JPS6158483B2 - - Google Patents
Info
- Publication number
- JPS6158483B2 JPS6158483B2 JP14440377A JP14440377A JPS6158483B2 JP S6158483 B2 JPS6158483 B2 JP S6158483B2 JP 14440377 A JP14440377 A JP 14440377A JP 14440377 A JP14440377 A JP 14440377A JP S6158483 B2 JPS6158483 B2 JP S6158483B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- resol
- catalyst
- laminate
- resol 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
Links
- 229920005989 resin Polymers 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 37
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 150000002989 phenols Chemical class 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- 239000011134 resol-type phenolic resin Substances 0.000 claims description 6
- 229920003987 resole Polymers 0.000 description 29
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 235000019256 formaldehyde Nutrition 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Description
【発明の詳細な説明】
この発明はレゾール型フエノール樹脂の製造方
法に関するものである。
従来から、フエノール類とホルムアルデヒド
を、pKaが10以上の第3アミンを触媒として反応
させることによりレゾール型フエノール樹脂(以
下レゾール樹脂と略す)を製造することが知られ
ていた。この方法は、フエノール類およびホルム
アルデヒドの反応率も高く、反応速度も速いので
あるが、得られたレゾール樹脂を用いて積層板を
製造する場合に、つぎのような問題が生じた。す
なわち、このようにして得られたレゾール樹脂の
分子量が低いと、積層板の積層成形時に樹脂流出
による「かすれ」が生じ、分子量が高いと、ワニ
スのゲルタイムが短かくなりすぎてレゾール樹脂
含浸紙(レジンペーパー)の乾燥性が極端に悪く
なるとともに樹脂の流動不足により「かすれ」が
生じた。一方、フエノール類とホルムアルデヒド
をアンモニア触媒下で反応させてレゾール樹脂を
製造する方法も広く行なわれている。この方法に
よれば、得られたレゾール樹脂の分子量が大きい
ため、これを用いて積層板を製造する場合には、
成形性が良好となる。ちなみに、レゾール樹脂の
分子量と溶融粘度の関係を示すと図面のようにな
る。図において、曲線Aはトリエチルアミン触媒
下で製造された分子量の大きなレゾール樹脂の
135℃の溶融粘度曲線、曲線Bは曲線Aの場合と
同じ触媒を用いて製造された分子量の小さなレゾ
ール樹脂の135℃の溶融粘度曲線、曲線Cはアン
モニア触媒下で製造されたレゾール樹脂の135℃
の溶融粘度曲線である。図から明らかなように分
子量の大きいレゾール樹脂ほど溶融粘度の変化が
ゆるやかであり、積層板の製造の際に成形性がよ
くなることがわかる。したがつて、アンモニア触
媒下で合成したレゾール樹脂を用いて積層板を製
造する場合には成形性は良好になる。しかしなが
ら、この方法では、レゾール樹脂生成反応に長時
間を要するとともに、フエノール類およびホルム
アルデヒド類の反応率が低くなるため製造効率が
悪かつた。また、この反応は臭気が強いという問
題もあつた。
したがつて、この発明の目的は、このような問
題のないレゾール型フエノール樹脂の製造方法を
提供することである。
この発明の特徴は、フエノール類とホルムアル
デヒドをアルカリ性触媒の存在下で反応させるこ
とによりレゾール型フエノール樹脂を製造する方
法において、アルカリ性触媒としてpKaが10以上
の第3アミンとアンモニアとを併用し、両者を、
(pKaが10以上の第3アミン)/(アンモニア)
のモル比が0.8〜2.0になるように混合して用いる
ことにある。すなわち、このようにすることによ
り、分子量が大きくてゲルタイムが長いレゾール
樹脂を効率よく、しかも臭気を低めた状態で製造
することができる。
つぎにこの発明を詳しく説明する。
この発明で用いるフエノール類とホルムアルデ
ヒドは通常用いられるものが用いられる。そして
それらの使用割合は、(ホルムアルデヒド)/
(フエノール類)のモル比で1.0〜1.5に選ぶこと
が好ましい。
アルカリ性触媒としては、トリエチルアミン、
トリメチルアミンのようなpKaが10以上の第3ア
ミンと、アンモニアとを複合して用いる。両者の
使用割合は、(第3アミン)/(アンモニア)の
モル比が0.8〜2.0になるようにすることが好まし
く、より好ましくは1.2〜1.5にすることである。
両者のモル比が0.8未満では原料反応率が低くか
つ反応が遅くなり、2.0を越えると積層板の製造
時に成形性が悪くなる。また、pKaが10未満の第
3アミンを用いると、反応速度が極めて遅くな
り、実際の樹脂製造には不満となる。これらの複
合触媒の使用量について特に制限はしない。反応
時間に応じて触媒の使用量を選べばよい。しかし
通常はフエノール1モルに対して複合触媒が0.05
〜0.02Nモルになるように用いられる。
このような複合触媒系を用いてレゾール樹脂を
製造する場合には、その触媒の種類および量に応
じて反応を行なわせ、分子量が280〜380の範囲に
なるように反応を終了させることが好ましい。こ
のようにして得られたレゾール樹脂のゲルタイム
は17分以上となり、ホルムアルデヒド反応率は95
%以上となる。この場合、ゲルタイムが16分以下
ではレジンペーパーに用いた場合に乾燥作業性が
悪くなる傾向がある。また、ホルムアルデヒド反
応率が95%未満では臭気が高くなり作業性が低下
する傾向がある。
このようにして効率よく製造されたレゾール樹
脂を用い、通常の方法で紙等の基材に含浸乾燥さ
せて樹脂含浸紙をつくり、それを複数枚積層成形
して積層板をつくつた。この場合、樹脂含浸紙の
乾燥作業性も良好であり、積層板の積層成形時に
も「かすれ」等が起きず良好な状態の積層板が得
られた。
なお、この発明は、耐衝撃性の大な積層板製造
用のアニリン変性レゾール樹脂の製造にも適用す
ることができる。そしてこの場合にも前述の場合
と同様の効果を期待することができる。そのよう
なアニリン変性レゾール樹脂を製造する場合に
は、例えば前述の触媒のほかにフエノール1モル
に対してアニリンを0.015〜0.045モル添加すれば
よい。
つぎに実施例について説明する。
実施例 1
300mlのフラスコに、フエノール94g(1モ
ル)、55%ホルマリン65g(1.2モル)、トリエチ
ルアミン0.005モル(0.51g)、2.5%NH30.0038モ
ル(0.26g)を加え、撹拌棒、温度計を装着して
撹拌し、30分後に沸騰させ、85分間その状態に保
つた後、冷却してレゾール樹脂を得た。このもの
の分子量は、296(高速液体クロマトグラフによ
り測定)であり、135℃におけるゲルタイムは、
22分18秒であり、ホルムアルデヒド反応率96.0%
であつた。このものを紙基材に含浸乾燥してレジ
ンペーパーを作成したところ、乾燥作業性は良好
であつた。これを複数枚重ねて成形を行なつた結
果、良好な積層板が得られた。すなわち、この結
果より、この実施例で得られたレゾール樹脂は良
好な成形性をもち、乾燥作業性も良好であること
がわかる。
実施例 2
トリエチルアミンと25%NH3触媒の使用割合お
よび触媒使用量を次表のように変えるとともに、
反応時間を次表のように変えた外は実施例1と同
様にしてレゾール樹脂をつくり、それを用いて積
層板をつくつた。この積層板も良好な状態であつ
た。
比較例 1、2
トリエチルアミンと25%NH3触媒の使用割合お
よび触媒使用量を次表のように変えるとともに、
反応時間を次表のように変えた外は実施例1と同
様にしてレゾール樹脂をつくり、それを用いてそ
れぞれ積層板をつくつた。この場合、それぞれ次
表に示すような問題が生じた。
実施例 3、4
実施例1、2においてアニリンをフエノール1
モルに対してそれぞれ次表に示す量だけ添加した
外は実施例1、2と同様にしてレゾール樹脂を得
た。このレゾール樹脂を用いて製造した積層板は
良好であり、耐衝撃性も良好であつた。
比較例 3、4
トリエチルアミンと25%NH3触媒の使用割合お
よび触媒使用量を次表のように変えるとともに、
反応時間を次表のように変えた外は実施例3、4
と同様にしてレゾール樹脂をつくり、それを用い
てそれぞれ積層板をつくつた。この場合、それぞ
れ次表に示すような問題が生じた。
参考例 1、2
触媒としてトリエチルアミンのみを次表に示す
量用い、反応時間を同表に示すように変えた外は
実施例1と同様にしてレゾール樹脂をつくり、そ
れを用いて積層板をつくつた。この場合、次表に
示すような問題が生じた。
参考例 3
触媒として25%アンモニアのみを次表に示す量
用い、反応時間を同表に示すように変えた外は実
施例1と同様にしてレゾール樹脂をつくり、それ
を用いて積層板をつくつた。この場合、次表に示
すような問題が生じた。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a resol type phenolic resin. It has been known to produce resol-type phenolic resins (hereinafter abbreviated as resol resins) by reacting phenols and formaldehyde with a tertiary amine having a pK a of 10 or more as a catalyst. Although this method has a high reaction rate of phenols and formaldehyde and a fast reaction rate, the following problems arose when producing a laminate using the obtained resol resin. In other words, if the molecular weight of the resol resin obtained in this way is low, "fading" will occur due to resin outflow during lamination molding of the laminate, and if the molecular weight is high, the gel time of the varnish will be too short and the resol resin impregnated paper will The drying properties of the (resin paper) became extremely poor, and "fading" occurred due to insufficient fluidity of the resin. On the other hand, a method of producing resol resins by reacting phenols and formaldehyde under an ammonia catalyst is also widely used. According to this method, since the molecular weight of the obtained resol resin is large, when manufacturing a laminate using this,
Good moldability. Incidentally, the relationship between the molecular weight and melt viscosity of resol resin is shown in the drawing. In the figure, curve A is for a resol resin with a large molecular weight produced under a triethylamine catalyst.
Curve B is the melt viscosity curve at 135°C of a resol resin with a small molecular weight produced using the same catalyst as in curve A. Curve C is the melt viscosity curve at 135°C of a resol resin produced under an ammonia catalyst. ℃
This is the melt viscosity curve of As is clear from the figure, it can be seen that the larger the molecular weight of the resol resin, the more gradual the change in melt viscosity, and the better the moldability during the production of a laminate. Therefore, when a laminate is manufactured using a resol resin synthesized under an ammonia catalyst, moldability is good. However, in this method, the resol resin production reaction required a long time and the reaction rate of phenols and formaldehydes was low, resulting in poor production efficiency. Another problem with this reaction was that it had a strong odor. Therefore, an object of the present invention is to provide a method for producing a resol type phenolic resin that is free from such problems. The feature of this invention is that in a method for producing a resol type phenolic resin by reacting phenols and formaldehyde in the presence of an alkaline catalyst, a tertiary amine having a pKa of 10 or more and ammonia are used together as the alkaline catalyst, both,
(Tertiary amine with pK a of 10 or more)/(ammonia)
The purpose is to mix and use them so that the molar ratio of the two is 0.8 to 2.0. That is, by doing so, a resol resin having a large molecular weight and a long gel time can be efficiently produced with reduced odor. Next, this invention will be explained in detail. The phenols and formaldehyde used in this invention are those commonly used. And their usage ratio is (formaldehyde)/
It is preferable to select a molar ratio of (phenols) from 1.0 to 1.5. As alkaline catalysts, triethylamine,
A tertiary amine with a pKa of 10 or more, such as trimethylamine, and ammonia are used in combination. The ratio of the two used is preferably such that the molar ratio of (tertiary amine)/(ammonia) is 0.8 to 2.0, more preferably 1.2 to 1.5.
If the molar ratio between the two is less than 0.8, the reaction rate of the raw materials will be low and the reaction will be slow, and if it exceeds 2.0, the moldability will deteriorate during the production of a laminate. Furthermore, when a tertiary amine with a pK a of less than 10 is used, the reaction rate becomes extremely slow, which is unsatisfactory for actual resin production. There is no particular restriction on the amount of these composite catalysts used. The amount of catalyst to be used may be selected depending on the reaction time. However, usually the composite catalyst is 0.05% per mole of phenol.
~0.02Nmol is used. When producing resol resin using such a composite catalyst system, it is preferable to carry out the reaction depending on the type and amount of the catalyst, and to terminate the reaction so that the molecular weight is in the range of 280 to 380. . The gel time of the resol resin thus obtained was more than 17 minutes, and the formaldehyde reaction rate was 95 minutes.
% or more. In this case, if the gel time is 16 minutes or less, drying workability tends to be poor when used for resin paper. Furthermore, if the formaldehyde reaction rate is less than 95%, the odor tends to increase and workability tends to decrease. Using the resol resin efficiently produced in this manner, resin-impregnated paper was made by impregnating and drying a base material such as paper using a conventional method, and a plurality of sheets of paper were laminated and molded to make a laminate. In this case, the drying workability of the resin-impregnated paper was also good, and a laminate in good condition was obtained without "fading" or the like during lamination molding of the laminate. The present invention can also be applied to the production of aniline-modified resol resins for producing laminates with high impact resistance. Also in this case, the same effects as in the above case can be expected. When producing such an aniline-modified resol resin, for example, 0.015 to 0.045 mol of aniline may be added to 1 mol of phenol in addition to the above-mentioned catalyst. Next, examples will be described. Example 1 94 g (1 mol) of phenol, 65 g (1.2 mol) of 55% formalin, 0.005 mol (0.51 g) of triethylamine, and 0.0038 mol (0.26 g) of 2.5% NH 3 were added to a 300 ml flask, and a stirring bar and thermometer were added. was attached and stirred, and after 30 minutes, it was brought to a boil, kept in that state for 85 minutes, and then cooled to obtain a resol resin. The molecular weight of this product is 296 (measured by high performance liquid chromatography), and the gel time at 135°C is:
22 minutes 18 seconds, formaldehyde reaction rate 96.0%
It was hot. When a resin paper was prepared by impregnating and drying this material into a paper base material, the drying workability was good. As a result of stacking a plurality of sheets and molding them, a good laminate was obtained. That is, the results show that the resol resin obtained in this example has good moldability and good drying workability. Example 2 The proportions and amounts of triethylamine and 25% NH 3 catalyst used were changed as shown in the table below, and
A resol resin was prepared in the same manner as in Example 1, except that the reaction time was changed as shown in the table below, and a laminate was made using it. This laminate was also in good condition. Comparative Examples 1 and 2 The proportions and amounts of triethylamine and 25% NH 3 catalyst used were changed as shown in the table below, and
A resol resin was prepared in the same manner as in Example 1, except that the reaction time was changed as shown in the table below, and laminates were made using the resin. In each case, problems occurred as shown in the table below. Examples 3 and 4 In Examples 1 and 2, aniline was replaced with phenol 1
A resol resin was obtained in the same manner as in Examples 1 and 2, except that the amounts shown in the table below were added based on the mole. The laminate produced using this resol resin was of good quality and had good impact resistance. Comparative Examples 3 and 4 The proportions and amounts of triethylamine and 25% NH 3 catalyst used were changed as shown in the table below, and
Examples 3 and 4 except that the reaction time was changed as shown in the table below.
Resole resin was made in the same manner as above, and laminates were made using it. In each case, problems occurred as shown in the table below. Reference Examples 1 and 2 A resol resin was produced in the same manner as in Example 1, except that only triethylamine was used as a catalyst in the amount shown in the table below, and the reaction time was changed as shown in the table, and a laminate was made using it. Ivy. In this case, problems as shown in the following table arose. Reference Example 3 A resol resin was produced in the same manner as in Example 1, except that only 25% ammonia was used as a catalyst in the amount shown in the table below, and the reaction time was changed as shown in the table, and a laminate was made using it. Ivy. In this case, problems as shown in the following table arose. 【table】
図面はレゾール樹脂の分子量と溶融粘度の関係
を説明する説明図である。
The drawing is an explanatory diagram illustrating the relationship between the molecular weight and melt viscosity of a resol resin.
Claims (1)
性触媒の存在下で反応させることによりレゾール
型フエノール樹脂を製造する方法において、アル
カリ性触媒としてpKaが10以上の第3アミンとア
ンモニアとを併用し、両者を、(pKaが10以上の
第3アミン)/(アンモニア)のモル比が0.8〜
2.0になるように混合して用いることを特徴とす
るレゾール型フエノール樹脂の製造方法。1. In a method for producing a resol type phenolic resin by reacting phenols and formaldehyde in the presence of an alkaline catalyst, a tertiary amine with a pK a of 10 or more and ammonia are used together as the alkaline catalyst, and both are combined into (pK Tertiary amine with a of 10 or more)/(ammonia) molar ratio from 0.8 to
1. A method for producing a resol type phenolic resin, which is characterized in that it is used by mixing it so that the amount of the resin becomes 2.0.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14440377A JPS5476694A (en) | 1977-11-30 | 1977-11-30 | Preparation of resol-type phenolic resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14440377A JPS5476694A (en) | 1977-11-30 | 1977-11-30 | Preparation of resol-type phenolic resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5476694A JPS5476694A (en) | 1979-06-19 |
JPS6158483B2 true JPS6158483B2 (en) | 1986-12-11 |
Family
ID=15361349
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14440377A Granted JPS5476694A (en) | 1977-11-30 | 1977-11-30 | Preparation of resol-type phenolic resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5476694A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2596249B2 (en) * | 1991-04-17 | 1997-04-02 | 新神戸電機株式会社 | Manufacturing method of phenolic resin molding material for injection molding |
-
1977
- 1977-11-30 JP JP14440377A patent/JPS5476694A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5476694A (en) | 1979-06-19 |
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