JPH0694530B2 - Novel phenol resin composition - Google Patents
Novel phenol resin compositionInfo
- Publication number
- JPH0694530B2 JPH0694530B2 JP61085065A JP8506586A JPH0694530B2 JP H0694530 B2 JPH0694530 B2 JP H0694530B2 JP 61085065 A JP61085065 A JP 61085065A JP 8506586 A JP8506586 A JP 8506586A JP H0694530 B2 JPH0694530 B2 JP H0694530B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- resin composition
- phenol resin
- weight
- novel phenol
- 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
Landscapes
- 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
硬化可能な新規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 novel phenol resin composition 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、ノボラック型フェノール樹脂100重量部、ヘ
キサメチレンテトラミン５〜20重量部、および、N,N−
ジフェニルチオウレアおよびN,N−ジエチルチオウレア
から選ばれた少なくとも１種のチオウレア類１〜15重量
部を含む新規フェノール樹脂用組成物に関する。The present invention comprises 100 parts by weight of a novolac type phenolic resin, 5 to 20 parts by weight of hexamethylenetetramine, and N, N-
The present invention relates to a novel phenol resin composition containing 1 to 15 parts by weight of at least one thiourea selected from diphenylthiourea and N, N-diethylthiourea.
本発明において対照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。Controls in the present invention are 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、チオウレア類としては、例えばN.N-ジフェニルチ
ォウレア、N.N-ジエチルチオウレア、N,N-ジメチルチオ
ウレアなどが好ましい。As the thioureas, for example, NN-diphenylthiourea, NN-diethylthiourea, N, N-dimethylthiourea 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.
チオウレア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が１〜15重量部
となる割合が好ましい。The compounding ratio of the thioureas is not particularly limited, but 1 to 15 parts by weight, relative to 100 parts by weight of the phenol resin, when 2 or more kinds are mixed, the total amount is preferably 1 to 15 parts by weight. .
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新規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 novel 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.
本発明にかかわる新規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 novel phenolic resin composition according to the present invention is 170 ° C.
Not only can it be cured and molded at the general molding temperatures above,
Even at a low temperature such as 130 ° C., which has been considered difficult in the past, curing and molding can be performed at an industrially useful speed.
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部とチオウレア類として第１表に示す
化合物５部とを配合し新規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 thioureas were mixed to obtain a novel 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 チオウレア類を用いないか、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
樹脂組成物を得て、成形材料とした。Comparative Examples 1 to 3 Phenolic resin compositions were obtained in the same manner as in Examples except that thioureas were not used, or instead of these compounds were added the compounds shown in Table 1, that is, the curing accelerators that are widely used at present. As 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。本発明の新規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. The novel phenolic resin composition of the present invention is 130 ° C.
It is understood that the curing is sufficiently advanced even at the low temperature. Also 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, for example, 130 ° C. of the example is equal or higher,
It is understood that the phenolic resin composition according to the present invention can be cured at an industrially useful rate even at a low temperature.
Claims (1)
ヘキサメチレンテトラミン５〜20重量部、および、N,N
−ジフェニルチオウレアおよびN,N−ジエチルチオウレ
アから選ばれた少なくとも１種のチオウレア類１〜15重
量部を含む新規フェノール樹脂用組成物。1. A novolak type phenolic resin 100 parts by weight,
Hexamethylenetetramine 5 to 20 parts by weight, and N, N
-A novel phenol resin composition containing 1 to 15 parts by weight of at least one thiourea selected from diphenylthiourea and N, N-diethylthiourea.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61085065A JPH0694530B2 (en) | 1986-04-15 | 1986-04-15 | Novel phenol resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61085065A JPH0694530B2 (en) | 1986-04-15 | 1986-04-15 | Novel phenol resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62241953A JPS62241953A (en) | 1987-10-22 |
| JPH0694530B2 true JPH0694530B2 (en) | 1994-11-24 |
Family
ID=13848226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61085065A Expired - Lifetime JPH0694530B2 (en) | 1986-04-15 | 1986-04-15 | Novel phenol resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0694530B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2206696C3 (en) * | 1972-02-12 | 1978-05-24 | Eib, Wilhelm, 7417 Pfullingen | Use of molecular compounds as additives to adhesives based on formaldehyde-releasing condensates |
-
1986
- 1986-04-15 JP JP61085065A patent/JPH0694530B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62241953A (en) | 1987-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3793286A (en) | Resin system based on furfuryl alcohol and halomethylated phenolics | |
| JPH0694530B2 (en) | Novel phenol resin composition | |
| EP0363539A1 (en) | Thermosetting resin composition for injection molding | |
| JPH0694529B2 (en) | Phenol resin composition | |
| JPH0618982B2 (en) | Resin composition for novel phenol | |
| JPH0694528B2 (en) | Composition for phenolic resin | |
| JPH0623295B2 (en) | Phenol resin composition | |
| US3792020A (en) | High-temperature stable modified aromatic amine-aldehyde molding powders modified with aromatic polycarboxylic compounds | |
| JPH0618983B2 (en) | Resin composition for phenol | |
| US3644570A (en) | Process for the preparation of rubber modified novolak resins | |
| US4263248A (en) | Phenolic resins with improved low temperature processing stability | |
| US4210732A (en) | Phenolic resins with improved low temperature processing stability | |
| US4264557A (en) | Phenolic resins with improved low temperature processing stability | |
| JPS6195735A (en) | Bonding agent of phenol resin for shell mold | |
| JPS62241949A (en) | Novel phenolic resin composition | |
| US3855173A (en) | High temperature stable modified aromatic amine-aldehyde molding powders modified with aromatic polycarboxylic acid, and molded article | |
| US2793105A (en) | Grinding wheels | |
| US2435554A (en) | Phenolic-alkyd resins | |
| JP5549830B2 (en) | Resin coated sand using phenolic novolac resin | |
| GB1566459A (en) | Phenolic resin composition for injection moulding | |
| JPS63132917A (en) | Production of quick-curing phenolic resin | |
| JPH02113021A (en) | Epoxy resin composition | |
| JPH1171497A (en) | Phenol resin composition | |
| JPH0559257A (en) | Phenolic resin composition | |
| JPH0343303B2 (en) |