JPH072896B2 - Fast curable phenol resin composition - Google Patents
Fast curable phenol resin compositionInfo
- Publication number
- JPH072896B2 JPH072896B2 JP62053075A JP5307587A JPH072896B2 JP H072896 B2 JPH072896 B2 JP H072896B2 JP 62053075 A JP62053075 A JP 62053075A JP 5307587 A JP5307587 A JP 5307587A JP H072896 B2 JPH072896 B2 JP H072896B2
- Authority
- JP
- Japan
- Prior art keywords
- phenol resin
- resin composition
- curing
- fast
- parts
- 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、ブレーキ材、断熱材、積層材或るいは繊維強
化成形材（以下FRPという）などに有用な速硬化性フェ
ノール樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a fast-curing phenol resin composition useful as a brake material, a heat insulating material, a laminated material, a fiber reinforced molding material (hereinafter referred to as FRP), or the like. .
フェノール樹脂は、耐熱性があり、作業性にも優れてい
ることにより、汎用樹脂として広く使用されている。し
かしながら、硬化のサイクルアップ、省エネルギーの観
点より、速硬化性、低温硬化性のフェノール樹脂が強く
求められている。Phenolic resins are widely used as general-purpose resins due to their heat resistance and excellent workability. However, from the viewpoint of curing cycle up and energy saving, there is a strong demand for a fast-setting and low-temperature-setting phenol resin.
また、フェノール樹脂のもう一つの特徴である難燃性を
生かしたFRPは、近年、脚光をあびているが、一般的に
はフェノール樹脂にトルエンスルホン酸などの強酸を添
加し、硬化を速めているが、混合時のポットライフが極
めて短かいこと並びに製品中に硬化剤として用いた酸が
残存するため金属に対する腐食性が大きいという問題が
ある。FRP, which makes use of the flame retardancy that is another characteristic of phenolic resins, has been in the limelight in recent years, but in general, strong acids such as toluene sulfonic acid are added to phenolic resins to accelerate curing. However, there is a problem that the pot life at the time of mixing is extremely short and that the acid used as a curing agent remains in the product, so that it is highly corrosive to metals.
さらに、プルトリュージョン法によるFRP成形にフェノ
ール樹脂を用いる場合にも、同様に、ポットライフと硬
化時間との良好なバランスが得られず、満足すべき成形
品が得られ難いという欠点がある。Further, when a phenol resin is used for FRP molding by the pull trough method, similarly, there is a drawback that a good balance between pot life and curing time cannot be obtained, and it is difficult to obtain a satisfactory molded product.
本発明は、上記事情に鑑み、低温硬化性及び速硬化性に
優れたフェノール樹脂組成物を、フェノール樹脂のポッ
トライフに殆んど影響を与えずに、得ることを目的とす
るものである。The present invention has been made in view of the above circumstances, and an object thereof is to obtain a phenol resin composition having excellent low-temperature curability and fast curability, while hardly affecting the pot life of the phenol resin.
本発明の速硬化性フェノール樹脂組成物は、 （Ａ） 液状レゾール型フェノール樹脂に （Ｂ） マンガン、コバルト、ニッケル、ランタン及び
白金からなる群から選ばれる少なくとも１種の遷移元素
の硫酸塩、塩酸塩、硝酸塩又はスルホン酸塩（以後、遷
移元素の塩類と略記する）を添加することによって、上
記目的を達成した。The fast-curing phenolic resin composition of the present invention comprises (A) a liquid resol-type phenolic resin (B) at least one transition element sulfate and hydrochloric acid selected from the group consisting of manganese, cobalt, nickel, lanthanum and platinum. The above object was achieved by adding a salt, a nitrate or a sulfonate (hereinafter abbreviated as transition element salts).
本発明のフェノール樹脂組成物における遷移元素の塩類
が如何なる作用をするのか、その詳細は不明であるが、
フェノール樹脂に添加された遷移塩素の塩類は、系の酸
性にして硬化速度を速くすると共に遷移元素とフェノー
ル樹脂との間でキレート結合が生成してフェノール樹脂
末端のメチロール基の活性を高めるという相乗作用によ
り、ポットライフに影響を与えずに低温硬化性、速硬化
性の優れた特性が得られるものと推定される。It is not known in detail how the salts of the transition element in the phenol resin composition of the present invention work,
The salt of transition chlorine added to the phenol resin synergizes the acidification of the system to accelerate the curing rate and the formation of a chelate bond between the transition element and the phenol resin to enhance the activity of the methylol group at the end of the phenol resin. It is presumed that, due to the action, excellent properties of low temperature curability and fast curability can be obtained without affecting the pot life.
本発明に於て使用する液状レゾール型フェノール樹脂
は、フェノール類１モルとアルデヒド類0.8〜4.0モルを
アルカリ性触媒の存在下で反応して得られる液状レゾー
ル型フェノール樹脂初期縮合物である。この初期縮合物
は酸で部分中和されていてもよい。又脱水し水を適当な
溶剤で置換してもよい。フェノール類としては、フェノ
ールおよびその同族体のクレゾール、キシレノール、ア
ルキルフェノール等があげられる。アルデヒド類として
はホルムアルデヒド、アセトアルデヒドおよびフルフラ
ール等があげられる。The liquid resol-type phenol resin used in the present invention is a liquid resol-type phenol resin initial condensate obtained by reacting 1 mol of a phenol with 0.8 to 4.0 mol of an aldehyde in the presence of an alkaline catalyst. This initial condensate may be partially neutralized with an acid. It may be dehydrated and the water may be replaced with a suitable solvent. Examples of phenols include phenol and its homologues such as cresol, xylenol, and alkylphenol. Examples of aldehydes include formaldehyde, acetaldehyde and furfural.
本発明で用いられる遷移元素の塩類は、マンガン、コバ
ルト、ニッケル、ランタン及び白金からなる群から選ば
れる少なくとも１種の遷移元素の硫酸塩、塩酸塩、硝酸
塩又はスルホン酸塩であり、好適例には塩化コバルト、
塩化ニッケル、硝酸プラチナ、硫酸マンガン、トルエン
スルホン酸ニッケルがその具体例として挙げられる。The salts of transition elements used in the present invention are sulfates, hydrochlorides, nitrates or sulfonates of at least one transition element selected from the group consisting of manganese, cobalt, nickel, lanthanum and platinum. Is cobalt chloride,
Specific examples thereof include nickel chloride, platinum nitrate, manganese sulfate, and nickel toluenesulfonate.
遷移元素の塩類の添加量はフェノール樹脂（固形分）10
0部に対し0.5部〜20部程度が作業上好ましいが、特に硬
化皮膜に導電性を附与したい場合には20部以上配合する
こともできる。Phenolic resin (solid content) 10
About 0.5 to 20 parts per 0 part is preferable in terms of work, but if it is desired to impart conductivity to the cured film, 20 parts or more may be added.
以下、本発明を実施例により説明する。尚、実施例中の
「部」は「重量部」を意味する。Hereinafter, the present invention will be described with reference to examples. In addition, "part" in an Example means a "weight part."
実施例１ フェノール樹脂中間体の製造 フェノール100部に37％ホルマリン水溶液103部を加えて
20％アンモニア水によりpH9.0に調整した後、100℃１時
間反応させ、反応終了後、直ちに80mmHgの減圧下で脱水
を開始させて、反応系の温度を55℃に維持した。脱水の
終点は、脱水量が20部となった時点とし、この脱水終了
時にメタノール60部を加え、不揮発分を50％に調整し
た。この時の重量平均分子量は1100、粘度は60cps、pH
は8.2、150℃硬化時間は2.5分であった。Example 1 Production of Phenolic Resin Intermediate To 100 parts of phenol was added 103 parts of 37% formalin aqueous solution.
After adjusting the pH to 9.0 with 20% aqueous ammonia, the reaction was carried out at 100 ° C. for 1 hour, and immediately after the reaction was completed, dehydration was started under a reduced pressure of 80 mmHg to maintain the temperature of the reaction system at 55 ° C. The end point of dehydration was when the dehydration amount reached 20 parts, and at the end of this dehydration, 60 parts of methanol was added to adjust the nonvolatile content to 50%. Weight average molecular weight at this time is 1100, viscosity is 60 cps, pH
The curing time was 8.2 and the curing time at 150 ° C was 2.5 minutes.
このフェノール樹脂中間体100部に対し、塩化コバルト
６水塩7.3部を添加し、40℃１時間混合、溶解し、目的
の速硬化性フェノール樹脂組成物107.3部を得た。この
時の塩化コバルトの添加量はフェノール樹脂固形分100
部に対して４部であった。To 100 parts of this phenol resin intermediate, 7.3 parts of cobalt chloride hexahydrate was added, mixed and dissolved at 40 ° C. for 1 hour to obtain 107.3 parts of a desired fast-curing phenol resin composition. The amount of cobalt chloride added at this time was 100% phenol resin solids.
It was 4 parts to parts.
この速硬化性フェノール樹脂組成物の150℃硬化時間
は、0.8分であり、硬化時間は約1/3に短縮された。又、
本発明品を５℃で１カ月保存した後の粘度は65cps、150
℃硬化時間は0.8分と、ほとんど径日変化を示めさなか
った。The 150 ° C. curing time of this fast-curing phenol resin composition was 0.8 minutes, and the curing time was shortened to about 1/3. or,
After storing the product of the present invention at 5 ° C for 1 month, the viscosity is 65 cps, 150
The ℃ curing time was 0.8 minutes, which showed almost no change over time.
実施例２〜5,比較例１〜６ 実施例１と同様の方法で、表−１に記載の各種塩類をフ
ェノール樹脂固型分100部に対して４部（無水換算にな
るように添加したフェノール樹脂組成物の試験結果を実
施例１の結果と併せて表−１に示す。Examples 2 to 5 and Comparative Examples 1 to 6 In the same manner as in Example 1, various salts shown in Table 1 were added to 4 parts of 100 parts of the phenol resin solid content (so as to be equivalent to anhydrous). The test results of the phenol resin composition are shown in Table 1 together with the results of Example 1.
この様に、遷移元素の塩類以外の塩を用いた場合、硬化
速度が早くなるものもあるが、フェノール樹脂に対する
溶解性がきわめて悪く、均一な硬化物を得ることができ
なかった。 As described above, when a salt other than the transition element salts is used, the curing rate may be increased, but the solubility in the phenol resin is extremely poor, and a uniform cured product cannot be obtained.
実施例６ 実施例１と同様の方法で、遷移元素の塩類の添加量を変
えた場合の硬化速度の変化を試験した。結果を表−２に
示す。添加塩としては塩化ニッケルを用いた。Example 6 In the same manner as in Example 1, the change in the curing rate when the addition amount of the salt of the transition element was changed was tested. The results are shown in Table-2. Nickel chloride was used as the added salt.
この様に添加量に応じて硬化時間は短縮され、その効果
は添加量20部程度でほぼ平衡に達した。 Thus, the curing time was shortened depending on the amount added, and the effect reached an equilibrium when the amount added was about 20 parts.
実施例７ 同様に従来の酸添加品との比較試験を行った結果を表−
３に示す。Example 7 Similarly, the results of a comparative test with a conventional acid-added product are shown in Table-
3 shows.
この様に本発明品はポットライフも長く、pHも弱酸性程
度となる。 As described above, the product of the present invention has a long pot life and its pH is weakly acidic.
応用例 実施例１の速硬化性フェノール樹脂組成物を用いてプル
トリュージン法によるフェノールFRP成形を行った。そ
の条件と製品物性を次に示す。Application Example Using the fast-curing phenol resin composition of Example 1, phenol FRP molding was carried out by the plutrudin method. The conditions and product properties are shown below.
表４ プルトリュージョン法成形条件 成形物形状 巾100mm×厚さ3mm平板 金型温度 120℃ 金型長さ 50cm 引き抜き速度 1m/min ガラス含有量 40％ ガラス構成 朱子織ガラスクロス／ガラスチョップド
マット／朱子織ガラスクロス 表５ 成形品物性 厚み 4mm 曲げ破断強度 23kg/mm2 曲げ弾性率 1210kg/mm2 この様に、従来のフェノール樹脂ではほとんど不可能な
ライン条件においてプルトリュージョン法によるフェノ
ールFRP成形が、本発明品を用いる事により可能となっ
た。又、従来では、強酸を添加し、硬化速度を早めてFR
P成形を行う例があるが、その場合、一般的には、必要
な硬化速度を得る為の硬化剤量を使用するとポットライ
フが短かいこと、及び、金属に対する腐食性が問題とな
るが、本発明品を用いる事により大巾に改善される。
尚、金属に対する腐食性がそれほど問題とならない用途
において、硬化時間をより短縮させたい場合には、本発
明品に無機もしくは有機の酸を併用する事により目的を
達する事ができる。Table 4 Molding conditions for the plutotrusion method Molded product width 100 mm x thickness 3 mm Flat plate mold temperature 120 ° C Mold length 50 cm Drawing speed 1 m / min Glass content 40% Glass composition Satin woven glass cloth / glass chopped mat / satin Woven glass cloth Table 5 Physical properties of molded products Thickness 4mm Bending rupture strength 23kg / mm 2 Bending elastic modulus 1210kg / mm 2 In this way, phenol FRP molding by the pull trough method can be performed under the line conditions almost impossible with conventional phenol resin. It became possible by using the product of the present invention. Also, in the past, strong acid was added to accelerate the curing speed and FR
Although there is an example of performing P molding, in that case, generally, when the amount of the curing agent used to obtain the required curing rate is used, the pot life is short, and the corrosiveness to the metal becomes a problem, It is greatly improved by using the product of the present invention.
In addition, in applications where the corrosiveness to metals is not so problematic, if it is desired to further shorten the curing time, the object can be achieved by using an inorganic or organic acid in combination with the product of the present invention.
本発明のフェノール樹脂組成物は、極めて硬化時間が短
縮され、また従来では殆んど硬化しないような低温での
硬化が可能となり、しかもポットライフも長くすること
ができ、成形材料として、種々の用途に有用である。INDUSTRIAL APPLICABILITY The phenol resin composition of the present invention has an extremely short curing time, can be cured at a low temperature that hardly cures in the prior art, and can have a long pot life. Useful for applications.
Claims (1)
金からなる群から選ばれる少なくとも１種の遷移元素の
硫酸塩、塩酸塩、硝酸塩又はスルホン酸塩とからなる速
硬化性フェノール樹脂組成物。1. A liquid resol-type phenol resin and (B) a sulfate, hydrochloride, nitrate or sulfonate of at least one transition element selected from the group consisting of manganese, cobalt, nickel, lanthanum and platinum. A fast-curing phenolic resin composition comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62053075A JPH072896B2 (en) | 1987-03-10 | 1987-03-10 | Fast curable phenol resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62053075A JPH072896B2 (en) | 1987-03-10 | 1987-03-10 | Fast curable phenol resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63221156A JPS63221156A (en) | 1988-09-14 |
| JPH072896B2 true JPH072896B2 (en) | 1995-01-18 |
Family
ID=12932688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62053075A Expired - Lifetime JPH072896B2 (en) | 1987-03-10 | 1987-03-10 | Fast curable phenol resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH072896B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5943590B2 (en) * | 1980-09-24 | 1984-10-23 | 東レ株式会社 | sheet-like material |
-
1987
- 1987-03-10 JP JP62053075A patent/JPH072896B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63221156A (en) | 1988-09-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |