JPS643904B2 - - Google Patents
Info
- Publication number
- JPS643904B2 JPS643904B2 JP6431983A JP6431983A JPS643904B2 JP S643904 B2 JPS643904 B2 JP S643904B2 JP 6431983 A JP6431983 A JP 6431983A JP 6431983 A JP6431983 A JP 6431983A JP S643904 B2 JPS643904 B2 JP S643904B2
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- conductive
- extrusion molding
- composition
- short fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Description
本発明は導電性フエノール樹脂押出成形用組成
物に関し、更に詳しくは、シリンダー、ロール、
パイプ及びその他の異形品をはじめとする成形
品、特に導電性と鏡状表面（表面粗さ0.25μ以下
で且つ５cm角当たりに存在する径10μ以上のボイ
ドの数が10個以下の高精度表面）の必要な精密成
形品を連続的に押出成形可能な導電性フエノール
樹脂押出成形用組成物に関する。
フエノール樹脂成形用組成物は、熱可塑性樹脂
成形用組成物に比較して熱時の機械的強度が優れ
ると共に、他の熱硬化性樹脂成形用組成物に比較
しても、機械的強度、耐熱性、物理性能等に優れ
且つ比較的安価であるため、種々の成形品に用い
られている。
そして、このようなフエノール樹脂組成物の特
性を利用して、これに導電性を付与せしめるため
に、シリカ、炭酸カルシウム等の充填材と共に、
黒鉛、カーボンブラツク、金属粉末等の導電性材
料を添加してなる導電性フエノール樹脂成形用組
成物が知られており、その体積固有抵抗も10-2〜
104Ω・cmのものが得られているのである。
しかしながら、かかる導電性フエノール樹脂成
形用組成物は、種々なる充填材が機械的強度やコ
スト抵減等の目的から補強剤として含有されてお
り、一般にその成形法も圧縮成形や射出成形等に
限定されていて、到底連続的な押出成形のできる
ものではなく、成形品自身も寸法精度、表面精度
等が粗く、前記する如き鏡状表面を必要とする精
密成形品の製造には用いられていないのが実情で
ある。
本発明は、かかる事情に基づいて発明されたも
のであつて、機械的強度、耐熱性、物理特性及び
比較的安価なフエノール樹脂を主体とする導電性
フエノール樹脂押出成形用組成物、特に鏡状表面
を必要とする精密成形品を製造するための導電性
フエノール樹脂押出成形用組成物を提供すること
を目的とし、この目的を達成するために、フエノ
ール樹脂を主体とする組成物において、導電性カ
ーボンブラツクと繊維長が30〜300μの短繊維と
を含有せしめてなる構成としたのである。
以下、本発明を詳説する。
本発明におけるフエノール樹脂としては、フエ
ノール、クレゾール等のフエノール類又はリグニ
ン、キシレン、ナフタレン等の変性フエノール類
と、ホルマリン、パラホルムアルデヒド等のアル
デヒド類とを所定のモル比に配合し、塩酸、硫酸
等の酸性触媒下で反応させて得られるノボラツク
型フエノール樹脂初期縮合物、あるいは、水酸化
ナトリウム、アンモニア、アミン等の塩基性触媒
下で反応させて得られるレゾール型フエノール樹
脂初期縮合物などが用いられる。ノボラツク型フ
エノール樹脂初期縮合物を用いる場合は、硬化剤
としてヘキサメチレンテトラミンを樹脂100重量
部に対して５〜20重量部添加する。
本発明における導電性カーボンブラツクとして
は、アセチレンブラツク、ケツチエンブラツク等
が用いられ、その組成物中の含有量は、フエノー
ル樹脂100重量部に対して、30〜100重量部が好ま
しい。これ以下では導電性に劣り、これ以上では
機械的強度が劣る。
又、本発明における短繊維としては、繊維長が
30〜300μの無機質あるいは有機質短繊維が用い
られる。無機質短繊維としては、ガラス繊維、カ
ーボン繊維、アスベスト繊維等が用いられ、有機
質繊維としては、ポリアミド繊維等が用いられ
る。そして、この短繊維は、フエノール樹脂100
重量部に対して10〜200重量部用いられる。
尚、本発明における導電性フエノール樹脂押出
成形用組成物には、上記以外の材料として、顔
料、滑剤、可塑剤等を適宜含有せしめることがで
きる。
かかる本発明の導電性フエノール樹脂押出成形
用組成物によれば、第１図に示す如き、導電性フ
エノール樹脂押出成形用組成物５をプランジヤー
１を用いて押出すようにしたシリンダ２と、該シ
リンダ２の先端に連結され、該プランジヤー１の
断面積より小さな内断面積を有し、且つ入口部に
テーパ面３ａが形成された所定の製品外形を与え
る加熱手段付きダイス３と、前記シリンダ２から
該ダイス３内に延びるマンドレル４とを備え、前
記プランジヤー１の押出作用によつて前記導電性
フエノール樹脂押出成形用組成物５を、加熱、硬
化せしめつつ、該ダイス３と該マンドレル４との
間隙を通じて所定の成形品を連続的に押出成形す
るよにした押出成形装置１０において、シリンダ
２からダイス３へ通ずる型内では、ダイス３の入
口部にテーパ面３ａが形成されているので、プラ
ンジヤー１の押出作用によつて押出される組成物
は、一度テーパ面３ａに衝突し型内で均一な流動
物を形成すると共に、組成物中に含有されている
繊維長30〜300μの短繊維が、溶解したフエノー
ル樹脂をテーパ面に付着させないよう下方へ押出
させるよう配向するので、押出成形性が顕著に向
上するのである。そして、このようにして成形さ
れた成形品は、不均一な残留応力が残ることもな
く、所定の導電性を有し且つ鏡状表面を有するの
である。
本発明によれば、繊維長が30μ以下の短繊維で
は上記効果は小さく、300μ以上の短繊維ではう
まく配向できず流動性に悪影響が出るので、30〜
300μのものが好適に用いられる。
又、短繊維の含有量はフエノール樹脂100重量
部に対して、10重量部以下では上記効果は小さ
く、200重量部以上では流動性に悪影響が出るば
かりでなく機械的強度が低下するので、10〜200
重量部の範囲で用いるのがよい。
次に、本発明の効果を具体的に示すために、以
下の実施例及び比較例に基づいて説明する。
実施例 １〜４
融点90℃のノボラツク型フエノール樹脂（住友
デユレツ製スミライトレジンPR−50072）を用
い、表−１に示す組成に従つて混合機で混合し、
ロール混練後粉砕してペレツト状導電性フエノー
ル樹脂押出成形用組成物を得た。次いでこの組成
物を第１図に示した構造の押出成形装置を用い
て、外径80φ、内径72φの中空パイプを連続的に
押出成形した。表−１にその時の押出成形性と、
得られた成形品の体積固有抵抗、表面粗さ、表面
ボイド等を測定した結果を示す。
比較例 １〜３
表−１に示す組成に従つて、実施例と同様にし
て導電性フエノール樹脂成形用組成物を得、この
組成物を実施例と同様にして成形品を得、同様の
特性を調べた。
The present invention relates to a composition for extrusion molding of conductive phenolic resin, and more particularly, to a composition for extrusion molding of a conductive phenolic resin.
Molded products such as pipes and other irregularly shaped products, especially conductive and mirror-like surfaces (high-precision surfaces with a surface roughness of 0.25μ or less and the number of voids of 10μ or more in diameter per 5cm square of 10 or less) ) It relates to a conductive phenolic resin extrusion molding composition that can continuously extrude the necessary precision molded products. Phenol resin molding compositions have superior mechanical strength when heated compared to thermoplastic resin molding compositions, and also have superior mechanical strength and heat resistance compared to other thermosetting resin molding compositions. It is used in a variety of molded products because it has excellent properties such as physical properties and is relatively inexpensive. In order to make use of the characteristics of the phenolic resin composition and impart conductivity to it, along with fillers such as silica and calcium carbonate,
Conductive phenolic resin molding compositions made by adding conductive materials such as graphite, carbon black, and metal powder are known, and their volume resistivity is 10 -2 ~
A value of 10 4 Ω・cm has been obtained. However, such conductive phenolic resin molding compositions contain various fillers as reinforcing agents for the purpose of mechanical strength and cost reduction, and the molding methods are generally limited to compression molding, injection molding, etc. However, continuous extrusion molding is not possible, and the molded product itself has rough dimensional accuracy and surface accuracy, so it is not used for manufacturing precision molded products that require mirror-like surfaces as described above. That is the reality. The present invention was invented based on the above circumstances, and provides a conductive phenolic resin extrusion molding composition mainly composed of a phenolic resin that has good mechanical strength, heat resistance, physical properties, and is relatively inexpensive. The purpose of the present invention is to provide a conductive phenolic resin extrusion molding composition for producing precision molded products that require a surface. It has a structure containing carbon black and short fibers with a fiber length of 30 to 300 μm. The present invention will be explained in detail below. The phenolic resin in the present invention is prepared by blending phenols such as phenol and cresol, or modified phenols such as lignin, xylene, and naphthalene, and aldehydes such as formalin and paraformaldehyde in a predetermined molar ratio, and using hydrochloric acid, sulfuric acid, etc. A novolak-type phenolic resin initial condensate obtained by reacting under an acidic catalyst, or a resol-type phenolic resin initial condensate obtained by reacting under a basic catalyst such as sodium hydroxide, ammonia, or an amine are used. . When a novolak type phenolic resin initial condensate is used, 5 to 20 parts by weight of hexamethylenetetramine is added as a curing agent per 100 parts by weight of the resin. As the conductive carbon black in the present invention, acetylene black, ketone black, etc. are used, and the content thereof in the composition is preferably 30 to 100 parts by weight per 100 parts by weight of the phenolic resin. If it is less than this, the conductivity will be poor, and if it is more than this, the mechanical strength will be poor. In addition, the short fibers in the present invention have a fiber length of
Inorganic or organic short fibers of 30 to 300 microns are used. As the inorganic short fibers, glass fibers, carbon fibers, asbestos fibers, etc. are used, and as the organic fibers, polyamide fibers, etc. are used. And this short fiber is made of 100% phenolic resin.
10 to 200 parts by weight are used. Incidentally, the conductive phenolic resin extrusion molding composition of the present invention may appropriately contain pigments, lubricants, plasticizers, etc. as materials other than those mentioned above. According to the conductive phenolic resin extrusion molding composition of the present invention, as shown in FIG. A die 3 with a heating means is connected to the tip of the cylinder 2, has an internal cross-sectional area smaller than the cross-sectional area of the plunger 1, and has a tapered surface 3a formed at the inlet portion, and is equipped with a heating means for giving the product a predetermined external shape; and a mandrel 4 extending from the die 3 into the die 3, and while the conductive phenolic resin extrusion molding composition 5 is heated and cured by the extrusion action of the plunger 1, the die 3 and the mandrel 4 are heated and cured. In an extrusion molding apparatus 10 that is configured to continuously extrude a predetermined molded product through a gap, a tapered surface 3a is formed at the entrance of the die 3 in the mold leading from the cylinder 2 to the die 3. The composition extruded by the extrusion action in step 1 once collides with the tapered surface 3a to form a uniform fluid within the mold, and the short fibers with a fiber length of 30 to 300μ contained in the composition are Since the melted phenol resin is oriented to be extruded downward so as not to adhere to the tapered surface, extrusion moldability is significantly improved. The molded product thus formed has a predetermined electrical conductivity and a mirror-like surface without residual uneven residual stress. According to the present invention, short fibers with a fiber length of 30μ or less have little effect, while short fibers with a fiber length of 300μ or more cannot be oriented well and have an adverse effect on fluidity.
A material having a diameter of 300μ is preferably used. In addition, if the content of short fibers is less than 10 parts by weight, the above effect will be small, and if it exceeds 200 parts by weight, not only will the flowability be adversely affected but also the mechanical strength will decrease. ~200
It is preferable to use within the range of parts by weight. Next, in order to concretely demonstrate the effects of the present invention, a description will be given based on the following examples and comparative examples. Examples 1 to 4 Using a novolac type phenolic resin (Sumitomo Durez Sumilite Resin PR-50072) with a melting point of 90°C, the composition was mixed in a mixer according to the composition shown in Table 1.
After roll kneading, the mixture was pulverized to obtain a pellet-like conductive phenolic resin extrusion molding composition. Next, this composition was continuously extruded into a hollow pipe having an outer diameter of 80φ and an inner diameter of 72φ using an extrusion molding apparatus having the structure shown in FIG. Table-1 shows the extrusion moldability at that time,
The results of measuring the volume resistivity, surface roughness, surface voids, etc. of the obtained molded product are shown. Comparative Examples 1 to 3 Conductive phenolic resin molding compositions were obtained in the same manner as in the examples according to the compositions shown in Table 1, and molded articles were obtained in the same manner as in the examples with this composition. I looked into it.
【表】
尚、上記実施例及び比較例においては次に示す
押出成形条件にて行なつた。
プランジヤー押出圧力；70Kg／cm2
ダイス入口部温度；140℃
表−１から明らかな如く、短繊維を含有しない
もの（比較例１）は連続押出成形不可であり、繊
維長が30μ以下のもの（比較例２）や300μ以上の
もの（比較例３）は、連続押出成形可能ではある
が、得られた成形品は鏡状表面が得られない。こ
れに対し、繊維長が30〜300μの範囲の短繊維を
含有せしめたもの（実施例１〜４）は、連続押出
成形可能であると共に、鏡状表面を有する成形品
を得ることができる。
なお、各実施例において得られた成形品の寸法
精度は、内、外径とも0.05mm以内であり、真円度
は、内、外径とも0.02mm以内であつた。
以上詳説した如く、本発明の導電性フエノール
樹脂押出成形用組成物は、圧縮成形あるいは射出
成形等によつて製作される精密成形品以外の一般
成形品において、無機質あるいは有機質充填剤を
補強剤として用いるのとは異なり、無機質あるい
は有機質短繊維を流動押出時での配向性に着目し
て含有せしめたことに特徴があるのであり、これ
によつて従来からの導電性フエノール樹脂組成物
の連続押出成形の困難さを見事に解決したもので
ある。[Table] In the above Examples and Comparative Examples, extrusion molding was carried out under the following extrusion conditions. Plunger extrusion pressure: 70 Kg/cm 2 Die inlet temperature: 140°C As is clear from Table 1, the one that does not contain short fibers (Comparative Example 1) cannot be continuously extruded, and the one with a fiber length of 30μ or less ( Comparative Example 2) and those with a diameter of 300μ or more (Comparative Example 3) can be continuously extruded, but the resulting molded products cannot have a mirror-like surface. On the other hand, those containing short fibers having a fiber length of 30 to 300 μm (Examples 1 to 4) can be continuously extruded and can provide molded products having mirror-like surfaces. The dimensional accuracy of the molded products obtained in each example was within 0.05 mm for both the inner and outer diameters, and the roundness was within 0.02 mm for both the inner and outer diameters. As explained in detail above, the conductive phenolic resin extrusion molding composition of the present invention can be used as a reinforcing agent with an inorganic or organic filler in general molded products other than precision molded products manufactured by compression molding, injection molding, etc. It is characterized by containing inorganic or organic short fibers with a focus on their orientation during fluidized extrusion, unlike conventional methods of continuous extrusion of conductive phenolic resin compositions. This is a brilliant solution to the difficulty of molding.
第１図は本発明を説明するための押出成形装置
の側面要部断面図である。
１……プランジヤー、２……シリンダ、３……
ダイス、３ａ……テーパ面、４……マンドレル、
５……導電性フエノール樹脂押出成形用組成物、
１０……押出成形装置。
FIG. 1 is a side sectional view of a main part of an extrusion molding apparatus for explaining the present invention. 1... Plunger, 2... Cylinder, 3...
Dice, 3a...Tapered surface, 4...Mandrel,
5... Conductive phenolic resin extrusion molding composition,
10...Extrusion molding device.
Claims (1)
物において、導電性カーボンブラツクと繊維長が
30〜300μの短繊維とを含有せしめてなることを
特徴とする導電性フエノール樹脂押出成形用組成
物。 ２ フエノール樹脂100重量部に対して、導電性
カーボンブラツクを30〜100重量部と、短繊維を
10〜200重量部とを含有せしめてなる特許請求の
範囲第１項記載の導電性フエノール樹脂押出成形
用組成物。[Claims] 1. In an extrusion molding composition mainly composed of phenolic resin, conductive carbon black and fiber length are
A composition for extrusion molding of a conductive phenolic resin, characterized in that it contains short fibers of 30 to 300μ. 2 For 100 parts by weight of phenolic resin, add 30 to 100 parts by weight of conductive carbon black and short fibers.
The conductive phenolic resin extrusion molding composition according to claim 1, which contains 10 to 200 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6431983A JPS59189160A (en) | 1983-04-12 | 1983-04-12 | Electrically conductive phenolic resin extrusion composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6431983A JPS59189160A (en) | 1983-04-12 | 1983-04-12 | Electrically conductive phenolic resin extrusion composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59189160A JPS59189160A (en) | 1984-10-26 |
| JPS643904B2 true JPS643904B2 (en) | 1989-01-24 |
Family
ID=13254791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6431983A Granted JPS59189160A (en) | 1983-04-12 | 1983-04-12 | Electrically conductive phenolic resin extrusion composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59189160A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4645717A (en) * | 1982-11-17 | 1987-02-24 | Charleswater Products, Inc. | Solution for use in impregnating paper for high-pressure antistatic laminates |
| JPS6178868A (en) * | 1984-09-27 | 1986-04-22 | Mitsui Toatsu Chem Inc | Thermosetting resin molding material |
| JPS6181459A (en) * | 1984-09-28 | 1986-04-25 | Mitsui Toatsu Chem Inc | Thermosetting resin composition |
| JPS61287951A (en) * | 1985-06-14 | 1986-12-18 | Toshiba Chem Corp | Phenolic resin composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49130967A (en) * | 1973-04-19 | 1974-12-16 | ||
| JPS51151794A (en) * | 1975-06-23 | 1976-12-27 | Teruo Nagano | Phenolic resin composition for extrusion |
| JPS523690A (en) * | 1975-06-26 | 1977-01-12 | Matsushita Electric Works Ltd | Phenolic resin compositions |
-
1983
- 1983-04-12 JP JP6431983A patent/JPS59189160A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59189160A (en) | 1984-10-26 |
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