JPH0694528B2 - Composition for phenolic resin - Google Patents
Composition for phenolic resinInfo
- Publication number
- JPH0694528B2 JPH0694528B2 JP61085062A JP8506286A JPH0694528B2 JP H0694528 B2 JPH0694528 B2 JP H0694528B2 JP 61085062 A JP61085062 A JP 61085062A JP 8506286 A JP8506286 A JP 8506286A JP H0694528 B2 JPH0694528 B2 JP H0694528B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- composition
- phenolic resin
- phenol resin
- 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
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- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は比較的低い温度領域でも工業的に有用な速度で
硬化可能なフェノール樹脂用組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a composition for a phenolic resin which can be cured at an industrially useful rate even in a relatively low temperature range.
フェノール樹脂は機械部品、電気部品、厨房用品などに
幅広く利用されているが近年生産性向上のため硬化時間
を短縮すること、および、製品の小型化または各種部品
の一体成形など製品の多様化に伴い、硬化時間の短縮に
加えて、なるべく低い温度で成形しうる材料の開発が強
く望まれるようになってきた。Phenolic resins are widely used in mechanical parts, electrical parts, kitchen products, etc., but in recent years they have been used for shortening the curing time to improve productivity, and for product diversification such as product miniaturization or integral molding of various parts. Accordingly, in addition to shortening the curing time, development of a material that can be molded at a temperature as low as possible has been strongly desired.
従来、かかる要件に対して、金属酸化物、ある種の酸ま
たは塩基などの化合物を使用することが試みられたが、
硬化時間の短縮となるべく低い温度でも成形しうるとい
う要件を満足するものではなかった。Conventionally, for such requirements, it has been attempted to use compounds such as metal oxides, certain acids or bases,
It did not satisfy the requirement that molding can be performed at a temperature as low as possible in order to shorten the curing time.
本発明は、フェノール樹脂100重量部、ヘキサメチレン
テトラミン５〜20重量部、および、ペンタメチレンジチ
オカルバミン酸ピペリジン塩、ピペコリルジオカルバミ
ン酸ピペコリン塩およびジブチルジチオカルバミン酸亜
鉛から選ばれた少なくとも１種のジチオ酸塩類１〜15重
量部を含むフェノール樹脂用組成物に関する。The present invention relates to 100 parts by weight of a phenol resin, 5 to 20 parts by weight of hexamethylenetetramine, and at least one dithio acid selected from pentamethylenedithiocarbamic acid piperidine salt, pipecolyl diiocarbamic acid pipecoline salt and zinc dibutyldithiocarbamate. The present invention relates to a phenol resin composition containing 1 to 15 parts by weight of salts.
本発明において対象となるものはヘキサメチレンテトラ
ミンにより硬化させることのできるフェノール樹脂の全
てであり、例えば、フェノール、およびクレゾール類、
キシレノール類、エチルフェノール、プロピルフェノー
ル、ブチルフェノール、アミルフェノール、オクチルフ
ェノール、ノニルフェノール、ドデシルフェノールなど
のC1〜C20のアルキル基を有するアルキルフェノール
類、ビスフェノールＡ、フェニルフェノール、クミルフ
ェノール、スチレン化フェノールなどのアルキルフェノ
ール類似構造を有するフェノール類、ビニルフェノー
ル、イソプロペニルフェノールなどのアルケニルフェノ
ール類などをホルムアルデヒド水溶液、パラホルムアル
デヒド、トリオキシメチレン、ヘキサメチレンテトラミ
ン、他の脂肪族アルデヒド、または置換基および非置換
芳香族アルデヒドなどと反応させてフェノール樹脂とし
たものである。The object of the present invention is all phenolic resins that can be cured with hexamethylenetetramine, such as phenol, and cresols,
Xylenols, ethylphenols, propylphenols, butylphenols, amylphenols, octylphenols, nonylphenols, dodecylphenols and other alkylphenols having C 1 to C 20 alkyl groups, bisphenol A, phenylphenols, cumylphenols, styrenated phenols, etc. Phenols having a structure similar to alkylphenol, alkenylphenols such as vinylphenol and isopropenylphenol, etc. are treated with formaldehyde aqueous solution, paraformaldehyde, trioxymethylene, hexamethylenetetramine, other aliphatic aldehydes, or substituents and unsubstituted aromatic aldehydes. It is made into a phenolic resin by reacting with.
また、ジチオ酸塩類としては、例えば、ペンタメチレン
ジチオカルバミン酸ピペリジン塩、ピペコリルジチオカ
ルバミン酸ピペコリン塩、ジブチルジチオカルバミン酸
亜鉛などが好ましい。Further, as dithioates, for example, pentamethylenedithiocarbamic acid piperidine salt, pipecolyl dithiocarbamic acid pipecoline salt, zinc dibutyldithiocarbamate and the like are preferable.
フェノール樹脂とヘキサメチレンテトラミンの配合比率
については何ら限定しないが、フェノール樹脂100重量
部に対して、ヘキサメチレンテトラミン５〜20重量部の
割合が好ましい。The mixing ratio of the phenol resin and hexamethylenetetramine is not limited at all, but the ratio of 5 to 20 parts by weight of hexamethylenetetramine is preferable with respect to 100 parts by weight of the phenol resin.
ジチオ酸塩類の配合比率も、特に限定するものではない
が、フェノール樹脂100重量部に対して、１〜15重量
部、２種以上配合する場合はその合計量ガ１〜15重量部
となる割合が好ましい。The mixing ratio of the dithio acid salts is not particularly limited, but is 1 to 15 parts by weight with respect to 100 parts by weight of the phenolic resin, and the total amount is 1 to 15 parts by weight when 2 or more kinds are mixed. Is preferred.
なお、要すれば、通常用いられる充填剤、補強材、滑
材、可塑化材、着色材、硬化促進剤などの添加剤を配合
してもよい。In addition, if necessary, additives such as a filler, a reinforcing material, a lubricant, a plasticizing material, a coloring material, and a curing accelerator which are usually used may be blended.
このようにして得られたフェノール樹脂用組成物は熱ロ
ールあるいはニーダーなど公知の技術により混合し整粒
して成形材料とすることができる。The phenol resin composition thus obtained can be mixed and sized by a known technique such as a hot roll or a kneader to obtain a molding material.
本発明にかかわるフェノール樹脂用組成物は170℃以上
での一般的成形温度で硬化成形しうるのみならず、従来
困難とされていた130℃のような低温においても工業的
に有用な速さで硬化成形を行うことができる。The composition for a phenol resin according to the present invention is not only capable of being cured and molded at a general molding temperature of 170 ° C. or higher, but also at an industrially useful speed even at a low temperature such as 130 ° C. which has hitherto been difficult. Curing and molding can be performed.
本発明を実施例により具体的に説明する。実施例中、部
は全て重量部である。The present invention will be specifically described with reference to examples. In the examples, all parts are parts by weight.
実施例１〜２ 市販のフェノールノボラック樹脂（三井東圧化学製、ノ
ボラック＃1000）100部、ヘキサメチレンテトラミン15
部、シリカ粉末137部、ガラス繊維13部、フルフラール
５部、ワックス３部とジチオ酸塩類として第１表に示す
化合物５部とを配合しフェノール樹脂用組成物を得た。
この組成物をロール温度90℃で２分間混練し、冷却後パ
ワーミル（スクリーン、4mm）で粉砕、整粒して成形材
料とした。Examples 1-2 Commercially available phenol novolac resin (Mitsui Toatsu Chemicals, Novolac # 1000) 100 parts, hexamethylene tetramine 15
Parts, silica powder 137 parts, glass fiber 13 parts, furfural 5 parts, wax 3 parts and 5 parts of the compounds shown in Table 1 as dithioates are mixed to obtain a phenol resin composition.
This composition was kneaded at a roll temperature of 90 ° C. for 2 minutes, cooled, pulverized and sized with a power mill (screen, 4 mm) to obtain a molding material.
比較例１〜３ ジチオ酸塩類を用いないか、あるいはこれらの代わりに
第１表に示す化合物、すなわち現在多用されている硬化
促進剤を配合した以外は実施例と同様にしてフェノール
樹脂用組成物を得て、成形材料とした。Comparative Examples 1 to 3 Compositions for phenolic resin were prepared in the same manner as in Examples, except that dithioates were not used, or instead of these compounds were added the compounds shown in Table 1, that is, curing accelerators which are now in widespread use. To obtain a molding material.
実施例および比較例にて得た成形材料を、第１表に示し
た硬化温度において、圧力100Kg/cm2、硬化時間２分の
条件にて圧縮成形し、直径80mm、厚さ2mmの試験片を作
成した。The molding materials obtained in Examples and Comparative Examples were compression-molded at a curing temperature shown in Table 1 under the conditions of a pressure of 100 Kg / cm 2 and a curing time of 2 minutes to obtain a test piece having a diameter of 80 mm and a thickness of 2 mm. It was created.
硬化度の目安として各試験片の成形直後のバーコール硬
度（アメリカ国、バーバー・コルマン社製、バーコール
GY-ZJ934-1 硬度計による）を測定した。結果を第１表
に示す。本発明のフェノール樹脂用組成物が130℃の低
温においても充分に硬化が進んでいることが理解され
る。また、比較例の170℃にて硬化させた試験片につい
て、それぞれ150℃、130℃まで冷却したときの硬度を
（ ）内に併示した。冷却により硬度は通常高くなる。
これらの数値に比較して、実施例の例えば130℃硬化の
試験片の成形直後の硬度が同等あるいはそれ以上である
ことからも、本発明にかかわるフェノール樹脂組成物
が、低温においても工業的に有用な速度で硬化可能であ
ることが理解される。As a measure of the degree of cure, the barcol hardness of each test piece immediately after molding (Barber Colman, USA, Barcor
GY-ZJ934-1 hardness meter) was measured. The results are shown in Table 1. It is understood that the phenol resin composition of the present invention is sufficiently cured even at a low temperature of 130 ° C. Further, the hardness of the test piece of Comparative Example cured at 170 ° C. when cooled to 150 ° C. and 130 ° C. is also shown in parentheses. Cooling usually increases hardness.
Compared to these numerical values, the hardness immediately after molding of the test piece of Example cured at 130 ° C. is equal to or higher than that, so that the phenol resin composition according to the present invention is industrially used even at a low temperature. It is understood that it can be cured at a useful rate.
Claims (1)
ンテトラミン５〜20重量部、および、ペンタメチレンジ
チオカルバミン酸ピペリジン塩、ピペコリルジチオカル
バミン酸ピペコリン塩およびジブチルジチオカルバミン
酸亜鉛から選ばれた少なくとも１種のジチオ酸塩類１〜
15重量部を含むフェノール樹脂用組成物。1. A phenol resin of 100 parts by weight, hexamethylenetetramine of 5 to 20 parts by weight, and at least one kind of dithio selected from pentamethylenedithiocarbamic acid piperidine salt, pipecolyldithiocarbamate pipecoline salt and zinc dibutyldithiocarbamate. Acid salts 1
A phenolic resin composition containing 15 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61085062A JPH0694528B2 (en) | 1986-04-15 | 1986-04-15 | Composition for phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61085062A JPH0694528B2 (en) | 1986-04-15 | 1986-04-15 | Composition for phenolic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62241950A JPS62241950A (en) | 1987-10-22 |
| JPH0694528B2 true JPH0694528B2 (en) | 1994-11-24 |
Family
ID=13848148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61085062A Expired - Lifetime JPH0694528B2 (en) | 1986-04-15 | 1986-04-15 | Composition for phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0694528B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5554399A (en) * | 1978-10-16 | 1980-04-21 | Asahi Denka Kogyo Kk | Anti-friction material |
-
1986
- 1986-04-15 JP JP61085062A patent/JPH0694528B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62241950A (en) | 1987-10-22 |
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