JPH0343303B2 - - Google Patents
Info
- Publication number
- JPH0343303B2 JPH0343303B2 JP56135844A JP13584481A JPH0343303B2 JP H0343303 B2 JPH0343303 B2 JP H0343303B2 JP 56135844 A JP56135844 A JP 56135844A JP 13584481 A JP13584481 A JP 13584481A JP H0343303 B2 JPH0343303 B2 JP H0343303B2
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- molding
- molding material
- parts
- cylinder
- 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 - Lifetime
Links
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 35
- 239000005011 phenolic resin Substances 0.000 claims description 24
- 239000012778 molding material Substances 0.000 claims description 22
- 229920001568 phenolic resin Polymers 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 13
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 5
- 238000000465 moulding Methods 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 235000013312 flour Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000314 lubricant Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
この発明は、成形時の収縮率が小さく、しかも
射出成形時のシリンダ安定性にすぐれたフエノー
ル樹脂成形材料に関する。
従来、フエノール樹脂を主成分とするフエノー
ル樹脂成形材料が、機械部品，食器，事務用品な
どさまざまな成形品に用いられている。それは、
フエノール樹脂が機械的強度，耐熱性が良好で、
かつ比較的安価であること等すぐれた特性を持つ
からである。しかしながら、このフエノール樹脂
成形材料は成形時の収縮率が比較的大きいため、
寸法精度の高い成形品等を得ることが困難であつ
た。
この問題を解決するため、特定粒度の木粉を樹
脂で被覆し、これを充填剤として成形材料に添加
する方法が考えられた。しかし、この方法による
と収縮率が小さくなる反面、シリンダ安定性が悪
くなるという問題が新たに生じた。
フエノール樹脂成形材料は、射出成形法により
成形されることが多い。それはこの成形方法が複
雑な形状の製品の大量生産に適しているからであ
る。射出成形法は、成形材料を加熱シリンダ内で
可塑化させ、ノズルより型の中に射出し、冷却固
化させて成形品を得る方法である。したがつて、
成形材料のシリンダ内での流動可能時間が短かけ
れば、成形が困難となる。
上記の充填剤を加えると、この流動可能時間が
短かくなり、シリンダ安定性が不充分となるので
ある。
このように、成形時の収縮率およびシリンダ安
定性を同時に満足させる成形材料を得ることは困
難であつた。
この発明は、このような事情に鑑みなされたも
ので、成形時の収縮率が小さく、しかもシリンダ
安定性にすぐれた成形材料を提供するものであ
る。
すなわち、この発明にかかるフエノール樹脂成
形材料は、変性フエノール樹脂および充填剤を含
むフエノール樹脂成形材料であつて、上記変性フ
エノール樹脂が、所定量のフエノール類の５〜35
重量％をジシクロペンタジエンで置き換えたもの
に対し所定量のホルムアルデヒド類を反応させて
得られたものであることを特徴としている。以
下、この発明を詳しく説明する。
主要成分は、変性フエノール樹脂である。この
変性フエノール樹脂は、普通のフエノール樹脂と
は異なり、フエノール樹脂の１部がジシクロペン
タジエンで置き換えられている。すなわち、所定
量のフエノール類の５〜35重量％がジシクロペン
タジエン類で置き換えられたものに対し、酸性下
あるいはアルカリ性下で、所定量のホルムアルデ
ヒド類を反応させて得られたノボラツク型あるい
はレゾール型の変性フエノール樹脂である。フエ
ノール類としては、フエノール，クレゾール，レ
ゾルシン等が用いられる。また、アルデヒド類と
してはホルムアルデヒド，パラホルムアルデヒド
等が用いられる。ジシクロペンタジエンは、反応
時、フエノール類に付加して高分子化するものと
考えられる。
この発明にかかるフエノール樹脂成形材料は、
変性フエノール樹脂と充填剤を含むものであつ
て、変性フエノール樹脂が上記のような変性フエ
ノール樹脂であるため、成形時の収縮率が小さ
く、しかもシリンダ安定性にすぐれているのであ
る。
この発明にかかるフエノール樹脂成形材料も、
普通のものと同様に、木粉、パルプ、綿屑、炭酸
カルシウムなどの充填剤を含み、使用目的その他
の必要に応じて、下記に例示されるような各種の
添加材料が加えられている。たとえば、水，フル
フラール，アニリンなどの可塑剤、石炭，酸化マ
グネシウムなどの促進剤，ステアリン酸およびそ
の塩などの滑剤、各種着色剤、ヘキサメチレンテ
トラミンなどの硬化剤、アニリン，レゾルシン，
アルキルフエノールなどの変性剤などである。
これらの原料を用いて成形材料をつくる方法
は、通常の方法による。
この発明にかかるフエノール樹脂成形材料は、
上記のように構成されるため、成形時の収縮率が
小さく、しかもシリンダ安定性にすぐれている。
つぎに、実施例について従来例と併せて説明す
る。
実施例および従来例のフエノール樹脂成形材料
を下記のようにしてつくつた。
（実施例）
まず、変性フエノール樹脂をつくつた。
フエノール 75重量部（以下「部」と略す）
ジシクロペンタジエン 19部
37％ホルマリン 68.9部
Ｆ／Ｐ＝0.85）
上記の原料配合物を酸性下，還流温度で60分間
反応させることにより、ノボラツク型変性フエノ
ール樹脂を得た。
得られた変性フエノール樹脂を用いて、下記の
配合で原料を混和し、フエノール樹脂成形材料を
つくつた。
変性フエノール樹脂 40部
木 粉 39部
炭酸カルシウム 10部
ヘキサメチレンテトラミン ８部
ステアリン酸 1.5部
着色剤 1.5部
（従来例）
まず、フエノール樹脂をつくつた。
フエノール 94部
37％ホルマリン 68.9部
（Ｆ／Ｐ＝0.85）
上記の原料を実施例と同様の反応条件で反応さ
せ、ノボラツク型フエノール樹脂を得た。
実施例において、フエノール樹脂のかわりに同
量の上記フエノール樹脂を用いるようにしたほか
は、実施例と同様にして、フエノール樹脂成形材
料をつくつた。
上記の実施例および従来例のフエノール樹脂成
形材料を用いて、射出成形法により成形品をつく
り、その際、シリンダ安定性および成形収縮率の
試験を行なつた。結果を第１表に示す。
成形条件および試験方法はつぎのとおりであ
る。成形条件は、100トン型射出成形機を用い、
シリンダ後部温度80℃，シリンダ前部温度100℃，
金型温度160℃とした。シリンダ安定性はシリン
ダ内部での流動可能時間であらわされ、その時の
成形材料の温度は100℃であつた。成形収縮率は
JIS Ｋ 6911による。
The present invention relates to a phenolic resin molding material that has a low shrinkage rate during molding and has excellent cylinder stability during injection molding. Conventionally, phenolic resin molding materials containing phenolic resin as a main component have been used for various molded products such as mechanical parts, tableware, and office supplies. it is,
Phenol resin has good mechanical strength and heat resistance,
This is because it has excellent characteristics such as being relatively inexpensive. However, this phenolic resin molding material has a relatively large shrinkage rate during molding, so
It has been difficult to obtain molded products with high dimensional accuracy. In order to solve this problem, a method was considered in which wood flour of a specific particle size was coated with resin and added to the molding material as a filler. However, although this method reduces the shrinkage rate, a new problem has arisen in that the cylinder stability deteriorates. Phenol resin molding materials are often molded by injection molding. This is because this molding method is suitable for mass production of products with complex shapes. In the injection molding method, a molding material is plasticized in a heated cylinder, injected into a mold through a nozzle, and cooled and solidified to obtain a molded product. Therefore,
If the time during which the molding material can flow within the cylinder is short, molding becomes difficult. Addition of the above-mentioned fillers shortens this flowable time and results in insufficient cylinder stability. As described above, it has been difficult to obtain a molding material that simultaneously satisfies the shrinkage rate and cylinder stability during molding. The present invention was made in view of the above circumstances, and it is an object of the present invention to provide a molding material that has a small shrinkage rate during molding and has excellent cylinder stability. That is, the phenolic resin molding material according to the present invention is a phenolic resin molding material containing a modified phenolic resin and a filler, wherein the modified phenolic resin contains a predetermined amount of 5 to 35 phenols.
It is characterized in that it is obtained by reacting a predetermined amount of formaldehyde with dicyclopentadiene in which the weight percent is replaced with dicyclopentadiene. This invention will be explained in detail below. The main component is a modified phenolic resin. This modified phenolic resin differs from ordinary phenolic resin in that part of the phenolic resin is replaced with dicyclopentadiene. That is, a novolak type or resol type obtained by reacting a prescribed amount of formaldehyde under acidic or alkaline conditions with a prescribed amount of phenols in which 5 to 35% by weight is replaced with dicyclopentadiene. This is a modified phenolic resin. As the phenols, phenol, cresol, resorcinol, etc. are used. Moreover, formaldehyde, paraformaldehyde, etc. are used as aldehydes. It is thought that dicyclopentadiene is added to phenols to form a polymer during the reaction. The phenolic resin molding material according to this invention is
It contains a modified phenolic resin and a filler, and since the modified phenolic resin is the above-mentioned modified phenolic resin, the shrinkage rate during molding is small and the cylinder stability is excellent. The phenolic resin molding material according to this invention also includes:
Like ordinary products, it contains fillers such as wood flour, pulp, cotton waste, and calcium carbonate, and various additive materials such as those exemplified below are added depending on the purpose of use and other needs. For example, water, plasticizers such as furfural and aniline, accelerators such as coal and magnesium oxide, lubricants such as stearic acid and its salts, various colorants, hardening agents such as hexamethylenetetramine, aniline, resorcinol,
These include modifiers such as alkylphenols. A molding material can be produced using these raw materials by a conventional method. The phenolic resin molding material according to this invention is
Since the structure is as described above, the shrinkage rate during molding is small and the cylinder stability is excellent. Next, an embodiment will be described together with a conventional example. The phenolic resin molding materials of Examples and Conventional Examples were prepared as follows. (Example) First, a modified phenolic resin was produced. Phenol 75 parts by weight (hereinafter referred to as "parts") Dicyclopentadiene 19 parts 37% Formalin 68.9 parts F/P = 0.85) The above raw material mixture was reacted under acidic conditions at reflux temperature for 60 minutes to undergo novolac type modification. A phenolic resin was obtained. Using the obtained modified phenolic resin, raw materials were mixed in the following formulation to produce a phenolic resin molding material. Modified phenolic resin 40 parts Wood flour 39 parts Calcium carbonate 10 parts Hexamethylenetetramine 8 parts Stearic acid 1.5 parts Colorant 1.5 parts (conventional example) First, phenolic resin was made. Phenol 94 parts 37% Formalin 68.9 parts (F/P=0.85) The above raw materials were reacted under the same reaction conditions as in the examples to obtain a novolak type phenolic resin. In the example, a phenolic resin molding material was prepared in the same manner as in the example except that the same amount of the above phenolic resin was used instead of the phenolic resin. Molded products were made by injection molding using the phenolic resin molding materials of the above examples and conventional examples, and tests for cylinder stability and mold shrinkage were conducted. The results are shown in Table 1. The molding conditions and test methods are as follows. The molding conditions were a 100 ton injection molding machine.
Cylinder rear temperature 80℃, cylinder front temperature 100℃,
The mold temperature was 160°C. Cylinder stability is expressed by the time during which it can flow inside the cylinder, and the temperature of the molding material at that time was 100°C. The molding shrinkage rate is
According to JIS K 6911.
【表】
実施例は、シリンダ安定性および成形収縮率いず
れの面でも、従来例よりすぐれている。[Table] The example is superior to the conventional example in terms of both cylinder stability and molding shrinkage rate.
Claims (1)
ノール樹脂成形材料であつて、上記変性フエノー
ル樹脂が、所定量のフエノール類の５〜35重量％
をジシクロペンタジエンで置き換えたものに対し
所定量のホルムアルデヒド類を反応させて得られ
たものであることを特徴とするフエノール樹脂成
形材料。1 A phenolic resin molding material containing a modified phenolic resin and a filler, in which the modified phenolic resin accounts for 5 to 35% by weight of a predetermined amount of phenols.
A phenolic resin molding material obtained by reacting a predetermined amount of formaldehyde with dicyclopentadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13584481A JPS5837021A (en) | 1981-08-28 | 1981-08-28 | Phenolic resin molding material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13584481A JPS5837021A (en) | 1981-08-28 | 1981-08-28 | Phenolic resin molding material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5837021A JPS5837021A (en) | 1983-03-04 |
| JPH0343303B2 true JPH0343303B2 (en) | 1991-07-02 |
Family
ID=15161076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13584481A Granted JPS5837021A (en) | 1981-08-28 | 1981-08-28 | Phenolic resin molding material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5837021A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH046829Y2 (en) * | 1985-11-01 | 1992-02-25 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441992A (en) * | 1977-09-09 | 1979-04-03 | Mitsui Toatsu Chem Inc | Preparation of modified phenol resin |
| JPS54154492A (en) * | 1978-03-18 | 1979-12-05 | Hoechst Ag | Modified novolak * preparation and use therefor |
| JPS55102621A (en) * | 1979-01-30 | 1980-08-06 | Hitachi Chem Co Ltd | Preparation of phenolic resin modified with polybutadiene |
-
1981
- 1981-08-28 JP JP13584481A patent/JPS5837021A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441992A (en) * | 1977-09-09 | 1979-04-03 | Mitsui Toatsu Chem Inc | Preparation of modified phenol resin |
| JPS54154492A (en) * | 1978-03-18 | 1979-12-05 | Hoechst Ag | Modified novolak * preparation and use therefor |
| JPS55102621A (en) * | 1979-01-30 | 1980-08-06 | Hitachi Chem Co Ltd | Preparation of phenolic resin modified with polybutadiene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5837021A (en) | 1983-03-04 |
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