JPH04318011A - Production of phenolic resin for molding material - Google Patents
Production of phenolic resin for molding materialInfo
- Publication number
- JPH04318011A JPH04318011A JP8430091A JP8430091A JPH04318011A JP H04318011 A JPH04318011 A JP H04318011A JP 8430091 A JP8430091 A JP 8430091A JP 8430091 A JP8430091 A JP 8430091A JP H04318011 A JPH04318011 A JP H04318011A
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- molding material
- molding
- phenol
- reaction
- 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
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 20
- 239000012778 molding material Substances 0.000 title claims abstract description 15
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 15
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 23
- 150000002989 phenols Chemical class 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000465 moulding Methods 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 5
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 4
- 229920002866 paraformaldehyde Polymers 0.000 abstract description 4
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920003987 resole Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide 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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、マイクロスイッチ等の
電気部品やヒートインシュレータ等の自動車部品の成形
のための成形材料用として適したフェノール樹脂の製造
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a phenolic resin suitable for use as a molding material for electrical parts such as microswitches and automobile parts such as heat insulators.
【0002】0002
【従来の技術】フェノール樹脂成形材料は、電気部品や
自動車部品の成形において金属部材のインサート成形を
行なう場合、アンモニア、メチルアミン等を発生しない
レゾール樹脂を使用している。このレゾール樹脂は、ホ
ルムアルデヒドとフェノール類をCa(OH)2、Na
OH、KOH、アンモニア等のアルカリ触媒存在下で反
応させて得たものであり、これに補強や増量材としての
充填材や添加剤を適宜配合して混練後、粉砕して成形材
料としている。BACKGROUND OF THE INVENTION Phenol resin molding materials are resol resins that do not generate ammonia, methylamine, etc. when insert molding metal parts in the molding of electrical and automobile parts. This resol resin is made by replacing formaldehyde and phenols with Ca(OH)2, Na
It is obtained by reacting in the presence of an alkali catalyst such as OH, KOH, or ammonia, and is mixed with appropriate fillers and additives as reinforcing or extenders, kneaded, and then ground to form a molding material.
【0003】0003
【発明が解決しようとする課題】上記レゾール樹脂は、
常温でも反応が進みやすく、貯蔵安定性がよくない。成
形材料にして、射出成形するときにも反応が進みやすく
、シリンダ安定性が悪い。また、未反応フェノール成分
が多く含まれているため、成形サイクルが長くなってし
まう。本発明が解決しようとする課題は、フェノール樹
脂の貯蔵安定性をよくし、成形材料としたときに、射出
成形のシリンダ安定性をよくすると共に成形サイクルを
短くすることである。[Problem to be solved by the invention] The above resol resin is
The reaction progresses easily even at room temperature, and storage stability is poor. When used as a molding material and injection molded, reactions tend to proceed, resulting in poor cylinder stability. Furthermore, since it contains a large amount of unreacted phenol component, the molding cycle becomes long. The problem to be solved by the present invention is to improve the storage stability of a phenolic resin and, when used as a molding material, to improve cylinder stability for injection molding and to shorten the molding cycle.
【0004】0004
【課題を解決するための手段】上記課題を解決するため
に、本発明に係る成形材料用フェノール樹脂は、次のよ
うにして製造する。まず、第1段目の反応として、ホル
ムアルデヒド/フェノール類のモル比を1.2〜1.3
とし、トリエチルアミン触媒存在下で反応を行なわせる
。
その後、アンモニア触媒存在下で第2段目の反応を行な
わせるものである。[Means for Solving the Problems] In order to solve the above problems, the phenolic resin for molding materials according to the present invention is produced as follows. First, in the first stage reaction, the molar ratio of formaldehyde/phenols was adjusted to 1.2 to 1.3.
and the reaction is carried out in the presence of a triethylamine catalyst. Thereafter, a second stage reaction is carried out in the presence of an ammonia catalyst.
【0005】[0005]
【作用】上記のような反応のさせかたにより、生成する
フェノール樹脂の分子量を大きくでき、未反応フェノー
ル成分を少なくすることができる。低分子量フェノール
樹脂や未反応のフェノール成分が少ないことから常温で
安定であり、成形材料にして射出成形したときには、シ
リンダ内で急激な硬化反応が起こらず安定であり、金型
内の高い温度では、速く硬化して成形サイクルを短くで
きる。ホルムアルデヒド/フェノール類のモル比は、1
.2未満では成形材料としたときの硬化性が十分でなく
、1.3を越えると射出成形をするときのシリンダ安定
性が低下する。[Operation] By carrying out the reaction as described above, the molecular weight of the phenol resin produced can be increased and the amount of unreacted phenol component can be reduced. It is stable at room temperature due to its low molecular weight phenolic resin and small amount of unreacted phenol components, and when injection molded as a molding material, it is stable without rapid curing reaction within the cylinder, and at high temperatures inside the mold. , it cures quickly and can shorten the molding cycle. The molar ratio of formaldehyde/phenols is 1
.. If it is less than 2, the curability when used as a molding material is insufficient, and if it exceeds 1.3, cylinder stability during injection molding will decrease.
【0006】[0006]
【実施例】本発明に係る実施例で使用するフェノール類
は、フェノール、クレゾール、キシレノール等の一価の
フェノール類、カテコール、レゾルシン等の多価のフェ
ノール類である。ホルムアルデヒドは、パラホルムアル
デヒド、ホルマリン等である。ホルムアルデヒド/フェ
ノール類のモル比は、好ましくは1.25〜1.3であ
る。EXAMPLES The phenols used in the examples of the present invention are monohydric phenols such as phenol, cresol and xylenol, and polyhydric phenols such as catechol and resorcinol. Formaldehyde includes paraformaldehyde, formalin, and the like. The formaldehyde/phenols molar ratio is preferably 1.25 to 1.3.
【0007】触媒として使用するトリエチルアミンの量
は、フェノール類とホルムアルデヒドの合計重量に対し
て0.3〜1%が適当である。少なすぎると、フェノー
ル樹脂製造の反応速度が遅くなり、未反応フェノールの
量も多くなる。そのため、得られたフェノール樹脂の硬
化速度も遅くなり、成形サイクルも長くなる傾向となる
。一方、トリエチルアミの量が多すぎると、フェノール
樹脂製造の反応が速くなり、制御が難しくなる。また、
アンモニアの使用量は、前記両者の合計重量に対して0
.2〜1%が適当である。少ないと、製造するフェノー
ル樹脂の高分子量化が十分でない。尚、1%より多く添
加しても、高分子量化の程度は変わらなくなる。The amount of triethylamine used as a catalyst is suitably 0.3 to 1% based on the total weight of phenols and formaldehyde. If it is too small, the reaction rate for producing phenolic resin will be slow and the amount of unreacted phenol will be large. Therefore, the curing speed of the obtained phenol resin tends to be slow, and the molding cycle also tends to be long. On the other hand, if the amount of triethylamide is too large, the reaction for producing phenolic resin will become faster and difficult to control. Also,
The amount of ammonia used is 0 based on the total weight of both of the above.
.. 2 to 1% is appropriate. If the amount is too low, the molecular weight of the produced phenol resin will not be sufficiently increased. Note that even if more than 1% is added, the degree of increase in molecular weight remains unchanged.
【0008】上記フェノール樹脂は、ガラス繊維のほか
、シリカ、ガラスパウダ、タルク、カオリン、クレー、
シリカ、アルミナ等の無機質充填材、添加剤としてカー
ボンブラック等の着色剤、ステアリン酸亜鉛、ステアリ
ン酸等の離型剤を適宜配合して、ヘンシェルミキサ、ロ
ール等混練機で混練し、粉砕して成形材料とする。[0008] In addition to glass fiber, the above phenolic resins include silica, glass powder, talc, kaolin, clay,
Inorganic fillers such as silica and alumina, coloring agents such as carbon black as additives, and mold release agents such as zinc stearate and stearic acid are appropriately blended, and the mixture is kneaded using a kneading machine such as a Henschel mixer or a roll, and then pulverized. Use as a molding material.
【0009】実施例1〜2、比較例1〜2表1に示す配
合で、フェノールとパラホルムアルデヒドをトリエチル
アミン存在下80℃で4時間反応させ、ついで、アンモ
ニアを添加して85℃で5時間反応させてレゾール樹脂
を得た。Examples 1-2, Comparative Examples 1-2 Using the formulations shown in Table 1, phenol and paraformaldehyde were reacted at 80°C for 4 hours in the presence of triethylamine, and then ammonia was added and the reaction was carried out at 85°C for 5 hours. A resol resin was obtained.
【0010】比較例3〜4
表1に示す配合で、フェノールとパラホルムアルデヒド
をCa(OH)2存在下80℃で4時間反応させ、つい
で、アンモニアを添加して85℃で5時間反応させてレ
ゾール樹脂を得た。Comparative Examples 3 to 4 Using the formulations shown in Table 1, phenol and paraformaldehyde were reacted at 80°C for 4 hours in the presence of Ca(OH)2, and then ammonia was added and the mixture was reacted at 85°C for 5 hours. A resol resin was obtained.
【0011】[0011]
【表1】[Table 1]
【0012】上記で得た各フェノール樹脂のゲル化時間
保持率(40℃で10日間置いたときのゲル化時間の初
期値に対する割合)を測定し、貯蔵安定性を評価した。
また、各フェノール樹脂中の未反応フェノールの量を測
定した。その結果を表2に示す。また、上記各フェノー
ル樹脂をガラス繊維、ガラスパウダ、添加剤と共にヘン
シェルミキサで混合混練後、粉砕、乾燥して成形材料と
した。この成形材料を射出成形して(シリンダ温度:前
部90℃,後部50℃、金型温度:180℃)、成形サ
イクルとシリンダ安定性について評価した。成形サイク
ルは、(射出時間+保圧時間)を短縮していき、成形可
能な最小時間を評価した。結果を表2に併せて示す。The gelation time retention rate (ratio of gelation time to the initial value when left at 40° C. for 10 days) of each of the phenolic resins obtained above was measured to evaluate storage stability. Additionally, the amount of unreacted phenol in each phenol resin was measured. The results are shown in Table 2. Further, each of the above-mentioned phenol resins was mixed and kneaded with glass fiber, glass powder, and additives in a Henschel mixer, and then ground and dried to obtain a molding material. This molding material was injection molded (cylinder temperature: front: 90°C, rear: 50°C, mold temperature: 180°C), and the molding cycle and cylinder stability were evaluated. For the molding cycle, (injection time + pressure holding time) was shortened, and the minimum moldable time was evaluated. The results are also shown in Table 2.
【0013】[0013]
【表2】[Table 2]
【0014】[0014]
【発明の効果】表2から明らかなように、本発明に係る
方法で製造されたフェノール樹脂は、ゲル化時間保持率
が大きく、貯蔵安定性のよいことがわかる。また、未反
応フェノールが少ないことから、成形サイクルの短い成
形材料となり、シリンダ内の低い温度では硬化が進まず
安定性に優れている。Effects of the Invention As is clear from Table 2, the phenol resin produced by the method according to the present invention has a high gelation time retention rate and good storage stability. In addition, since there is little unreacted phenol, it becomes a molding material with a short molding cycle, and has excellent stability because it does not harden at low temperatures inside the cylinder.
Claims (1)
を1.2〜1.3とし、トリエチルアミン触媒存在下で
第1段目の反応を行なわせ、その後アンモニア触媒存在
下で第2段目の反応を行なわせることを特徴とする成形
材料用フェノール樹脂の製造法。Claim 1: The molar ratio of formaldehyde/phenols is 1.2 to 1.3, the first stage reaction is carried out in the presence of a triethylamine catalyst, and then the second stage reaction is carried out in the presence of an ammonia catalyst. A method for producing a phenolic resin for molding materials, characterized by the following steps:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3084300A JP2596249B2 (en) | 1991-04-17 | 1991-04-17 | Manufacturing method of phenolic resin molding material for injection molding |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3084300A JP2596249B2 (en) | 1991-04-17 | 1991-04-17 | Manufacturing method of phenolic resin molding material for injection molding |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04318011A true JPH04318011A (en) | 1992-11-09 |
JP2596249B2 JP2596249B2 (en) | 1997-04-02 |
Family
ID=13826629
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3084300A Expired - Fee Related JP2596249B2 (en) | 1991-04-17 | 1991-04-17 | Manufacturing method of phenolic resin molding material for injection molding |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2596249B2 (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5476694A (en) * | 1977-11-30 | 1979-06-19 | Matsushita Electric Works Ltd | Preparation of resol-type phenolic resin |
JPS61171717A (en) * | 1985-01-25 | 1986-08-02 | Shin Kobe Electric Mach Co Ltd | Production of oiticica oil-modified phenolic resin |
-
1991
- 1991-04-17 JP JP3084300A patent/JP2596249B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5476694A (en) * | 1977-11-30 | 1979-06-19 | Matsushita Electric Works Ltd | Preparation of resol-type phenolic resin |
JPS61171717A (en) * | 1985-01-25 | 1986-08-02 | Shin Kobe Electric Mach Co Ltd | Production of oiticica oil-modified phenolic resin |
Also Published As
Publication number | Publication date |
---|---|
JP2596249B2 (en) | 1997-04-02 |
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