JPS642619B2 - - Google Patents
Info
- Publication number
- JPS642619B2 JPS642619B2 JP11623684A JP11623684A JPS642619B2 JP S642619 B2 JPS642619 B2 JP S642619B2 JP 11623684 A JP11623684 A JP 11623684A JP 11623684 A JP11623684 A JP 11623684A JP S642619 B2 JPS642619 B2 JP S642619B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- formaldehyde
- laminate
- phenols
- 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
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- 150000002989 phenols Chemical class 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims 1
- 239000002383 tung oil Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- -1 cresol xylenol Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
（産業上の利用分野）
本発明は電気絶縁板として用いられるフエノー
ル樹脂積層板の製造法に関する。
（発明の背景）
最近、絶縁材料等に民生用電子機器に使用され
る積層板および銅張り積層板は、加工設備の自動
化、省力化等の観点から常温又は常温付近の比較
的低温での打抜加工性の優れたものが要求されて
いる。
このため乾性油として桐油で変性したフエノー
ルホルムアルデヒド樹脂が利用されている。しか
し、桐油等による変性のため硬化速度が遅く、架
橋密度も低下するため、積層板中の樹脂は硬化不
足になりやすく、耐熱性、耐溶剤性、等の特性が
低下する。また打抜加工の際には、架橋密度が低
いため層間はくり等が発生しやすい。
すなわち従来の桐油−フエノール類の反応物は
桐油に対するフエノールの付加モル数が低く、ま
た桐油の重合物を生成するため、ホルムアルデヒ
ドとの反応すなわち、樹脂化反応、および硬化反
応で反応速度、および硬化速度が低下し、諸特性
低下の原因になつていた。
また一方この対策として桐油１モルに対して６
モルのメタクレゾール付加した反応物も提案され
ているが、量産性、経済性を考えると十分ではな
かつた。
（発明の目的）
本発明の目的は、打抜加工性に優れるフエノー
ル樹脂積層板の製造法を提供するものである。
（発明の構成）
本発明はフエノール類とホルムアルデヒドとを
２価以上の多価アミンの存在下で反応させた反応
生成物を、乾性油変性フエノールホルムアルデヒ
ド樹脂に添加した樹脂成分を、積層板用基材に含
浸、乾燥し、積層成型することを特徴とするフエ
ノール樹脂積層板の製造法である。
フエノール類としては、フエノール、アルキル
フエノール（例えばクレゾールキシレノール、エ
チルフエノール、ブチルフエノール）、フエニル
フエノール、ビスフエノールＡ、レゾルシール等
が用いられる。
ホルムアルデヒドとして、パラホルムアルデヒ
ドを用いることも出来る。
２価以上の多価アミンとしては、炭素数２〜６
の脂肪族炭化水素を骨格とし、アミノ基を１分子
中に２〜４個もつものが好ましい。このような多
価アミンとして、ジアミン（例えばエチレンジア
ミン、トリエチレンジアミン、プトレツシン、ガ
ダベリン、ヘキサメチレンジアミン）トリアミン
（例えばジエチレントリアミン）テトラミン（例
えばトリエチレンテトラミン）等が用いられる。
フエノール類、ホルムアルデヒド、多価アミン
は、フエノール類１モルに対して多価アミン1/5
〜１モル、ホルムアルデヒド1/2〜１モルを60℃
〜120℃、30分〜５時間反応させるのが好ましい。
このフエノール類−ホルムアルデヒド−多価ア
ミンの反応生成物は、乾性油変性フエノール樹脂
と架橋するのが好ましく、２核体から５核体程度
の比較的低分子のものが好ましい。
フエノール類−ホルムアルデヒド−多価アミン
の反応生成物は、乾性油変性フエノールホルムア
ルデヒド樹脂100重量部に対して１重量部から20
重量部添加される。
乾性油変性フエノールホルムアルデヒド樹脂
は、桐油等の乾性油とフエノール類とを反応さ
せ、ホルムアルデヒドでレゾール化して製造され
る。
以上の樹脂成分を有機溶剤に溶解しワニスと
し、紙、ガラス布、ガラス不織布等の基材に含
浸、乾燥しプリプレグを得、プリプレグの必要枚
数を常法に従つて加熱加圧、積層成型し、フエノ
ール樹脂積層板を製造する。
実施例
桐油87.5ｇ、フエノール141ｇパラトルエンス
ルホン酸0.08ｇを混合し、110℃１時間反応させ
る。この反応物にパラターシヤリーフエノール41
ｇパラホルムアルデヒド60ｇ25％アンモニア水６
ｇを入れ80℃３時間反応させた。
つぎに反応液を減圧下で水を除去する脱水が進
むにつれて液温は除々に上昇し70℃になると反応
物は透明になる。引続き脱水を行いゲルタイムが
３分30秒になつた時脱水を止め急冷し、樹脂を
得た。又、エチレンジアミン９ｇ、フエノール48
ｇ、パラホルムアルデヒド17ｇを加え、80℃２時
間反応させ、つぎに反応液を減圧下で水を除去し
液温が80℃になるまで脱水を行い、バツトにあけ
急冷させ樹脂を得る。樹脂の樹脂分100重量
部に対して樹脂の樹脂分を５重量部混合し、メ
タノール、アセトン１：１の混合溶剤に溶かして
50重量％の樹脂ワニスを製造した。
予め、下塗り用水溶性フエノールホルムアルデ
ヒドワニスで下塗りをほどこしたクラフト紙に上
記ワニスを含浸し、ついで乾燥して被着樹脂分50
重量％のプリプレグを得た。このものを所定枚数
重ね合せ、160〜165℃80Kg／cm2の積層条件で60分
加熱加圧して厚さ1.6mmの積層板を得た。この積
層板の諸特性を別表に示す。
比較例
実施例で得られた樹脂にメタノール、アセト
ン１：１の混合溶剤に溶かして50重量％の樹脂ワ
ニスを製造し、実施例と同様の方法を用い積層板
を得た。この積層板の諸特性を別表に示す。
(Industrial Application Field) The present invention relates to a method for manufacturing a phenolic resin laminate used as an electrical insulating board. (Background of the Invention) Recently, laminates and copper-clad laminates used as insulating materials in consumer electronic devices have been manufactured at room temperature or a relatively low temperature near room temperature from the viewpoint of automating processing equipment and saving labor. There is a demand for products with excellent punchability. For this reason, phenol formaldehyde resin modified with tung oil is used as a drying oil. However, due to modification with tung oil or the like, the curing speed is slow and the crosslinking density is reduced, so the resin in the laminate tends to be insufficiently cured and properties such as heat resistance and solvent resistance are reduced. Furthermore, during punching, interlayer peeling is likely to occur due to the low crosslinking density. In other words, the conventional reaction product of tung oil and phenols has a low number of moles of phenol added to tung oil, and also produces a polymer of tung oil, so the reaction rate and curing reaction with formaldehyde, that is, the resinization reaction and curing reaction, are low. The speed was reduced, which caused deterioration of various characteristics. On the other hand, as a countermeasure for this, 6 ml per mole of tung oil is
A reactant with a molar amount of meta-cresol added has also been proposed, but this has not been sufficient in terms of mass production and economy. (Object of the Invention) An object of the present invention is to provide a method for producing a phenolic resin laminate having excellent punching workability. (Structure of the Invention) The present invention uses a resin component obtained by adding a reaction product of phenols and formaldehyde in the presence of a divalent or higher polyvalent amine to a drying oil-modified phenol formaldehyde resin as a substrate for a laminate. This is a method for producing a phenolic resin laminate, which is characterized by impregnating the material, drying it, and laminating it. As the phenols, phenol, alkylphenol (for example, cresol xylenol, ethylphenol, butylphenol), phenylphenol, bisphenol A, resolcil, etc. are used. Paraformaldehyde can also be used as formaldehyde. The polyvalent amine having a valence of 2 or more has 2 to 6 carbon atoms.
It is preferable to have an aliphatic hydrocarbon skeleton and 2 to 4 amino groups in one molecule. As such polyvalent amines, diamines (eg, ethylenediamine, triethylenediamine, putrescine, gadaverine, hexamethylenediamine), triamines (eg, diethylenetriamine), tetramines (eg, triethylenetetramine), and the like are used. For phenols, formaldehyde, and polyvalent amines, the proportion of polyvalent amines is 1/5 per mole of phenols.
~1 mol, formaldehyde 1/2~1 mol at 60℃
It is preferable to react at ~120°C for 30 minutes to 5 hours. The reaction product of phenols-formaldehyde-polyvalent amine is preferably crosslinked with the drying oil-modified phenol resin, and is preferably a relatively low-molecular product of about 2- to 5-nuclear bodies. The reaction product of phenols-formaldehyde-polyvalent amine is 1 to 20 parts by weight per 100 parts by weight of the dry oil-modified phenol formaldehyde resin.
Added in parts by weight. The drying oil-modified phenol-formaldehyde resin is produced by reacting a drying oil such as tung oil with phenols and converting the mixture into a resol with formaldehyde. The above resin components are dissolved in an organic solvent to make a varnish, impregnated into a base material such as paper, glass cloth, glass non-woven fabric, etc., and dried to obtain a prepreg.The required number of prepregs are heated and pressurized and laminated by a conventional method. , manufactures phenolic resin laminates. Example 87.5g of tung oil, 141g of phenol and 0.08g of para-toluenesulfonic acid were mixed and reacted at 110°C for 1 hour. This reactant contains paratasya leaf phenol 41
g Paraformaldehyde 60g 25% ammonia water 6
g was added and reacted at 80°C for 3 hours. Next, water is removed from the reaction solution under reduced pressure.As dehydration progresses, the temperature of the solution gradually increases until it reaches 70°C, at which point the reaction product becomes transparent. Dehydration was continued, and when the gel time reached 3 minutes and 30 seconds, dehydration was stopped and the mixture was rapidly cooled to obtain a resin. Also, 9g of ethylenediamine, 48g of phenol
g, and 17 g of paraformaldehyde were added and reacted for 2 hours at 80°C. Next, water was removed from the reaction solution under reduced pressure, dehydration was carried out until the liquid temperature reached 80°C, and the mixture was poured into a vat and quenched to obtain a resin. Mix 5 parts by weight of the resin content with 100 parts by weight of the resin content, and dissolve it in a mixed solvent of methanol and acetone 1:1.
A 50% by weight resin varnish was produced. Craft paper that has been undercoated with a water-soluble phenol formaldehyde varnish for undercoating is impregnated with the above varnish, and then dried to reduce the adhered resin content to 50%.
% prepreg by weight was obtained. A predetermined number of these sheets were stacked and heated and pressed for 60 minutes under lamination conditions of 160 to 165° C. and 80 kg/cm 2 to obtain a laminate with a thickness of 1.6 mm. The properties of this laminate are shown in the attached table. Comparative Example A 50% by weight resin varnish was prepared by dissolving the resin obtained in the example in a 1:1 mixed solvent of methanol and acetone, and a laminate was obtained using the same method as in the example. The properties of this laminate are shown in the attached table.
【表】
（発明の効果）
本発明によれば耐熱性、耐溶剤性、打抜加工性
に優れた積層板を製造することが出来る。[Table] (Effects of the Invention) According to the present invention, a laminate having excellent heat resistance, solvent resistance, and punching workability can be manufactured.
Claims (1)
上の多価アミンの存在下で反応させた反応生成物
を、乾性油変性フエノールホルムアルデヒド樹脂
に添加した樹脂成分を積層板用基材に含浸、乾燥
し、積層成型することを特徴とするフエノール樹
脂積層板の製造法。1 A reaction product obtained by reacting phenols and formaldehyde in the presence of a polyvalent amine having a valence of 2 or more is added to a dry oil-modified phenol formaldehyde resin, and the resin component is impregnated into a base material for a laminate, dried, and laminated. A method for producing a phenolic resin laminate, characterized by molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11623684A JPS60260642A (en) | 1984-06-06 | 1984-06-06 | Preparation of phenolic resin laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11623684A JPS60260642A (en) | 1984-06-06 | 1984-06-06 | Preparation of phenolic resin laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60260642A JPS60260642A (en) | 1985-12-23 |
| JPS642619B2 true JPS642619B2 (en) | 1989-01-18 |
Family
ID=14682180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11623684A Granted JPS60260642A (en) | 1984-06-06 | 1984-06-06 | Preparation of phenolic resin laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60260642A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09267644A (en) * | 1996-01-30 | 1997-10-14 | Hara Kunihito | Sun shade sheet for vehicle glass |
-
1984
- 1984-06-06 JP JP11623684A patent/JPS60260642A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09267644A (en) * | 1996-01-30 | 1997-10-14 | Hara Kunihito | Sun shade sheet for vehicle glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60260642A (en) | 1985-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3947393A (en) | Resin composition for laminates and prepared therefrom | |
| JPS642619B2 (en) | ||
| JPS60192732A (en) | Production of laminated sheet | |
| JPH047375B2 (en) | ||
| JPS6128691B2 (en) | ||
| JPS61121931A (en) | Manufacture of phenolic resin laminated sheet | |
| JPS61121932A (en) | Manufacture of phenolic resin laminated sheet | |
| JPH04224857A (en) | Phenol resin composition | |
| JP3302176B2 (en) | Resin composition for laminated board and laminated board using the same | |
| JPS59182815A (en) | Oil-modified phenolic resin and electrical laminated board using the same | |
| JPS6049216B2 (en) | Manufacturing method of laminates | |
| JPH0680859A (en) | Phenolic resin composition | |
| JPH075768B2 (en) | Epoxy resin laminate | |
| JPS6250318A (en) | Production of modified phenolic resin for laminated sheet | |
| JPH0480823B2 (en) | ||
| JPH05318688A (en) | Phenolic resin laminated plate | |
| JPS6250129A (en) | Manufacture of paper base-material phenol-resin laminated board | |
| JPS5853909A (en) | Preparation of modified phenolic resin composition for flame retardant laminate | |
| JPS61296016A (en) | Production of modified phenolic resin for laminated board | |
| JPS60115613A (en) | Production of thermosetting resin | |
| JPH03140355A (en) | Thermosetting resin composition for laminate | |
| JPS6172028A (en) | Production of laminate | |
| JPH07224134A (en) | Phenolic resin composition and laminated plate therefrom | |
| JPH05318641A (en) | Phenol resin laminate | |
| JPH06320697A (en) | Manufacture of phenol resin laminated plate |