JPH0464858B2 - - Google Patents
Info
- Publication number
- JPH0464858B2 JPH0464858B2 JP60017521A JP1752185A JPH0464858B2 JP H0464858 B2 JPH0464858 B2 JP H0464858B2 JP 60017521 A JP60017521 A JP 60017521A JP 1752185 A JP1752185 A JP 1752185A JP H0464858 B2 JPH0464858 B2 JP H0464858B2
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- tung oil
- oil
- acid
- modified phenolic
- 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 22
- 239000002383 tung oil Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 9
- 238000003475 lamination Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 description 14
- 239000000123 paper Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 8
- 240000002834 Paulownia tomentosa Species 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000019499 Citrus oil Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- CUXYLFPMQMFGPL-FWSDQLJQSA-N alpha-Eleostearic acid Natural products CCCCC=CC=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-FWSDQLJQSA-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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000010500 citrus oil Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- IXLCRBHDOFCYRY-UHFFFAOYSA-N dioxido(dioxo)chromium;mercury(2+) Chemical compound [Hg+2].[O-][Cr]([O-])(=O)=O IXLCRBHDOFCYRY-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 description 1
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000007517 lewis acids Chemical class 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 235000019488 nut oil Nutrition 0.000 description 1
- 239000010466 nut oil Substances 0.000 description 1
- -1 octylphenol Chemical compound 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Organic Insulating Materials (AREA)
Description
産業上の利用分野
本発明は、フエノール樹脂積層板の製造法に関
する。
従来の技術
フエノール樹脂積層板あるいはその銅張り積層
板には、従来桐油変性のフエノール樹脂が広く用
いられている。桐油は、共役二重結合を有しフエ
ノール類との反応性が優れているため、その変性
フエノール樹脂を用いることにより、優れた電気
性能および打抜加工性を有する積層板が得られ
る。しかし桐油は価格が大幅に変動し易く、安定
した原料確保が困難な欠点がある。
一方、オイチシカ油は、桐油に比べ価格的に安
定した原料であり、桐油の主成分α−エレオステ
アリン酸と同様の共役トリエン構造を有するα−
リカン酸を主成分とするため、桐油とよく似た反
応性を示す。
発明が解決しようとする問題点
しかし、α−リカン酸は、α−エレオステアリ
ン酸と異なり、分子鎖中にケト基を有する。また
オイチシカ油は、桐油に比べ飽和脂肪酸の含有量
が多い。さらに、粘度が高いなど物理的、化学的
性質に相違点がある。例えば、オイチシカ油変性
フエノール樹脂は、桐油変性フエノール樹脂に比
べ耐酸性、耐アルカリ性、耐溶剤性は劣る欠点が
ある。従つて、これを使用した積層板あるいは銅
張り積層板が、例えばプリント回路製造工程の何
等かのドラブルで高温、高濃度の酸液、アルカリ
液または有機溶剤に長時間接したとき、その表面
が変色または肌荒れをおこす惧れがある。
本発明は、オイチシカ油変性フエノール樹脂を
用いた積層板において、上述の欠点を除去するも
ので、電気性能、打抜加工性、耐酸性、耐アルカ
リ性、耐溶剤性ともに優れた積層板あるいは金属
箔張り積層板を提供することを目的とする。
問題点を解決するための手段
上記目的を達成するために、本発明は、オイチ
シカ油変性フエノール樹脂含浸基材層の表面に桐
油変性フエノール樹脂含浸基材層を配置して積層
成形することを特徴とする。
作 用
本発明による積層板は、耐酸性、耐アルカリ
性、耐溶剤性に優れた桐油変性フエノール樹脂含
浸基材を表面に配置しているので、オイチシカ油
変性フエノール樹脂の有している前記欠点を排除
しながら、他の優れた特性を発揮できる。
実施例
本発明に用いるオイチシカ油変性フエノール樹
脂は、石炭酸、クレゾール、キシレノール、ブチ
ルフエノール、オクチルフエノール、ノニルフエ
ノール、カシユーナツトオイル、ウルシオール、
シゾルシンナフトール、ノボラツク、ビスフエノ
ールＡ、ビスフエノールＦなどのフエノール類と
オイチシカ油を塩酸、硫酸、燐酸などの無機酸、
トルエンスルフオン酸、キシレンスルフオン酸な
どの有機酸あるいはルイス酸などの酸性触媒存在
下で反応させた後、更にアンモニア、ヘキサメチ
レンテトラミン、エチレンジアミン、ジエチレン
トリアミン、ジメチルアミン、ジエチルアミン、
トリメチルアミン、トリエチルアミンなどの塩基
性触媒存在下でホルマリン、パラホルムアルデヒ
ドなどのホルムアルデヒド類を反応して得られ
る。
また、桐油変性フエノール樹脂は、桐油を上述
のオイチシカ油の場合と同様の方法で反応させて
得ることができる。
本発明に用いる基材としては、リンター紙、ク
ラフト紙などの繊維素系原紙、綿布、ガラス布、
ガラス不織布、合成繊維布、その不織布などがあ
る。繊維素系基材の場合、予め水溶性のフエノー
ル樹脂初期縮合物、メラミン樹脂初期縮合物を含
浸したものを用いることも可能である。
本発明を図面によつて説明すると、第１図にお
いて、オイチシカ油変性フエノール樹脂含浸基材
層１の両表面に桐油変性フエノール樹脂含浸基材
層２，２′を配置構成し、これを金属鏡面板に挾
んで加熱加圧して積層板を得る。
また、第２図は、本発明の他の例で、オイチシ
カ油変性フエノール樹脂含浸基材層１の両表面に
桐油変性フエノール樹脂含浸基材層２，２′を配
置し、さらにその片側表面に金属箔３を配置構成
し、これを同様に金属鏡面板に挾んで加熱加圧し
て金属箔張り積層板を得る。なお、金属箔３に、
耐酸、耐アルカリ、耐溶剤性の優れた接着剤を塗
布したものを用い積層成形するときは、金属箔側
の桐油変性フエノール樹脂含浸基材層２は省略し
てもよい。
実施例 １
石炭酸530ｇ、オイチシカ油470ｇ、パラトルエ
ンスルフオン酸0.6ｇを混合し、95〜100℃にて
120分間反応させた後、更に、トリエチルアミン
22ｇ、85％パラホルムアルデヒド245ｇを加え、
90〜95℃にて６時間反応した後、メタノールを加
えて希釈し50％濃度のオイチシカ油変性フエノー
ル樹脂ワニスを得た。
別に、合成クレゾール（メタクレゾール60％、
パラクレゾール40％）580ｇ、桐油420ｇ、パラト
ルエンスルフオン酸0.5ｇを加え、80℃にて90分
間反応させた後、更に、25％アンモニア水35ｇ、
85％パラフオルムアルデヒド240ｇを加え、75〜
80℃にて４時間反応した。減圧下脱水した後、ト
ルエン／メタノール＝50／50溶剤を加え希釈し50
％濃度の桐油変性フエノール樹脂ワニスを得た。
予め水溶性フエノール樹脂初期縮合物で下塗り
を施したクラフト紙に、上記オイチシカ油変性フ
エノール樹脂ワニスを含浸乾燥して塗工紙（以下
塗工紙という）を得た。
別に、上記と同一の下塗り処理クラフト紙に、
上記桐油変性フエノール樹脂ワニスを含浸乾燥し
て塗工紙（以下塗工紙という）を得た。
塗工紙を６プライ積層した両表面に塗工紙
を各１プライを重ね合わせ、更にその片側最表面
に35ｍμ銅箔を配した後、これをステンレス鏡面
板の間に挾み、160℃、圧力100Kgｆ／cm2にて55分
間加熱加圧して1.6mm厚さの銅張り積層板（以下
本発明品という）を得た。
比較例 １
比較のため、塗工紙のみを８プライを重ね合
わせてその片側に実施例１と同一の35ｍμ銅箔を
配置し、実施例１と同一条件にて積層成形して
1.6mm厚さの銅張り積層板（以下比較品という）
を得た。
得られた各銅張り積層板の性能比較を第１表に
示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for manufacturing a phenolic resin laminate. Prior Art Tung oil-modified phenolic resin has been widely used for phenolic resin laminates or copper-clad laminates thereof. Tung oil has a conjugated double bond and has excellent reactivity with phenols, so by using the modified phenolic resin, a laminate with excellent electrical performance and punching workability can be obtained. However, the price of tung oil tends to fluctuate significantly, and it is difficult to secure a stable supply of raw materials. On the other hand, Oiticica oil is a more stable raw material in terms of price than tung oil, and has an α-triene structure similar to α-eleostearic acid, the main component of tung oil.
Because its main component is lycanic acid, it exhibits reactivity similar to tung oil. Problems to be Solved by the Invention However, α-lycanic acid, unlike α-eleostearic acid, has a keto group in its molecular chain. Oiticica oil also has a higher content of saturated fatty acids than tung oil. Furthermore, there are differences in physical and chemical properties such as higher viscosity. For example, phenolic resins modified with citrus oil have a disadvantage of being inferior in acid resistance, alkali resistance, and solvent resistance compared to tung oil-modified phenolic resins. Therefore, when a laminate or copper-clad laminate using this material comes into contact with high temperature, high concentration acid solution, alkaline solution, or organic solvent for a long time, for example, during some kind of trouble in the printed circuit manufacturing process, its surface may deteriorate. There is a risk of discoloration or skin irritation. The present invention eliminates the above-mentioned drawbacks in a laminate using Oiticica oil-modified phenolic resin, and is a laminate or metal foil that has excellent electrical performance, punching workability, acid resistance, alkali resistance, and solvent resistance. The purpose is to provide stretched laminates. Means for Solving the Problems In order to achieve the above object, the present invention is characterized in that a base material layer impregnated with tung oil modified phenolic resin is arranged on the surface of a base material layer impregnated with Oiticica oil modified phenolic resin, and lamination molding is performed. shall be. Function The laminate according to the present invention has a base material impregnated with tung oil-modified phenolic resin having excellent acid resistance, alkali resistance, and solvent resistance on its surface. While eliminating it, other excellent characteristics can be exhibited. Examples The oiticica oil-modified phenolic resin used in the present invention includes carbolic acid, cresol, xylenol, butylphenol, octylphenol, nonylphenol, oak nut oil, urushiol,
Phenols such as Schizorcinnaphthol, Novolac, Bisphenol A, and Bisphenol F and Oiticica oil are combined with inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid.
After reacting in the presence of an organic acid such as toluenesulfonic acid or xylene sulfonic acid or an acidic catalyst such as a Lewis acid, ammonia, hexamethylenetetramine, ethylenediamine, diethylenetriamine, dimethylamine, diethylamine,
It is obtained by reacting formaldehydes such as formalin and paraformaldehyde in the presence of a basic catalyst such as trimethylamine or triethylamine. Further, the tung oil-modified phenolic resin can be obtained by reacting tung oil in the same manner as in the case of the above-mentioned oiticica oil. The base materials used in the present invention include cellulose base papers such as linter paper and kraft paper, cotton cloth, glass cloth,
There are glass nonwoven fabrics, synthetic fiber fabrics, and their nonwoven fabrics. In the case of a cellulose base material, it is also possible to use one impregnated in advance with a water-soluble phenolic resin initial condensate or melamine resin initial condensate. To explain the present invention with reference to drawings, in FIG. 1, tung oil-modified phenolic resin-impregnated base material layers 2 and 2' are arranged on both surfaces of a tung oil-modified phenolic resin-impregnated base material layer 1, and these are arranged as metal mirrors. It is sandwiched between face plates and heated and pressed to obtain a laminate. FIG. 2 shows another example of the present invention, in which tung oil-modified phenolic resin-impregnated base layers 2 and 2' are arranged on both surfaces of the euticica oil-modified phenolic resin-impregnated base layer 1, and further, on one side of the base material layers 2 and 2' are arranged. The metal foil 3 is arranged and configured, and is similarly sandwiched between metal mirror plates and heated and pressed to obtain a metal foil-clad laminate. In addition, in the metal foil 3,
When laminated and molded using an adhesive coated with an adhesive having excellent acid resistance, alkali resistance, and solvent resistance, the tung oil-modified phenolic resin impregnated base layer 2 on the metal foil side may be omitted. Example 1 530 g of carbolic acid, 470 g of oiticica oil, and 0.6 g of para-toluenesulfonic acid were mixed and heated at 95 to 100°C.
After reacting for 120 minutes, add triethylamine
Add 22g and 245g of 85% paraformaldehyde,
After reacting at 90 to 95°C for 6 hours, methanol was added to dilute the mixture to obtain a 50% Oiticica oil-modified phenolic resin varnish. Separately, synthetic cresol (metacresol 60%,
After adding 580 g of para-cresol (40%), 420 g of tung oil, and 0.5 g of para-toluenesulfonic acid and reacting at 80°C for 90 minutes, further add 35 g of 25% ammonia water,
Add 240g of 85% paraformaldehyde to 75~
The reaction was carried out at 80°C for 4 hours. After dehydrating under reduced pressure, dilute with toluene/methanol = 50/50 solvent.
% concentration of tung oil modified phenolic resin varnish was obtained. A coated paper (hereinafter referred to as coated paper) was obtained by impregnating kraft paper, which had been undercoated with a water-soluble phenolic resin initial condensate in advance, with the above-mentioned Oiticica oil-modified phenolic resin varnish and drying it. Separately, on the same primed kraft paper as above,
The above tung oil-modified phenolic resin varnish was impregnated and dried to obtain coated paper (hereinafter referred to as coated paper). Layer 1 ply of coated paper on both surfaces of 6 plies of coated paper, then place 35mmμ copper foil on the outermost surface of one side, sandwich it between stainless steel mirror plates, and heat at 160℃ and pressure 100Kgf. /cm 2 for 55 minutes to obtain a 1.6 mm thick copper-clad laminate (hereinafter referred to as the product of the present invention). Comparative Example 1 For comparison, 8 plies of coated paper were stacked together, the same 35mmμ copper foil as in Example 1 was placed on one side, and lamination molding was performed under the same conditions as in Example 1.
1.6mm thick copper-clad laminate (hereinafter referred to as comparison product)
I got it. Table 1 shows a comparison of the performance of each of the copper-clad laminates obtained.
【表】
発明の効果
上述の如く、本発明は、耐酸性、耐アルカリ
性、耐溶剤性が優れた桐油変性フエノール樹脂の
層を表面に配置構成しているので、高温、高濃
度、長時間の過酷な条件に積層板が接触しても変
色、肌荒れなどの劣化を防止することができる。
そして、オイチシカ油変性フエノール樹脂を用い
ながら、電気絶縁性、打抜加工性等その他の特性
は十分保持している点、その工業的価値は極めて
大なるものである。[Table] Effects of the Invention As mentioned above, the present invention has a layer of tung oil modified phenol resin with excellent acid resistance, alkali resistance, and solvent resistance on the surface, so it can withstand high temperatures, high concentrations, and long periods of time. Even if the laminate comes into contact with harsh conditions, it can prevent deterioration such as discoloration and rough skin.
Furthermore, while using Oiticica oil-modified phenolic resin, other properties such as electrical insulation and punching workability are sufficiently maintained, and its industrial value is extremely great.
第１図は本発明による積層板の層構成を示す断
面、第２図は同他の例を示す断面図である。
１はオイチシカ油変性フエノール樹脂含浸基材
層、２，２′は桐油変性フエノール樹脂含浸基材
層。
FIG. 1 is a cross-sectional view showing the layer structure of a laminate according to the present invention, and FIG. 2 is a cross-sectional view showing another example. 1 is a base material layer impregnated with a phenolic resin modified with citrus oil, and 2 and 2' are base material layers impregnated with a phenolic resin modified with tung oil.
Claims (1)
の表面に桐油変性フエノール樹脂含浸基材層を配
置して積層成形することを特徴とする積層板の製
造法。1. A method for manufacturing a laminate, which comprises arranging a base material layer impregnated with tung oil modified phenolic resin on the surface of a base material layer impregnated with phenolic resin modified with tung oil and performing lamination molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60017521A JPS61175039A (en) | 1985-01-31 | 1985-01-31 | Manufacture of phenol resin laminated board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60017521A JPS61175039A (en) | 1985-01-31 | 1985-01-31 | Manufacture of phenol resin laminated board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61175039A JPS61175039A (en) | 1986-08-06 |
| JPH0464858B2 true JPH0464858B2 (en) | 1992-10-16 |
Family
ID=11946254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60017521A Granted JPS61175039A (en) | 1985-01-31 | 1985-01-31 | Manufacture of phenol resin laminated board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61175039A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2610707B2 (en) * | 1990-11-01 | 1997-05-14 | 日立化成工業株式会社 | Manufacturing method of thermosetting resin laminate |
-
1985
- 1985-01-31 JP JP60017521A patent/JPS61175039A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61175039A (en) | 1986-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3947393A (en) | Resin composition for laminates and prepared therefrom | |
| JPH0464858B2 (en) | ||
| JPH04211941A (en) | Copper-plated polyether imide laminated plate with high separation strength | |
| JPH04363240A (en) | Phenol resin laminate and its manufacture | |
| JPH0574609B2 (en) | ||
| JPS59182815A (en) | Oil-modified phenolic resin and electrical laminated board using the same | |
| JPS608014B2 (en) | Manufacturing method of laminates | |
| JPH04224857A (en) | Phenol resin composition | |
| JP3065383B2 (en) | Manufacturing method of phenolic resin laminate | |
| JPH05320298A (en) | Production of oil-modified phenolic resin for use in laminate | |
| JPS59182816A (en) | Oil-modified phenolic resin and electrical laminated board using the said resin | |
| JPS57209916A (en) | Production of oil-modified phenol resin for laminate | |
| JPS58164613A (en) | Production of oil-modified phenolic resin for laminate | |
| JPH0579092B2 (en) | ||
| JPS59174628A (en) | Production of laminated plate | |
| JPS6172028A (en) | Production of laminate | |
| JPS61121932A (en) | Manufacture of phenolic resin laminated sheet | |
| JPS6172029A (en) | Production of laminate | |
| JPH04364941A (en) | Phenol resin laminated sheet | |
| JPS58118813A (en) | Production of oil-modified phenolic resin | |
| JPH05220882A (en) | Production of phenol resin laminated sheet | |
| JPH0680859A (en) | Phenolic resin composition | |
| JPH05154955A (en) | Production of phenol resin laminated sheet | |
| JPS58164612A (en) | Production of oil-modified phenolic resin for laminate | |
| JPS60262644A (en) | Manufacture of phenol resin laminated board |