JPH0359060A - Phenol resin molding material - Google Patents
Phenol resin molding materialInfo
- Publication number
- JPH0359060A JPH0359060A JP19272789A JP19272789A JPH0359060A JP H0359060 A JPH0359060 A JP H0359060A JP 19272789 A JP19272789 A JP 19272789A JP 19272789 A JP19272789 A JP 19272789A JP H0359060 A JPH0359060 A JP H0359060A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- molding material
- string
- phenolic resin
- resin molding
- 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
- 239000012778 molding material Substances 0.000 title claims abstract description 43
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 35
- 239000003365 glass fiber Substances 0.000 claims abstract description 20
- 229920003986 novolac Polymers 0.000 claims abstract description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 7
- 239000004917 carbon fiber Substances 0.000 claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000742 Cotton Polymers 0.000 claims abstract description 4
- 229920000297 Rayon Polymers 0.000 claims abstract description 4
- 239000002964 rayon Substances 0.000 claims abstract description 4
- 239000004952 Polyamide Substances 0.000 claims abstract description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 3
- 229920002647 polyamide Polymers 0.000 claims abstract description 3
- 229920000728 polyester Polymers 0.000 claims abstract description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 3
- 239000005033 polyvinylidene chloride Substances 0.000 claims abstract description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 28
- 229920001568 phenolic resin Polymers 0.000 claims description 28
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- 229920006231 aramid fiber Polymers 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 5
- 238000005520 cutting process Methods 0.000 abstract description 3
- 241000531908 Aramides Species 0.000 abstract 1
- 229920003235 aromatic polyamide Polymers 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000748 compression moulding Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000019492 Cashew oil Nutrition 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 239000010467 cashew oil Substances 0.000 description 1
- 229940059459 cashew oil Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は機械的強度に優れ、射出成形可能なフェノール
系樹脂成形材料に関するものであり、さらに詳しくは自
動車部品や電気部品などの構造部品成形用として好適に
使用されるフェノール系樹脂成形材料に関するものであ
る。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a phenolic resin molding material that has excellent mechanical strength and is injection moldable. The present invention relates to a phenolic resin molding material suitably used for commercial purposes.
従来から前記構造部品としては、主として鋼、アルミニ
ウム等の金属が使用されているが、近年、自動車等の燃
費向上の為、該部品の軽量化を目的として金属からプラ
スチックへの代替が盛んに行なわれるようになってきた
。該プラスチックとしては各種エンジニアリング・プラ
スチックが主として検討されているが、自動車エンジン
回り部品のように熱間クリープ性、耐熱老化性等の長期
信頼性を要求される部品に関しては熱硬化性樹脂成形材
料（特にガラス繊維強化フェノール樹脂底形材料）が適
用されつつある。Traditionally, metals such as steel and aluminum have been mainly used for the above-mentioned structural parts, but in recent years, in order to improve the fuel efficiency of automobiles, metals have been increasingly replaced with plastics in order to reduce the weight of these parts. I'm starting to be able to do it. Various engineering plastics are mainly being considered as such plastics, but thermosetting resin molding materials ( In particular, glass fiber-reinforced phenolic resin bottom materials are being applied.
ガラス繊維強化熱硬化性樹脂成形材料は射出成形、トラ
ンスファー底形、圧縮成形により各種部品に供されてお
り、その−船釣製法は以下のとおりである。Glass fiber-reinforced thermosetting resin molding materials are used for various parts by injection molding, transfer molding, and compression molding, and the manufacturing method thereof is as follows.
ガラス繊維、熱硬化性樹脂、硬化剤、離型剤、染顔料、
溶剤等をミキサーで混合し、得られた混合物を加熱され
たロールで充分混練し、シート状になった材料を取り出
し、冷却後、粉砕して粒状の成形材料を得る。この方法
における射出成形用材料が特開昭６０−１０１１４０号
公報に開示されている。Glass fiber, thermosetting resin, curing agent, mold release agent, dye and pigment,
The solvent and the like are mixed in a mixer, the resulting mixture is sufficiently kneaded with heated rolls, the sheet-like material is taken out, cooled, and pulverized to obtain a granular molding material. A material for injection molding using this method is disclosed in Japanese Patent Application Laid-Open No. 101140/1983.
また、別の方法として含浸法により成形材料が得られる
が、その圧縮成形用材料については特公昭５１−３３９
４５号公報に開示されている。In addition, as another method, a molding material can be obtained by an impregnation method, but the material for compression molding was published in Japanese Patent Publication No. 51-339.
It is disclosed in Publication No. 45.
しかしながら、射出成形用のガラス繊維強化熱硬化性性
樹脂成形材料のほとんどが、特開昭６０−１０１１４０
号公報に開示されているように、ロールおよびニーダ−
等で加熱混練されている為に、材料中のガラス繊維の平
均繊維長はほとんど０．５ ｍｍ以下となり、従ってシ
ャルピー衝撃強さも６〜７ｋｇｆ−ａｍ／ｃｎｆが限度
であった。また、圧縮成形用の材料としては特公昭５１
＝ ３３９４５号公報に見られるように、例えば１イン
チ（２５，４ｍｍ）長に切断した材料を圧縮成形した成
形品において４０〜５０ ｋｇｆ・ｃｍ ／ ｃｎｆの
シャルピー衝撃強さが得られてはいるものの、射出成形
に適用した場合、ホッパー落ちが悪く、スクリューでか
みこみにくく、また充填不良を起こすなど連続成形がで
きないという大きな課題を抱えており、実用に適してい
なかった。However, most of the glass fiber reinforced thermosetting resin molding materials for injection molding are
As disclosed in the publication, rolls and kneaders
Because the glass fibers in the material were heated and kneaded, the average fiber length of the glass fibers in the material was almost 0.5 mm or less, and the Charpy impact strength was also limited to 6 to 7 kgf-am/cnf. In addition, as a material for compression molding,
= As seen in Publication No. 33945, for example, a Charpy impact strength of 40 to 50 kgf cm/cnf is obtained in a molded product made by compression molding a material cut into 1 inch (25.4 mm) length. When applied to injection molding, it had major problems such as poor hopper drop, difficulty in screwing in, and the inability to perform continuous molding due to filling defects, making it unsuitable for practical use.
本発明は上記従来技術に鑑みなされたもので、その目的
は機械的強度、特に衝撃強さに優れた成形品を与える１
〜ＩＯＭ長の射出成形可能なフェノール系樹脂成形材料
を提供することを目的としてなされたものである。The present invention was made in view of the above-mentioned prior art, and its purpose is to provide a molded product with excellent mechanical strength, particularly impact strength.
The purpose of this invention is to provide a phenolic resin molding material that can be injection molded with a length of ~IOM.
前記のごとくガラス繊維強化熱硬化性樹脂成形材料をロ
ールやニーダ−等で加熱混練した場合、ガラス繊維長は
ほとんど０．５印以下となる為、本発明者らは成形材料
中に１〜１０ｍｍ長の繊維を保持させるという観点から
ひも状体を樹脂を主成分とする液体に含浸、乾燥、切断
するという工程に着目した。更に、従来の含浸法による
成形材料は１インチ（２５，４ｍａ＋）長程度に切断さ
れていた為、成形性が圧縮成形に限定されていたものを
１〜１０ｍｍに切断すると驚くべきことに射出成形が可
能となり、更に驚くべきことに射出成形品において１５
〜２５ ｋｇｆ−ｃｍ／ｃｕｔのシャルピー衝撃強さが
得られることを見い出し、本発明を完成するにいたった
。As mentioned above, when a glass fiber reinforced thermosetting resin molding material is heated and kneaded using a roll or a kneader, the glass fiber length is almost 0.5 mm or less, so the present inventors added 1 to 10 mm in the molding material. From the perspective of retaining long fibers, we focused on the process of impregnating a string-like body with a liquid whose main component is resin, drying it, and cutting it. Furthermore, molding materials made using the conventional impregnation method were cut into lengths of about 1 inch (25.4 mm), so moldability was limited to compression molding, but when cut into 1-10 mm pieces, surprisingly injection molding was possible. is now possible, and even more surprisingly, 15
It was discovered that a Charpy impact strength of ~25 kgf-cm/cut could be obtained, and the present invention was completed.
即ち、本発明は短繊維及び又は長繊維より構成されるひ
も状体を７ボラフク型フエノール系樹脂を主成分とする
液体に含浸し、加熱乾燥後、１〜１０ ｍｍ長に切断し
て成る射出成形可能なフェノール系樹脂成形材料に関す
るものである。That is, the present invention is an injection method in which a string-like body composed of short fibers and/or long fibers is impregnated with a liquid containing a 7-borafuku type phenolic resin as a main component, dried by heating, and then cut into lengths of 1 to 10 mm. This invention relates to a moldable phenolic resin molding material.
本発明により得られるフェノール系樹脂成形材料の特徴
は以下のとおりである。The characteristics of the phenolic resin molding material obtained by the present invention are as follows.
１）射出成形において、ホッパー落ち及びスクリューの
かみこみが良好で、かつ、充填性が良好である。1) In injection molding, hopper drop and screw engagement are good, and filling properties are good.
２〉射出成形で得られた成形品の耐熱性、機械的強度、
寸法安定性が優れている。2> Heat resistance and mechanical strength of molded products obtained by injection molding,
Excellent dimensional stability.
３）同成形品の熱間クリープ性、耐熱老化性等の長期信
頼性に優れている。3) The molded product has excellent long-term reliability such as hot creep resistance and heat aging resistance.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に用いられるノボラック型フェノール系樹脂（以
下ノボラック樹脂と略す）はフェノール類とアルデヒド
類を酸性触媒の存在下に反応させて得られるものであり
、無変性タイプ、又はノボラック樹脂の製造時に必要に
応じて任意の変性剤を添加し、反応又は混合して得られ
る変性タイプノボラック樹脂等が例示される。このよう
な変性剤としては、カシュー油、トール油等の油類やメ
ラミン樹脂、キシレン樹脂、イミド樹脂等の樹脂類が好
適なものとして挙げられる。これらのノボラック樹脂は
単独又は混合して使用できる。The novolak type phenolic resin (hereinafter abbreviated as novolak resin) used in the present invention is obtained by reacting phenols and aldehydes in the presence of an acidic catalyst, and is necessary for the production of unmodified type or novolak resin. Examples include modified novolac resins obtained by adding and reacting or mixing an arbitrary modifier depending on the conditions. Suitable examples of such modifiers include oils such as cashew oil and tall oil, and resins such as melamine resin, xylene resin, and imide resin. These novolac resins can be used alone or in combination.
本発明に用いられるひも状体は、例えば短繊維及び又は
長繊維より構成されるロービング状やヤーン状等のもの
であり、ガラス繊維、カーボン繊維、アラミド繊維、レ
ーヨン繊維、ポリビニルアルコールｌｌ！維、ポリアク
リロニトリルｗｌ維、ポリアミド繊維、ポリエステル繊
維、ポリ塩化ビニリデン繊維および綿糸から成るものが
好適であり、更に好ましくは、ガラス繊維、カーボン繊
維、アラミド繊維、レーヨン繊維および綿糸などから戒
るものが好適である。これらは単独で使用しても良いし
、２種以上組み合わせて使用しても良い。The string-like body used in the present invention is, for example, a roving-like or yarn-like body composed of short fibers and/or long fibers, such as glass fiber, carbon fiber, aramid fiber, rayon fiber, polyvinyl alcohol! Preferably, those consisting of fibers, polyacrylonitrile fibers, polyamide fibers, polyester fibers, polyvinylidene chloride fibers, and cotton threads, and more preferably those made of glass fibers, carbon fibers, aramid fibers, rayon fibers, and cotton threads. suitable. These may be used alone or in combination of two or more.
該ひも状体は必要に応じてシランカップリング剤、エポ
キシ樹脂およびフェノール樹脂などであらかじめ表面処
理されたものも用いられる。ひも状体の断面形状、断面
寸法は特に限定されるわけではないが、断面積を円に換
算した直径が１〜５ｍｍ程度の断面寸法のものが好まし
い。The string-like body may be surface-treated in advance with a silane coupling agent, epoxy resin, phenol resin, etc., if necessary. Although the cross-sectional shape and cross-sectional size of the string-like body are not particularly limited, it is preferable that the cross-sectional size is about 1 to 5 mm in diameter when the cross-sectional area is converted into a circle.
本発明のフェノール系樹脂成形材料は、例えばノボラッ
ク樹脂、硬化剤、硬化促進剤、離型剤、染顔料、溶剤及
び必要に応じて加えられる各種添加剤をそれぞれ所定の
割合で加熱混合し、得られた液体にひも状体を含浸し、
８０〜１２０℃にて加熱乾燥後、１〜１０帥長、好まし
くは２〜６Ｉ！ｌＩ！ｌ長に切断して得られる。該成形
材料のカット長を１〜１０ｍｍ長に限定した理由は、１
閣未満では射出成形可能であるが衝撃強さの低い成形品
しか得られず、また１０ｍｍを越えると衝撃強さは高い
ものの射出成形時の充填性、連続成形性が困難となるた
め好ましくないからである。The phenolic resin molding material of the present invention can be obtained by heating and mixing, for example, a novolak resin, a curing agent, a curing accelerator, a mold release agent, dyes and pigments, a solvent, and various additives added as necessary in predetermined proportions. The string-like body is impregnated with the liquid,
After heating and drying at 80-120°C, the length is 1-10 cm, preferably 2-6 I! lI! Obtained by cutting into l length. The reason why the cut length of the molding material was limited to 1 to 10 mm is as follows:
If the thickness is less than 10 mm, injection molding is possible, but only a molded product with low impact strength can be obtained, and if it exceeds 10 mm, although the impact strength is high, filling properties and continuous moldability during injection molding become difficult, which is not desirable. It is.
本発明で使用される液体としては、メタノール、アセト
ン、テトラヒドロフランなどの有機溶剤を使用する均一
溶液あるいは氷、界面活性剤等を使用するエマルジョン
液等が挙げられる。Examples of liquids used in the present invention include homogeneous solutions using organic solvents such as methanol, acetone, and tetrahydrofuran, and emulsion liquids using ice, surfactants, and the like.
成形材料中のひも状体の体積含有率は、特に限定されな
いが、２０〜６０％、好ましくは３０〜５０％の範囲に
設定するのが望ましい。Although the volume content of the string-like body in the molding material is not particularly limited, it is desirable to set it in the range of 20 to 60%, preferably 30 to 50%.
このようにして得られたフェノール系樹脂成形材料は射
出成形可能であるが、圧縮成形やトランスファー底形に
も利用できることは言うまでもない。The phenolic resin molding material thus obtained can be injection molded, but it goes without saying that it can also be used for compression molding and transfer bottom molding.
以下、実施例により本発明をさらに詳細に説明するが、
本発明はこれらになんら限定されるものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these in any way.
なお、フェノール系樹脂成形材料の性能は次に示す方法
に従って測定した。The performance of the phenolic resin molding material was measured according to the method shown below.
（１〉射出成形性
成形機−ＲＪ−１４０Ｃ（名機製作所■製）金型−イン
ジェクションファミリー
成形条件−金型温度＝１７５±５℃
シリンダー温度（前／後）：
８５±５℃／３０±５℃
射出圧： １０００〜１２００ ｋｇｆ／ｃｄ射出時間
：６±２秒
硬化時間：６０秒
上記の条件で各材料について射出成形を行ない、５０シ
ヨツトの連続射出成形が可能か否かで射出成形性を判定
した。(1> Injection molding machine - RJ-140C (manufactured by Meiki Seisakusho ■) Mold - Injection family molding conditions - Mold temperature = 175 ± 5 ° C Cylinder temperature (front / back): 85 ± 5 ° C / 30 ± 5℃ Injection pressure: 1000-1200 kgf/cd Injection time: 6±2 seconds Curing time: 60 seconds Injection molding was performed for each material under the above conditions, and injection moldability was determined by whether continuous injection molding of 50 shots was possible. was determined.
○：連続射出成形可能
×：連続射出成形不能
（２）シャルピー衝撃強さ及び曲げ強さ前記射出成形に
より得られた試験片を用いてＪＩＳ−Ｋ ６９１１に準
じて測定した。○: Continuous injection molding possible ×: Continuous injection molding impossible (2) Charpy impact strength and bending strength Measured according to JIS-K 6911 using the test piece obtained by the above injection molding.
（３） ２００℃ｘ ｔｏｏｏ時間加熱処理後の曲げ
強さ保持率
前記射出成形により得られた曲げ強さ試験片を２００℃
Ｘ１００Ｏ時間加熱処理後、ＪＩＳ−Ｋ ６９１１Ｌ：
準じ曲げ強さを測定し、初期値を基準にして保持率を求
めた。(3) Bending strength retention rate after heat treatment at 200°C for too long The bending strength test piece obtained by the above injection molding was heated at 200°C.
After heat treatment for X100 hours, JIS-K 6911L:
The bending strength was measured in a similar manner, and the retention rate was determined based on the initial value.
また実施例及び比較例で使用したひも状体の種類は以下
に示すとおりである。Moreover, the types of string-like bodies used in Examples and Comparative Examples are as shown below.
（１）ガラス繊維ロービング
日本硝子繊維■製、ＲＥＲ２３１Ｘ−ＦＷ２８９７、繊
維径：１３ｊ−、番手：２３１０ ｔｅｘ（２）炭素繊
維ロービング
東邦レーヨン■製、）ＩＴ＾−７−１２０００繊維径ニ
アＪｌｌ、番手：ａｉｏ ｔａｘ（３〉アラミド繊維
奇人■製、テクノーラ）ＩＦＹ Ｔ−２４１Ｊ繊維径＝
１２μ、番手：８３Ｑｔｅｘ
実施例１
ノボラック型フェノール樹脂
（数平均分子量： ５５０） １００重量
部へキサメチレンテトラミン １５〃酸化マグ
ネシウム ３ 〃ステアリン酸カルシ
ウム ３ 〃シランカップリング剤
（日本ユニカー■製、Ａ−１１００） １ 〃
グリセリン ５ 〃スピリットブ
ラック ２ 〃メタノール
７０重量部上記各原料を温度計、コンデン
サー及び撹拌機を備えた溶解釜に仕込み、よく撹拌し均
一混合液にした後、含浸槽に移した。(1) Glass fiber roving made by Nippon Glass Fiber ■, RER231X-FW2897, fiber diameter: 13j-, count: 2310 tex (2) Carbon fiber roving made by Toho Rayon ■, IT^-7-12000 fiber diameter near Jll, count : aio tax (3> made by Aramid Fiber Kijin■, Technora) IFY T-241J fiber diameter =
12μ, count: 83Qtex Example 1 Novolac type phenol resin (number average molecular weight: 550) 100 parts by weight Hexamethylenetetramine 15 Magnesium oxide 3 Calcium stearate 3 Silane coupling agent (Nippon Unicar ■, A-1100) 1 〃
Glycerin 5 Spirit Black 2 Methanol
70 parts by weight of each of the above raw materials were charged into a dissolving vessel equipped with a thermometer, a condenser, and a stirrer, stirred thoroughly to make a uniform mixture, and then transferred to an impregnating tank.
つぎにあらかじめフェノール樹脂用に表面処理されたガ
ラス繊維ロービングを上記混合液に含浸し、１００〜１
２０℃の加熱炉で乾燥後、４ｍｍ長に切断し、ガラス繊
維の体積含有率が４０％であるフェノール樹脂成形材料
を得た。該成形材料のスパイラルフローは３４０ｆｆｌ
Ｉ！ｌであった。Next, a glass fiber roving whose surface has been previously treated for phenolic resin is impregnated with the above mixed solution, and
After drying in a heating oven at 20°C, it was cut into 4 mm lengths to obtain a phenolic resin molding material having a glass fiber volume content of 40%. The spiral flow of the molding material is 340ffl
I! It was l.
実施例２
シランカップリング剤を除いた以外は実施例１と同じ配
合及び方法で混合液を製造し、あらかじめフェノール樹
脂用に表面処理されたカーボン繊維ロービングを上記混
合液に含浸し、１００〜１２０℃の加熱炉で乾燥後、４
帥長に切断し、カーボン繊維の体積含有率が４５％であ
るフェノール樹脂成形材料を得た。該成形材料のスパイ
ラルフローは４００ｍｍであった。Example 2 A mixed solution was produced using the same formulation and method as in Example 1, except that the silane coupling agent was removed, and a carbon fiber roving whose surface had been previously treated for phenolic resin was impregnated with the above mixed solution. After drying in a heating oven at 4℃
It was cut into lengths to obtain a phenolic resin molding material having a carbon fiber volume content of 45%. The spiral flow of the molding material was 400 mm.
実施例３
あらかじめフェノール樹脂用に表面処理されたアラミド
繊維ロービングを使用した以外は実施例２と同じ方法で
、カット長が４１Ｘｌｆｌ＋でかつアラミド繊維の体積
含有率が３５％であるフェノール樹脂成形材料を得た。Example 3 A phenolic resin molding material with a cut length of 41Xlfl+ and an aramid fiber volume content of 35% was prepared in the same manner as in Example 2, except that an aramid fiber roving that had been previously surface-treated for phenolic resin was used. Obtained.
該成形材料のスパイラルフローは２８０ｍｎ＋であった
。The spiral flow of the molding material was 280 mn+.
実施例４
実施例１と同様の方法で、カット長が２ｍｍでかつガラ
ス繊維の体積含有率が４０％であるフェノール樹脂成形
材料を得た。該成形材料のスパイラルフローは３７０ｕ
であった。Example 4 A phenolic resin molding material having a cut length of 2 mm and a glass fiber volume content of 40% was obtained in the same manner as in Example 1. The spiral flow of the molding material is 370u
Met.
実施例５
実施例１と同様の方法で、カット長が６印でかつガラス
繊維の体積含有率が４０％であるフェノール樹脂成形材
料を得た。該成形材料のスパイラルフローは３００ｍｍ
であった。Example 5 A phenolic resin molding material having a cut length of 6 marks and a glass fiber volume content of 40% was obtained in the same manner as in Example 1. The spiral flow of the molding material is 300mm
Met.
比較例１
ノボラック型フェノール樹脂 １００重量部ガラス
繊維
〈チョツプドストランド、３關長） １５０ 〃ヘ
キサメチレンテトラミン １５〃酸化マグネシ
ウム ３ 〃ステアリン酸カルシウ
ム ３ 〃シランカップリング剤
（日本ユニカー鞠製、Ａ−１１００） １〃グリ
セリン ５ 〃スピリットブラッ
ク ２ 〃メタノール
１０〃上記各原料をヘンセルミキサーで混合し
、８０〜９０℃でロール混練後、粉砕してフェノール樹
脂成形材料を得た。この材料のガラス繊維の平均繊維長
は０．２ｕであり、その体積含有率は４０％であった。Comparative Example 1 Novolac type phenol resin 100 parts by weight Glass fiber (chopped strand, 3 length) 150 Hexamethylenetetramine 15 Magnesium oxide 3 Calcium stearate 3 Silane coupling agent (Nippon Unicar Mari, A-1100) ) 1 Glycerin 5 Spirit Black 2 Methanol
10. The above raw materials were mixed in a Hensel mixer, kneaded with rolls at 80 to 90°C, and then pulverized to obtain a phenolic resin molding material. The average fiber length of the glass fibers in this material was 0.2u, and its volume content was 40%.
該成形材料のスパイラルフローは４００ｒｍｓであった
。The spiral flow of the molding material was 400 rms.
比較例２
実施例１と同様の方法でカット長が０．５ ｍｍでかつ
ガラス繊維の体積含有率が４０％であるフェノール樹脂
成形材料を得た。該成形材料のスパイラルフローは３８
０叩であった。Comparative Example 2 A phenolic resin molding material having a cut length of 0.5 mm and a glass fiber volume content of 40% was obtained in the same manner as in Example 1. The spiral flow of the molding material is 38
It was 0 hits.
比較例３
実施例１と同様の方法で、カット長が２５ｍｍでかつガ
ラス繊維の体積含有率が４０％であるフェノール樹脂成
形材料を得た。該成形材刺のスパイラルフローは１００
關であった。Comparative Example 3 A phenolic resin molding material having a cut length of 25 mm and a glass fiber volume content of 40% was obtained in the same manner as in Example 1. The spiral flow of the molding material barb is 100
It was relevant.
実施例１〜５及び比較例１〜３の結果を第１表に示す。The results of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1.
表かられかるごとく、比較例１及び２により得られた成
形材料は射出成形性はともに良好であったが、シャルピ
ー衝撃強さはそれぞれ５ｋｇｆ−ｃｍ／ｃｎｆ及び？
ｋｇｆ−ｃｍ／ｃ＋＋ｆであり、実施例１〜５の１５〜
２５ｋｇｆ−ＣＩ！ｌ／ｃｄに比べかなり低ＩＪ４であ
った。また、比較例３により得られた成形材料は、射出
成形においてホッパー落ちが悪く、スクリューでかみこ
みが悪く、また充電不良を起こし、連続成形が不可能で
あった。As can be seen from the table, the injection moldability of the molding materials obtained in Comparative Examples 1 and 2 was good, but the Charpy impact strength was 5 kgf-cm/cnf and ?5 kgf-cm/cnf, respectively.
kgf-cm/c++f, and 15 to 5 in Examples 1 to 5.
25kgf-CI! The IJ4 was considerably lower than l/cd. In addition, the molding material obtained in Comparative Example 3 did not easily fall into the hopper during injection molding, was poorly screwed in, and caused poor charging, making continuous molding impossible.
以上、説明したように、本発明のフェノール系樹脂成形
材料によれば以下のような効果が得られる。As explained above, according to the phenolic resin molding material of the present invention, the following effects can be obtained.
１）従来のフェノール樹脂成形材料を使用して射出成形
にて得られる成形品のシャルピー衝撃強さがせいぜい６
〜７ｋｇｆ−ｃｍ／ｃＩＩ！が限度であるのに対し、本
発明品によれば開底形で１５〜２５ｋｇｆ−ＣＩ１１／
ｃｒｌのシャルピー衝撃強さが得られる。すなわち、２
〜４倍の衝撃強さが得られる。1) The Charpy impact strength of molded products obtained by injection molding using conventional phenolic resin molding materials is 6 at most.
~7kgf-cm/cII! However, according to the product of the present invention, the open-bottom type can handle 15 to 25 kgf-CI11/
A Charpy impact strength of crl is obtained. That is, 2
~4 times the impact strength can be obtained.
２）射出成形において、ホッパー落ち、スクリューでの
かみこみ、充填性が良好であり、連続成形性に優れてい
る。2) In injection molding, hopper drop, screw bite, and filling properties are good, and continuous moldability is excellent.
３〉射出成形にて得られる成形品の熱間クリープ性、耐
熱老化性及び耐ヒートサイクル性等の長期信頼性に優れ
ている。3> The molded product obtained by injection molding has excellent long-term reliability such as hot creep resistance, heat aging resistance, and heat cycle resistance.
上記効果が得られることから、本発明のフェノール系樹
脂成形材料はヒートインシュレーター、インテークマニ
ホールド、コンミテータ−、シリンダーヘッドカバー、
オイルパン等の自動車部品や大型ブレーカ−等の電気部
品など構造部品の成形に好適に使用される。Since the above effects can be obtained, the phenolic resin molding material of the present invention can be used for heat insulators, intake manifolds, commutators, cylinder head covers,
It is suitably used for molding structural parts such as automobile parts such as oil pans and electrical parts such as large breakers.
Claims (1)
ボラック型フェノール系樹脂を主成分とする液体に含浸
し、加熱乾燥後、１〜１０ｍｍ長に切断して成る射出成
形可能なフェノール系樹脂成形材料。 ２）ひも状体が、ガラス繊維、カーボン繊維、アラミド
繊維、レーヨン繊維、ポリビニルアルコール繊維、ポリ
アクリロニトリル繊維、ポリアミド繊維、ポリエステル
繊維、ポリ塩化ビニリデン繊維および綿糸から選ばれた
少くとも一種からなる請求項１記載のフェノール系樹脂
成形材料。[Scope of Claims] 1) A string-like body composed of short fibers and/or long fibers is impregnated with a liquid mainly composed of novolak type phenolic resin, heated and dried, and then cut into lengths of 1 to 10 mm. A phenolic resin molding material that can be injection molded. 2) A claim in which the string-like body is made of at least one selected from glass fiber, carbon fiber, aramid fiber, rayon fiber, polyvinyl alcohol fiber, polyacrylonitrile fiber, polyamide fiber, polyester fiber, polyvinylidene chloride fiber, and cotton yarn. 1. The phenolic resin molding material described in 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1192727A JPH083029B2 (en) | 1989-07-27 | 1989-07-27 | Phenolic resin molding material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1192727A JPH083029B2 (en) | 1989-07-27 | 1989-07-27 | Phenolic resin molding material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0359060A true JPH0359060A (en) | 1991-03-14 |
| JPH083029B2 JPH083029B2 (en) | 1996-01-17 |
Family
ID=16296062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1192727A Expired - Lifetime JPH083029B2 (en) | 1989-07-27 | 1989-07-27 | Phenolic resin molding material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH083029B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916987A (en) * | 1996-05-29 | 1999-06-29 | Mitsui Chemicals, Inc. | Thiol and Sulfur-containing O-(meth) acrylate compounds and use thereof |
| JP2012096368A (en) * | 2010-10-29 | 2012-05-24 | Sumitomo Bakelite Co Ltd | Molded article, high-strength member, and method of manufacturing the molded article |
| JP2023153505A (en) * | 2022-04-05 | 2023-10-18 | 住友ベークライト株式会社 | resin molding material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS629616A (en) * | 1985-07-08 | 1987-01-17 | 松下電器産業株式会社 | Composite capacitor |
| JPS6375039A (en) * | 1986-09-18 | 1988-04-05 | Showa Highpolymer Co Ltd | Production of fiber-reinforced phenolic resin molded article |
-
1989
- 1989-07-27 JP JP1192727A patent/JPH083029B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS629616A (en) * | 1985-07-08 | 1987-01-17 | 松下電器産業株式会社 | Composite capacitor |
| JPS6375039A (en) * | 1986-09-18 | 1988-04-05 | Showa Highpolymer Co Ltd | Production of fiber-reinforced phenolic resin molded article |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916987A (en) * | 1996-05-29 | 1999-06-29 | Mitsui Chemicals, Inc. | Thiol and Sulfur-containing O-(meth) acrylate compounds and use thereof |
| US6114485A (en) * | 1996-05-29 | 2000-09-05 | Mitsui Chemicals, Inc. | Thiol and sulfur-containing O-(meth)acrylate compounds and use thereof |
| US6265510B1 (en) | 1996-05-29 | 2001-07-24 | Mitsui Chemicals, Inc. | Thiol and sulfur-containing O-(meth)acrylate compounds and use thereof |
| US6369269B2 (en) | 1996-05-29 | 2002-04-09 | Mitsui Chemicals, Inc. | Thiol and sulfur-containing O-(meth)acrylate compounds and use thereof |
| JP2012096368A (en) * | 2010-10-29 | 2012-05-24 | Sumitomo Bakelite Co Ltd | Molded article, high-strength member, and method of manufacturing the molded article |
| JP2023153505A (en) * | 2022-04-05 | 2023-10-18 | 住友ベークライト株式会社 | resin molding material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH083029B2 (en) | 1996-01-17 |
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