbacks.
本発明のもう一つの目的は、上記繊維強化フェノール・
ホルムアルデヒド樹脂引抜成形製品のポストキュア方法
を提供することにある。Another object of the present invention is to
An object of the present invention is to provide a method for post-curing formaldehyde resin pultrusion products.
本発明のさらにもう一つの目的は、上記方法によって作
られた繊維強化フェノール・ホルムアルデヒド樹脂引抜
成形製品を提供することにある。Yet another object of the present invention is to provide a fiber-reinforced phenol-formaldehyde resin pultrusion product made by the above method.
本発明は、繊維強化フェノール・ホルムアルデヒド樹脂
引出成形方法に関する。すなわち、複数本の繊維、紗束
、線、縄、布、マットなどを液体フェノール・ホルムア
ルデヒド樹脂に含没させ、引抜法によって繊維などが加
熱した金型を通過して、硬化後得られた所要形状の繊維
強化フェノール・ホルムアルデヒド樹脂引抜成形品であ
る。その特徴は、上記液体フェノール・ホルムアルデヒ
ド樹脂が含浸作業中に加熱されて８００〜２０００ｃｐ
ｓの粘度を保持することにある。しかし、上記の樹脂は
、一般的に２５℃で３０００〜５０００ｃｐｓの粘度を
有する。The present invention relates to a fiber reinforced phenol-formaldehyde resin pultrusion method. That is, multiple fibers, gauze bundles, wires, ropes, cloth, mats, etc. are impregnated in liquid phenol/formaldehyde resin, and the fibers are passed through a heated mold using a pultrusion method, and the desired material is obtained after curing. It is a fiber-reinforced phenol formaldehyde resin pultrusion molded product. Its feature is that the liquid phenol/formaldehyde resin is heated to 800 to 2000 cp during the impregnation process.
The purpose is to maintain a viscosity of s. However, the above resins generally have a viscosity of 3000-5000 cps at 25°C.
本発明方法では、比較的高い架橋程度のフェノール・ホ
ルムアルデヒドを用い、特殊な三段式加熱金型を採用す
る。その中で、１段目の温度は１００〜１７０℃の範囲
にあり、２段目の温度は１５０〜２００℃の範囲にあり
、３段目の温度は１４０〜１９０℃範囲（；ある。２段
目の温度は他の二段より高い。本発明に採用される樹脂
が比較的高い程度まで架橋したものであり、それに含浸
作業が比較的高温で行なわれ、１段目の温度が１００℃
以上に保持されているので、樹脂中の副生水をできるだ
け充分に追い出すことができる。２段目の温度が２００
℃以下とするのは繊維が高速で金型を通過する時、樹脂
中に副生じた水が金型の出口で急速に膨張することを避
けるためである。The method of the present invention uses phenol formaldehyde with a relatively high degree of crosslinking and employs a special three-stage heating mold. Among them, the temperature of the first stage is in the range of 100 to 170°C, the temperature of the second stage is in the range of 150 to 200°C, and the temperature of the third stage is in the range of 140 to 190°C. The temperature of the first stage is higher than the other two stages.The resin used in the present invention is cross-linked to a relatively high degree, and the impregnation operation is carried out at a relatively high temperature, and the temperature of the first stage is 100℃.
Since the amount of water is maintained above, the by-product water in the resin can be expelled as fully as possible. The temperature of the second stage is 200
The reason why the temperature is below 0.degree. C. is to prevent the water produced in the resin from rapidly expanding at the outlet of the mold when the fiber passes through the mold at high speed.
本発明方法に使用されるフェノール・ホルムアルデヒド
樹脂が上記米国特許第４．４１９．４４０号に述べられ
たものより相対的に高架橋度を有するので、比較的低温
の金型を含没繊維がかなり高速で通過しても充分な硬化
を遂げることができる。しかし、本発明方法に使用され
るフェノール・ホルムアルデヒド樹脂が比較的高い粘度
を持つので、含浸作業中に樹脂は均一に繊維の間に分布
することが難かしい。以上の欠点を克服するため、本発
明方法は繊維含浸作業中に上記の樹脂を加熱して、操作
できるまでの範囲に粘度を下げる。本発明方法が開示さ
れるまで、比較的高い粘度のフェノール・ホルムアルデ
ヒド樹脂が引抜成形による繊維補強複合材料の製造には
使用できないと見なされるが、本発明方法は今まで不可
能な一種の高速繊維補強フェノール自ホルムアルデヒド
の引抜成形方法を提供する。Because the phenol-formaldehyde resin used in the method of the present invention has a relatively higher degree of crosslinking than that described in the above-mentioned U.S. Pat. Sufficient curing can be achieved even if the material is passed through the process. However, because the phenol-formaldehyde resin used in the method of the present invention has a relatively high viscosity, it is difficult to uniformly distribute the resin among the fibers during the impregnation operation. To overcome the above disadvantages, the method of the present invention heats the above-mentioned resin during the fiber impregnation operation to reduce the viscosity to a manageable range. Until the disclosure of the method of the present invention, relatively high viscosity phenol-formaldehyde resins are considered unusable for the production of fiber-reinforced composite materials by pultrusion; A method for pultrusion of reinforced phenol autoformaldehyde is provided.
（課題を解決するための手段）
本発明は、繊維強化フェノールφホルムアルデヒド樹脂
引抜成形品の製法に関する。より具体的には、本発明は
、連続型補強繊維をフェノール・ホルムアルデヒドで含
浸し、引抜きながら加熱した成形金型を通過させて、硬
化後得られた所要形状の繊維強化フェノール・ホルムア
ルデヒド樹脂成形品に関する。その特徴は、上記フェノ
ール・ホルムアルデヒド樹脂が温度２５℃下で３０００
〜５０００ｃｐｓの粘度を持ち、そして上記の繊維念浸
工程を行う時、上記フェノール命ホルムアルデヒド樹脂
が加熱されて、粘度範囲を８００〜２０００ｃｐｓで維
持することができることである。本発明方法では、特殊
な三段式加熱金型を使用し１段目の温度は約１４０〜１
７０℃の範囲で、、２段目Φ温度は約１５０〜２００の
範囲で、３段目の温度は１４０〜１９０℃の範囲にあり
、２段目の温度は他の二段より高い。上記フェノール・
ホルムアルデヒド樹脂引抜成形品は、選択的にポストキ
ュアによってその物性をさらに強めることもできる。(Means for Solving the Problems) The present invention relates to a method for producing a fiber-reinforced phenol φ formaldehyde resin pultrusion molded product. More specifically, the present invention provides a fiber-reinforced phenol-formaldehyde resin molded product having a desired shape obtained by impregnating continuous reinforcing fibers with phenol-formaldehyde and passing through a heated molding die while drawing. Regarding. The feature is that the above phenol formaldehyde resin has a temperature of 3000℃ at a temperature of 25℃.
The phenol-formaldehyde resin has a viscosity of ~5000 cps, and when performing the fiber deep dipping process, the phenol-formaldehyde resin can be heated to maintain the viscosity range from 800 to 2000 cps. In the method of the present invention, a special three-stage heating mold is used, and the temperature of the first stage is approximately 140 to 1
In the range of 70°C, the second stage Φ temperature is in the range of about 150-200°C, the third stage temperature is in the range of 140-190°C, and the second stage temperature is higher than the other two stages. The above phenol
Formaldehyde resin pultruded products can also be selectively post-cured to further enhance their physical properties.
（作用）
本発明方法に使用されるフェノールΦホルムアルデヒド
樹脂は、周知のフェノール舎ホルムアルデヒド・レゾー
ル樹脂を基材としてまたは修飾して変性されるものであ
る。(Function) The phenol Φ formaldehyde resin used in the method of the present invention is modified by using the well-known phenol formaldehyde resol resin as a base material or by modifying it.
フェノール・ホルムアルデヒド・レゾール樹脂の製造は
、通常塩基性触媒の存在下で過剰のホルムアルデヒドあ
るいはその類似品をフェノールと縮合反応させて得られ
たものである。これらのフェノール・ホルムアルデヒド
・レゾール樹脂の反応条件及び反応に適したアルデヒド
類とフェノール類化合物の選択はすでに周知であり、例
えば米国特許第４．４１９．４４０号には詳しい製法が
記載されている。本発明は該米国特許の内容を参考資料
とする。しかし、本発明は、米国特許第４．４１９．４
４０号あるいは第４．５８７．２９１号に記載されてい
るように反応がホルムアルデヒドの含有量が２％以下、
フェノール含有量が５％以下まで進まなければならない
という制限を必要としなくて、ただ樹脂の固形分が６０
％、ホルムアルデヒドの含有量が約１０％になればよい
わけである。Phenol-formaldehyde resol resins are usually produced by condensing excess formaldehyde or its analogs with phenol in the presence of a basic catalyst. The reaction conditions for these phenol-formaldehyde resol resins and the selection of aldehydes and phenolic compounds suitable for the reaction are already well known, and a detailed manufacturing method is described, for example, in US Pat. No. 4,419,440. The present invention is made by reference to the contents of said US patent. However, the present invention is based on U.S. Pat.
No. 40 or No. 4.587.291, the reaction is carried out with a formaldehyde content of 2% or less,
There is no need for a restriction that the phenol content must go below 5%, just a resin solids content of 60%.
%, and the formaldehyde content should be about 10%.
上記フェノール・ホルムアルデヒド樹脂に、適量の触媒
を添加してから、好ましい温度で反応させると、２５℃
での粘度が３０００〜５０００ｃｐｓである樹脂が得ら
れる。。粘度測定は、ＡＳＴＭ Ｄ２３９３によって
ブルックフィールド粘度計を用いて行う。その時、樹脂
の固形分は約８５％で、ホルムアルデヒドの含有量は約
２％以下である。When an appropriate amount of catalyst is added to the above phenol-formaldehyde resin and reacted at a preferable temperature, 25℃
A resin having a viscosity of 3000 to 5000 cps is obtained. . Viscosity measurements are performed using a Brookfield viscometer according to ASTM D2393. At that time, the solid content of the resin is about 85%, and the formaldehyde content is about 2% or less.
上記触媒は、基本的に英国特許第１．３８３．２７７号
に記載されている。本発明は該特許の内容を参考資料と
する。触媒はパラトルエンスルホン酸、フェノールスル
ホン酸またはリン酸を使うものが最も好ましい。添加量
は、樹脂全量の２〜１０重量％で、最も好ましくは４〜
８重量％である。反応温度は、７０〜１００℃で、最も
好ましいくは８５〜９５℃である。一般的に反応時間は
１２時間以上である。触媒のほかに、少量の周知の変性
用二価あるいは多価アルコール類を選択的に添加するこ
とができる。これらの変性用二価あるいは多価アルコー
ル類は、すでに英国特許第１．３６３，２２７号と米国
特許第４．４１９．４４０号に記載されている。The above catalyst is essentially described in British Patent No. 1.383.277. The present invention uses the contents of this patent as reference material. Most preferably, the catalyst uses para-toluenesulfonic acid, phenolsulfonic acid or phosphoric acid. The amount added is 2 to 10% by weight of the total amount of resin, most preferably 4 to 10% by weight.
It is 8% by weight. The reaction temperature is 70-100°C, most preferably 85-95°C. Generally the reaction time is 12 hours or more. In addition to the catalyst, small amounts of known modifying dihydric or polyhydric alcohols can optionally be added. These modifying dihydric or polyhydric alcohols have already been described in British Patent No. 1.363,227 and US Pat. No. 4.419.440.
本発明方法に添加される変性用二価あるいは多価アルコ
ール類の添加量は、樹脂全量の約１５重量％以下である
。The amount of the modifying dihydric or polyhydric alcohol added to the method of the present invention is about 15% by weight or less based on the total amount of the resin.
上記触媒を添加、反応して得られた２５℃での粘度３０
００〜５０００ｃｐｓを持つ樹脂には、さらに無機質フ
ィラー、例えば炭酸カルシウム、シリカ及び滑石粉など
を入れて、引抜成形品の機械的性質を高めることもでき
る。フィラーの添加量は樹脂全量の約５〜１０重量％で
ある。また、樹脂と繊維との結合状態を改善するために
、カップリング剤、例えばシラン類の化合物を添加する
こともできる。上記変性フェノール・ホルムアルデヒド
・レゾール樹脂が含浸槽に置れている時、その温度は粘
度８００〜２０００ｃｐｓに保持できる温度で、好まし
くは１２００〜１５００ｃｐＳである。周知のように、
温度が高ければ、高いほど樹脂の粘度が低《なる。しか
し、加熱時間が長ければ長いほど樹脂の粘度が高くなる
。本発明の一つの好ましい例によれば温度が５５℃で上
記の樹脂粘度は始めの１３００ｃｐｓから徐々に高くな
って、４時間後には１６００ｃｐｓで、８時間後には２
０００ｃｐｓぐらいになる。なお、温度が９０℃で、上
記の樹脂粘度は始めの１０００ｃｐｓから、４時間後に
は２０００ｃｐｓになってしまう。したがって、含浸槽
におけ樹脂の温度は所要製品のサイズ、形状、及び繊維
の種類と量によって変えることができる。The viscosity at 25°C obtained by adding and reacting the above catalyst is 30
Resins with 00 to 5000 cps may also include inorganic fillers such as calcium carbonate, silica, and talcum powder to enhance the mechanical properties of the pultrusion. The amount of filler added is about 5 to 10% by weight based on the total amount of resin. Further, in order to improve the bonding state between the resin and the fibers, a coupling agent such as a silane compound may be added. When the modified phenol formaldehyde resol resin is placed in the impregnation bath, the temperature is such that the viscosity can be maintained at 800 to 2000 cps, preferably 1200 to 1500 cps. As is well known,
The higher the temperature, the lower the viscosity of the resin. However, the longer the heating time, the higher the viscosity of the resin. According to one preferred embodiment of the present invention, at a temperature of 55° C., the resin viscosity increases gradually from an initial 1300 cps to 1600 cps after 4 hours and 2.0 cps after 8 hours.
It will be about 000cps. Note that when the temperature was 90° C., the viscosity of the resin was initially 1000 cps, but after 4 hours it became 2000 cps. Therefore, the temperature of the resin in the impregnation bath can be varied depending on the size and shape of the desired product and the type and amount of fibers.
本発明の実施例に適した繊維には、繊維、紗東、線、縄
、布あるいはマットなど連続形補強繊維がすべて含まれ
ている。通常採用されてる材質は、ガラス繊維、炭素繊
維、ポリアミド繊維（アラミド）あるいはハイブリッド
繊維などの有機と無機繊維である。Fibers suitable for embodiments of the present invention include all continuous reinforcing fibers such as fibres, gauze, wire, rope, cloth or mats. The materials commonly employed are organic and inorganic fibers such as glass fibers, carbon fibers, polyamide fibers (aramids) or hybrid fibers.
本発明方法において、フェノール・ホルムアルデヒド樹
脂が引抜成形される時、少量の水が副生するので、架橋
反応が発熱反応であっても金型にある樹脂はやはり徐々
に昇温する。したがって、本発明方法に金型の末端温度
はエボキシ樹脂と不飽和ポリエステルの引抜成形金型と
違うように、比較的高い温度を保持するので、短い時間
で硬化反応を終えることができる。金型の温度は樹脂の
滞留時間が短いので、一般的に樹脂の温度より１０〜２
０℃高くなる。製品のサイズと形状も金型の温度設計に
大いに影響する。本発明の一つの実施例として、長さ８
２（１４！Ｉ１．幅１． ２７ｃｏｒ、高さ０．３９
ＣＩＩ１の穴を持つ両片対称式金型を使用した時、温度
が２００℃以上になると、引抜速度を下げなければなら
ないということが判った。そうしないと、樹脂中の水が
高温で急速に蒸発するので、引抜成形品が金型の出口で
膨張し、製品の内部が空洞となって、物性が悪くなって
しまう。本発明のフェノール・ホルムアルデヒド樹脂は
すべて相当高い程度まで架橋されているので、上記の金
型の温度が２００℃以下であっても、１００ｃａ＋／分
の速度で引抜成形を行なうこともできる。樹脂に副生さ
れた水をできるだけ完全に追い出すため、本発明は三段
式の加熱金型を採用する。それぞれの温度範囲は１００
〜１７０℃、１６０〜２００℃、および１４０〜１９０
℃である。温度範囲がそれぞれ１４０〜１６０℃、１７
０〜１９０℃、および１５０〜１８０℃であることが一
番好ましい。In the method of the present invention, when the phenol-formaldehyde resin is pultruded, a small amount of water is produced as a by-product, so even if the crosslinking reaction is exothermic, the temperature of the resin in the mold will still gradually rise. Therefore, unlike the pultrusion molds for epoxy resin and unsaturated polyester, the end temperature of the mold is maintained at a relatively high temperature in the method of the present invention, so that the curing reaction can be completed in a short time. Since the residence time of the resin is short, the temperature of the mold is generally 10 to 2 times higher than the temperature of the resin.
0℃ higher. The size and shape of the product also greatly affect the temperature design of the mold. In one embodiment of the invention, length 8
2 (14! I1. Width 1.27cor, height 0.39
When using a double-sided symmetrical mold with CII1 holes, it was found that when temperatures exceeded 200°C, the drawing speed had to be reduced. Otherwise, the water in the resin will evaporate rapidly at high temperatures, causing the pultruded product to expand at the exit of the mold, creating a hollow interior and deteriorating its physical properties. All of the phenol-formaldehyde resins of the present invention are crosslinked to a fairly high degree so that pultrusion can be carried out at a rate of 100 ca+/min even at temperatures below 200 DEG C. in the molds described above. In order to completely expel the water by-produced in the resin, the present invention employs a three-stage heating mold. Each temperature range is 100
~170°C, 160-200°C, and 140-190
It is ℃. Temperature range is 140~160℃, 17
Most preferably, the temperature is 0 to 190°C, and 150 to 180°C.
フェノール・ホルムアルデヒド樹脂の引抜成形工程は、
反応が縮合反応に属するので、エポキシ樹脂あるいは不
飽和ポリエステル樹脂のような高い硬化度を達成するこ
とができない。したがって、必要により選択的に引抜成
形品をさらにポストキュア処理すると、製品に一番好ま
しい物性を持たせることができる。ポストキュア処理の
温度と時間は一般的に１００℃で１２時間以上であるな
らよい物性をもたらすことができるが、もし２００℃で
進めるならば１〜２時間が好ましい。The pultrusion process of phenol formaldehyde resin is
Since the reaction belongs to a condensation reaction, it is not possible to achieve a high degree of curing as with epoxy resins or unsaturated polyester resins. Therefore, if the pultrusion molded product is selectively further subjected to post-cure treatment if necessary, it is possible to impart the most desirable physical properties to the product. Generally, the temperature and time of the post-cure treatment can provide good physical properties if the temperature and time are 100° C. for 12 hours or more, but if the temperature and time are 100° C. and 12 hours or more, 1 to 2 hours is preferable if the temperature is 200° C.
典型的な引抜成形の操作は繊維材料を樹脂槽に充分に含
浸させてから、穴を通過させなが残余の樹脂を除去する
。加熱金型の中に引抜成形品が硬化されてから所要の長
さで切られる。米国特許第３，２４４．７８４号は引抜
成形装置に適した機械が述べられているので、当特許の
内容は本発明の参考資料とする。A typical pultrusion operation involves thoroughly impregnating the resin bath with the fibrous material and then passing it through a hole to remove residual resin. The pultruded product is cured in a heated mold and then cut to the required length. No. 3,244,784 describes a machine suitable for pultrusion equipment, and the contents of that patent are incorporated by reference into the present invention.
（実施例）
以下の実施例は、本発明の実施例をさらに詳しく説明す
るのに役立つであろう。なお、これらの実施例は、本発
明の範囲を限定する唯一のものではない。特に断らない
限り以下実施例の温度は摂氏で表し、組成比例は重量を
基準とする。EXAMPLES The following examples will serve to further illustrate embodiments of the invention. Note that these examples are not the only ones that limit the scope of the invention. Unless otherwise specified, temperatures in the following examples are expressed in degrees Celsius, and compositional proportions are based on weight.
実施例１
含浸樹脂の製法：
含浸樹脂の製法は、下記第１表に示したように配合を行
う。その中に成分（１）、（２）、（３）および（４）
は９０℃で２４時間連続撹拌し、反応液が冷却する前に
成分（５）を加えて均一になるまで充分に撹拌する。Example 1 Method for manufacturing impregnated resin: The method for manufacturing impregnated resin involves blending as shown in Table 1 below. Ingredients (1), (2), (3) and (4)
The mixture is continuously stirred at 90°C for 24 hours, and before the reaction mixture is cooled, component (5) is added and stirred thoroughly until the mixture becomes homogeneous.
第１表
成分 重量（ｇ）
（１）フェノールφホルム
アルデヒド樹脂 １３００（２）ｐ一トリ
エンスルホン酸 ６５（３）ポリブロビレン
グリコール ６５（４）カップリング剤
１３（５）滑石粉＋シリカ
１３０ただし、各成分は次のものを使用した。Table 1 Ingredients Weight (g) (1) Phenol φ formaldehyde resin 1300 (2) p-trienesulfonic acid 65 (3) Polybrobylene glycol 65 (4) Coupling agent
13(5) Talc powder + silica
130 However, the following components were used.
（１）台湾長春公司ＰＰ−．６５０、フェノールとホル
ムアルデヒドを原料とするレゾール樹脂。固形分６０％
、遊離ホルムアルデヒド含有量は９．９％である。(1) Taiwan Changchun Corporation PP-. 650, resol resin made from phenol and formaldehyde. Solid content 60%
, the free formaldehyde content is 9.9%.
《２》日本純薬工業株式会社製、試薬級。<2> Manufactured by Nippon Pure Chemical Industries, Ltd., reagent grade.
＜３）Ｐｏｌｙｐｒｏｐｙｌｅｎｅ ｇｌｙｃｏ＋平均
分子量２００ 〜３００。<3) Polypropylene glyco+average molecular weight 200 to 300.
（４）米国ユニオン・カーバイド社製Ａ−１１０００（
５）滑石粉は台湾長興化工公司製。比重２．７１、シリ
カは台湾弘発実業公南製。比重２．１引抜成形の操作：
上記含浸樹脂を含浸槽に入れて、５５℃の温度を維持す
る。２６本のニットーボ−（Ｎｉｔｔｏｂｏ）ＲＳ−２
４０ガラス繊維を含浸槽に含浸させながら通過させる。(4) A-11000 manufactured by Union Carbide Corporation (USA)
5) Talcum powder was manufactured by Changxing Chemical Co., Ltd. in Taiwan. The specific gravity is 2.71, and the silica is manufactured by Hongfa Industrial Co., Ltd. in Taiwan. Specific gravity 2.1 pultrusion operation: The above impregnated resin is placed in an impregnating bath and the temperature is maintained at 55°C. 26 Nittobo RS-2
40 glass fibers are passed through the impregnating tank while being impregnated.
ガラス繊維の比重は２．５４で一本繊維の直径は１４μ
量、その引張強度は４．９８ ＸＩＯ５ｐｓ１。含浸さ
れたガラス繊維は、長さ８２ｃｍ，幅１．２７ ｃｍ高
さ０．３１９ｃｍの穴を持つ両片対称電熱式金型に導入
され、三段式で金型の加熱を制御する。２段目電熱板の
長さは約４０（Ｊ，１段目および３段目の長さは約１５
国。電熱板は同距離感覚で金型の両側にすえつけられて
いる。The specific gravity of glass fiber is 2.54 and the diameter of one fiber is 14μ.
quantity, its tensile strength is 4.98 XIO5ps1. The impregnated glass fibers are introduced into a two-sided symmetrical electrothermal mold with holes 82 cm long, 1.27 cm wide and 0.319 cm high, and the heating of the mold is controlled in three stages. The length of the second stage electric heating plate is approximately 40 (J, the length of the first and third stages is approximately 15
Country. The electric heating plates are placed on both sides of the mold at the same distance.
引抜成形品の物性測定：
上記方法で得られた製品はガラス繊維の含有量が６０容
量％。種々の通過速度金型温度で得られた製品の曲げ強
度は下記第２表に示されている。Measurement of physical properties of pultruded product: The product obtained by the above method has a glass fiber content of 60% by volume. The bending strengths of the products obtained at various pass rates and mold temperatures are shown in Table 2 below.
曲げ強度の測定はＡＳＴＭ Ｄ７９０によって行なっ
た。Bending strength measurements were made according to ASTM D790.
第２表に示されているように、金型温度が２００℃以上
、通過速度が７０ｃｒｏ／分以上になると上記の引抜成
形品は、樹脂中に含有する水が金型の出口で急速に膨張
するので内部が空洞になって物性の／ＩＩＩ定はできな
い。As shown in Table 2, when the mold temperature is 200°C or higher and the passing speed is 70 cro/min or higher, the water contained in the resin expands rapidly at the exit of the mold. Therefore, the interior is hollow and the /III properties cannot be determined.
通過速度が１１００１！ｌ／分、金型温度が１６０−１
９０−１７０℃で得られた成型製品は各種ポストキュア
時間及び温度で処理されて、曲げ強度と衝撃強さに対す
る影響は下記第３表に示されている。衝撃強さの測定は
、ＡＳＴＭ Ｄ２５６試験法によって行なわれる。シ
ャルピ一方法によって長さ１２．７±Ｏ．ｌｃｍ，幅１
．２７ ｃｃｍ，深度０．２５ ｃｕｒの溝を持つ製品
サンプルを作って測定を行なった。Passing speed is 11001! l/min, mold temperature 160-1
The molded products obtained at 90-170°C were treated with various post-cure times and temperatures, and the effects on flexural strength and impact strength are shown in Table 3 below. Impact strength measurements are made by ASTM D256 test method. Length 12.7±O. by Charpy method. lcm, width 1
．． A product sample with a groove of 27 ccm and a depth of 0.25 cur was made and measured.
また上記１００℃、２４時間ボストキュア処理された製
品と未処理製品の違う温度での誘電率はＡＳＴＭ Ｄ
−１５０によって測定され、結果は下記第４表に示され
ている。In addition, the dielectric constants at different temperatures of the above-mentioned 100℃, 24-hour post-cured product and untreated product are ASTM D
-150 and the results are shown in Table 4 below.
第４表
誘電率
ながら含浸させ、ついで得られた含浸物を加熱金型を通
過させて所定形状に引抜成形することを特徴とする繊維
強化フェノール曝ホルムアルデヒド樹脂の引抜成形方法
であるから、比較的高粘度のフェノール・ホルムアルデ
ヒド樹脂を成形して、繊維補強複合の引抜成形品を製造
する方法を提供できる。Table 4 This is a pultrusion molding method for fiber-reinforced phenol-exposed formaldehyde resin, which is characterized by impregnating the resin with a dielectric constant, and then passing the impregnated material through a heating mold to pultrude it into a predetermined shape. A method for manufacturing a fiber-reinforced composite pultrusion product by molding a high-viscosity phenol-formaldehyde resin can be provided.
」−記第３表に示されているように比較的好ましいポス
トキュア条件は、１００℃２４時間以上であることが判
った。また、第３表および第４表から、フェノール令ホ
ルムアルデヒ゜ド引抜成形品は、その物性および誘電率
がポストキュア処理によって著しく高められることが判
った。As shown in Table 3, it was found that a relatively preferable post-cure condition is 100° C. for 24 hours or more. Furthermore, from Tables 3 and 4, it was found that the physical properties and dielectric constant of the phenol-formaldehyde pultrusion molded product were significantly improved by post-curing treatment.
（発明の効果）(Effect of the invention)
Claims (2)
た液体フェノール・ホルムアルデヒド樹脂の粘度を８０
０〜１２００ｃｐｓの範囲に維持させながら含浸させ、
ついで（ｂ）得られた含浸物を加熱金型を通過させて引
抜成形することを特徴とする繊維強化フェノール・ホル
ムアルデヒド樹脂の引抜成形方法。(1) (a) The viscosity of liquid phenol formaldehyde resin heated to 45 to 65°C is 80°C.
Impregnation while maintaining the range of 0 to 1200 cps,
Then (b) a method for pultrusion molding a fiber-reinforced phenol-formaldehyde resin, which comprises passing the obtained impregnated product through a heating mold and pultrusion molding it.
成形品をさらにポストキュア処理してなる特許請求の範
囲第１項に記載の方法。(2) The method according to claim 1, wherein the fiber-reinforced phenol-formaldehyde resin molded product is further subjected to a post-cure treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1032561A JPH0717026B2 (en) | 1989-02-10 | 1989-02-10 | Method of pultrusion molding of fiber reinforced phenol / formaldehyde resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1032561A JPH0717026B2 (en) | 1989-02-10 | 1989-02-10 | Method of pultrusion molding of fiber reinforced phenol / formaldehyde resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02235726A true JPH02235726A (en) | 1990-09-18 |
| JPH0717026B2 JPH0717026B2 (en) | 1995-03-01 |
Family
ID=12362323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1032561A Expired - Lifetime JPH0717026B2 (en) | 1989-02-10 | 1989-02-10 | Method of pultrusion molding of fiber reinforced phenol / formaldehyde resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717026B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109228084A (en) * | 2018-09-14 | 2019-01-18 | 天津工业大学 | A kind of preparation method of the thermosetting phenolic resin tensile sample of high solvent content |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53111370A (en) * | 1976-12-22 | 1978-09-28 | Sea Log Corp | Production of fiber reinforced resin structure |
| JPS54118467A (en) * | 1978-03-06 | 1979-09-13 | Hitachi Chem Co Ltd | Manufacturing of laminate impregnated with thermosetting synthetic resin |
-
1989
- 1989-02-10 JP JP1032561A patent/JPH0717026B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53111370A (en) * | 1976-12-22 | 1978-09-28 | Sea Log Corp | Production of fiber reinforced resin structure |
| JPS54118467A (en) * | 1978-03-06 | 1979-09-13 | Hitachi Chem Co Ltd | Manufacturing of laminate impregnated with thermosetting synthetic resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109228084A (en) * | 2018-09-14 | 2019-01-18 | 天津工业大学 | A kind of preparation method of the thermosetting phenolic resin tensile sample of high solvent content |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0717026B2 (en) | 1995-03-01 |
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