JPS62283132A - Production of laminate for electricity - Google Patents
Production of laminate for electricityInfo
- Publication number
- JPS62283132A JPS62283132A JP11988387A JP11988387A JPS62283132A JP S62283132 A JPS62283132 A JP S62283132A JP 11988387 A JP11988387 A JP 11988387A JP 11988387 A JP11988387 A JP 11988387A JP S62283132 A JPS62283132 A JP S62283132A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated polyester
- polyester resin
- laminate
- crosslinking agent
- copper
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 230000005611 electricity Effects 0.000 title 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000011889 copper foil Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010030 laminating Methods 0.000 claims abstract description 4
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 abstract description 22
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- 229920006305 unsaturated polyester Polymers 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- -1 1,3-butylene Chemical group 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920001447 polyvinyl benzene Polymers 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
本発明は印刷回路基板用銅張り積層板にの製造法に関し
、さらに詳しくは、電気的特性、機械的強度、耐熱特性
、および吸湿特性の改良された不飽和ポリエステル樹脂
と基材と銅箔とから構成される銅張り積層板の製造法に
関する。Detailed Description of the Invention 3. Detailed Description of the Invention The present invention relates to a method for manufacturing a copper-clad laminate for printed circuit boards, and more specifically, to improve electrical properties, mechanical strength, heat resistance properties, and moisture absorption properties. This invention relates to a method for manufacturing a copper-clad laminate comprising an improved unsaturated polyester resin, a base material, and a copper foil.
本発明でいう積層板とは、銅張り積層板に用いられる積
層板を意味し、その形状は厚みがおよそ０．５〜５１朧
であるような板状物をいい、銅張り板は特に印刷回路用
として好適なものをいう。上記の如き積層板は不飽和ポ
リエステルｔｉ４脂と紙基材によって構成することがで
きる。The laminate used in the present invention refers to a laminate used for copper-clad laminates, and its shape refers to a plate-like product with a thickness of approximately 0.5 to 51 mm. Refers to something suitable for circuit use. The above-mentioned laminate can be constructed from unsaturated polyester TI4 resin and paper base material.
不飽和ポリエステル樹脂は、例えば不飽和二塩基酸、飽
和二塩基酸およびグリコールの共重合体からなる不飽和
ポリエステル鎖と分子間架橋用ビニルモノマーの混合物
を有機過酸化物等を触媒として硬化せしめて得られる。Unsaturated polyester resin is produced by curing a mixture of an unsaturated polyester chain consisting of a copolymer of an unsaturated dibasic acid, a saturated dibasic acid, and a glycol, and a vinyl monomer for intermolecular crosslinking using an organic peroxide or the like as a catalyst. can get.
架橋用ビニルモノマーとしてはスチレンを用いるのが一
般的である。Styrene is generally used as the crosslinking vinyl monomer.
このような不飽和ポリエステル樹脂は通常未硬化時にお
いては室温において液状であり、基材への含浸の際に溶
剤を必要としない点で本発明に通している。従って本発
明の積層板とは例えば上記せる如き不飽和ポリエステル
樹脂液を例えばクラフト紙に含浸し、必要枚数積層した
後硬化させることによって製造できる。硬化反応は熱以
外にも光、電子線、放射線等による硬化も可能であり、
本発明はそれらについて何ら制限するものではない。Such unsaturated polyester resins are generally liquid at room temperature when uncured, and are suitable for the present invention in that they do not require a solvent when impregnated into a substrate. Therefore, the laminate of the present invention can be produced by impregnating, for example, kraft paper with an unsaturated polyester resin liquid as described above, laminating the required number of sheets, and then curing. In addition to heat, curing reactions can also be performed using light, electron beams, radiation, etc.
The present invention does not limit them in any way.
不飽和ポリエステル樹脂は使用される架橋用モノマーの
種類や配合比率によって、その硬化物の性状は大きく変
化し、従って、このことは該樹脂と基材との複合材であ
る積層板の特性に対しても大きな影響を持つ。The properties of the cured product of unsaturated polyester resin vary greatly depending on the type and blending ratio of the crosslinking monomer used, and this may affect the properties of the laminate, which is a composite material of the resin and the base material. It has a big impact.
樹脂には架橋用モノマーの他、難燃剤、難燃助剤、充項
剤、着色剤、硬化触媒のような通常電気用積層板に配合
される添加剤を配合しても良いことは勿論である。Of course, in addition to the crosslinking monomer, the resin may also contain additives that are usually added to electrical laminates, such as flame retardants, flame retardant aids, fillers, colorants, and curing catalysts. be.
従来、架橋剤として用いられている単量体は最も広く使
われているのがスチレンでその反応性、硬化後の諸性状
がすぐれており、入手が容易であることも大きな利点で
ある。Conventionally, the most widely used monomer as a crosslinking agent is styrene, which has excellent reactivity and various properties after curing, and has the great advantage of being easily available.
酢酸ビニルは沸点が低い欠点があり、メチルメタクリレ
ートは反応性が悪い短所があり、ビニルトルエンはスチ
レンより沸点が高い特徴を持っている。Vinyl acetate has the disadvantage of a low boiling point, methyl methacrylate has the disadvantage of poor reactivity, and vinyltoluene has a higher boiling point than styrene.
アリル系ではジアリルツクレート、トリアリルシアヌレ
ート等があるが、反応性が低く、高温で長時間硬化さ↓
る必要があり、特に耐熱性を望む場合の特殊原料として
用いられる。Allyl-based products include diallyl tucrate and triallyl cyanurate, but they have low reactivity and cannot be cured at high temperatures for long periods of time↓
It is used as a special raw material when heat resistance is required.
これら架橋剤はモノビニル系は単官能性であり、アリル
系およびジビニル系は多官能性である。These crosslinking agents are monofunctional in monovinyl type, and polyfunctional in allyl type and divinyl type.
併しこれらの従来知られている架橋剤を用いて作られた
不飽和ポリエステル樹脂と基材とからなる積層板は何れ
も吸湿性が悪く、ソリ等の外観及び電気的特性に欠点が
あり、電気用積層板として満足すべきものは得られなか
った。However, all laminates made of unsaturated polyester resin and base material made using these conventionally known crosslinking agents have poor hygroscopicity and have defects in appearance and electrical properties such as warpage. A satisfactory electrical laminate could not be obtained.
そこで本発明者はこれらの欠点を解決すべく、架橋剤に
ついて鋭意研究した結果、本発明に到達したものである
。Therefore, in order to solve these drawbacks, the present inventor conducted intensive research on crosslinking agents, and as a result, arrived at the present invention.
本発明の積層板の製法は架橋剤としてスチレン及び／ま
たはその単官能性誘導体と多官能性炭化水素系ビニル単
量体とを併用した不飽和ポリエステル樹脂を用いること
を特徴とする。The method for manufacturing a laminate of the present invention is characterized by using an unsaturated polyester resin containing styrene and/or its monofunctional derivative and a polyfunctional hydrocarbon vinyl monomer as a crosslinking agent.
すなわち、本発明は架橋剤としてスチレン及び／又はそ
の単官能性誘導体と多官能性炭化水素系ビニル単量体と
を併用した不飽和ポリエステル樹脂と基材と銅箔とが接
合されてなる印刷回路基板用銅張り積層板の製造方法で
ある。That is, the present invention provides a printed circuit in which an unsaturated polyester resin using styrene and/or its monofunctional derivative and a polyfunctional hydrocarbon vinyl monomer as a crosslinking agent, a base material, and a copper foil are bonded. This is a method for manufacturing a copper-clad laminate for a board.
本発明により吸湿時の寸法安定性にすぐれており、吸湿
によるソリなどの外観の変化がなく、且つ機械的特性の
変化も少ない電気用積層板が始めて得られるようになっ
たのであり、その工業的意義は大きい。The present invention has made it possible for the first time to obtain an electrical laminate that has excellent dimensional stability when absorbing moisture, does not undergo changes in appearance such as warping due to moisture absorption, and has little change in mechanical properties, and is now available in the industry. This is of great significance.
本発明で用いられる不飽和ポリエステル鎖は例えばエチ
レングリコール等の多価アルコール、無水フクル酸等の
飽和多塩基酸、無水マレイン酸等の不飽和多塩基酸を反
応させて合成され、その基礎的構造は次式によって示さ
れる一般的によく知られているものである。The unsaturated polyester chain used in the present invention is synthesized by reacting a polyhydric alcohol such as ethylene glycol, a saturated polybasic acid such as fucuric anhydride, and an unsaturated polybasic acid such as maleic anhydride, and its basic structure is generally well known and is expressed by the following equation.
無水フタル酸の如き飽和酸をマレイン酸の如き不飽和酸
に適当に組合わせることによりエステル鎖の粘度、反応
性、単量体との相溶性を調整し硬化後の諸性状を改良す
ることができる。その混合割合を特に制限するものでは
ない。不飽和二塩基酸としては無水マレイン酸の他にマ
レイン酸、フマール酸、イタコン酸等が用いられ、飽和
二塩基酸としては無水フタル酸の他に四塩化無水フタル
酸、ヘット酸、アジピン酸等が用いられる。By appropriately combining a saturated acid such as phthalic anhydride with an unsaturated acid such as maleic acid, it is possible to adjust the viscosity, reactivity, and compatibility of the ester chain with the monomer and improve various properties after curing. can. There is no particular restriction on the mixing ratio. In addition to maleic anhydride, maleic acid, fumaric acid, itaconic acid, etc. are used as unsaturated dibasic acids, and as saturated dibasic acids, in addition to phthalic anhydride, tetrachlorophthalic anhydride, Hett's acid, adipic acid, etc. are used. is used.
二価アルコールとしてはエチレングリコールの他にプロ
ピレングリコール、１．３−ブチレンゲリコール、ジエ
チレングリコール、トリエチレングリコール、ジプロピ
レングリコール、２，２−ジエチルプロパンジオール−
１，３等が用いられる。In addition to ethylene glycol, dihydric alcohols include propylene glycol, 1,3-butylene gelicol, diethylene glycol, triethylene glycol, dipropylene glycol, and 2,2-diethylpropanediol.
1, 3, etc. are used.
本発明では上記のポリマー鎖に架橋剤としてスチレン及
び／又はその単官能性誘導体（例えばビニルトルエン等
）から選ばれた一種又は二種以上の混合物と、多官能性
炭化水素系ビニル単量体の一種又は二種以上の混合物と
からなるものを用いる。本発明では該不飽和ポリエステ
ル鎖に架）喬剤を混合したものを不飽和ポリエステル樹
脂または不飽和ポリエステル樹脂液と呼ぶ。In the present invention, one or a mixture of two or more selected from styrene and/or its monofunctional derivatives (for example, vinyltoluene, etc.) and a polyfunctional hydrocarbon vinyl monomer are added to the above polymer chain as a crosslinking agent. Use one type or a mixture of two or more types. In the present invention, a mixture of the unsaturated polyester chains and a crosslinking agent is called an unsaturated polyester resin or an unsaturated polyester resin liquid.
多官能性炭化水素系ビニル単量体とはエチレン性不飽和
基を二つ以上分子中に含み、その分子が炭化水素からな
る化合物をいう。例えばジビニルベンゼンの如きポリビ
ニルベンゼンおよびその誘導体等がある。そして、これ
らの多官能性炭化水素系ビニル単量体としてはスチレン
およびその単官能性誘導体と共重合し得る化合物でなく
てはならず、共重合速度恒数がほぼ等しくて均一な共重
合物を与えるものが好ましい。さらに硬化生成物の耐熱
性および機械的性質を害しない単量体を用いることが好
ましい。A polyfunctional hydrocarbon vinyl monomer is a compound containing two or more ethylenically unsaturated groups in its molecule, and the molecule is composed of a hydrocarbon. Examples include polyvinylbenzene such as divinylbenzene and derivatives thereof. These polyfunctional hydrocarbon vinyl monomers must be compounds that can be copolymerized with styrene and its monofunctional derivatives, and must be homogeneous copolymers with approximately equal copolymerization rate constants. It is preferable to give Furthermore, it is preferable to use monomers that do not impair the heat resistance and mechanical properties of the cured product.
上記理由から多官能性炭化水素系ビニルｓｉｔ体として
はジビニルベンゼンを主体とするものが好適である。For the above-mentioned reasons, it is preferable that the polyfunctional hydrocarbon vinyl sit form mainly consists of divinylbenzene.
本発明においてはスチレンおよびその単官能性誘導体と
多官能性炭化水素系ビニル単量体との配合比率が重要で
あって、例えばスチレンに対するジビニルベンゼンの比
率が５〜６０重量％であるモノマー混合物を不飽和ポリ
エステル樹脂に対して２０〜６０重量％添加するような
組成物を用いる。架橋剤の不飽和ポリエステルに対する
理論添加量（エステル中の二重結合数に相当する単量体
量）を越える量を使用すると、スチレンの場合スチレン
の二量体、三量体がエステル分子間の架橋にあずかる可
能性が強くなり、硬化に際しての発熱や収縮が大きくな
るばかりでなく、硬化物は機械的性質が劣化し、化学的
安定性、電気的性質、耐熱性、耐湿性が低下することが
知られているが、本発明の架橋剤ではこのようなことが
なく、むしろ硬化物の性能が向上することは驚（べきこ
とである。In the present invention, the blending ratio of styrene and its monofunctional derivatives to the polyfunctional hydrocarbon vinyl monomer is important; for example, a monomer mixture in which the ratio of divinylbenzene to styrene is 5-60% by weight is used. A composition is used in which it is added in an amount of 20 to 60% by weight based on the unsaturated polyester resin. If the amount of crosslinking agent exceeds the theoretical amount added to unsaturated polyester (the amount of monomer corresponding to the number of double bonds in the ester), in the case of styrene, styrene dimers and trimers will form between the ester molecules. The possibility of crosslinking increases, which not only increases heat generation and shrinkage during curing, but also deteriorates the mechanical properties of the cured product and reduces chemical stability, electrical properties, heat resistance, and moisture resistance. However, it is surprising that this does not occur with the crosslinking agent of the present invention, and rather the performance of the cured product is improved.
しかしながら、架橋剤としてスチレンとジビニルベンゼ
ンとの混合物を用いたとき、組成物全体に占めるジビニ
ルベンゼンの比率の増加は場合によって、得られる硬化
物の若干のもろさを招く。However, when a mixture of styrene and divinylbenzene is used as a crosslinking agent, an increase in the proportion of divinylbenzene in the total composition may lead to some brittleness of the resulting cured product.
従って、不飽和ポリエステル鎖の構造や用いる基材との
関連において望ましいジビニルベンゼンの混合比率が決
定される。あるいはジビニルベンゼン単独の代わりにジ
ビニルベンゼンよりも柔構造を与える多官能性炭化水素
系単量体、例えばシクロペンタジェン等とジビニルベン
ゼンとの混合物をスチレンと共に架橋剤として用いるこ
ともできる。Therefore, the desired mixing ratio of divinylbenzene is determined in relation to the structure of the unsaturated polyester chain and the substrate used. Alternatively, instead of divinylbenzene alone, a mixture of divinylbenzene and a polyfunctional hydrocarbon monomer that provides a softer structure than divinylbenzene, such as cyclopentadiene, can be used together with styrene as a crosslinking agent.
多官能性炭化水素系ビニル単量体の配合の効果は、特に
基材がクラフト紙等のごときセルロース繊維を主成分と
した紙であるときに特に顕著である。すなわち本発明に
おける電気用積層板においては、特に耐熱性が向上し、
あるいは吸湿時の寸法安定性、ソリなどの外観、吸湿時
の耐熱性、吸湿時の機械的強度の保持率、吸湿時の電気
絶縁性等が著しく向上する。本発明においては積層板の
製造時に銅箔を同時に積層し、接着剤を用い、あるいは
用いることなくして、銅張り積層板を作ることができる
し、あるいは積層板を製造した後、接着剤を用いて、銅
箔を接合して銅張り積層板となすことも可能である。銅
張り積層板は片面ないし両面銅張りにすることも任意で
ある。The effect of blending the polyfunctional hydrocarbon vinyl monomer is particularly remarkable when the base material is paper mainly composed of cellulose fibers, such as kraft paper. That is, in the electrical laminate according to the present invention, the heat resistance is particularly improved,
Alternatively, dimensional stability when absorbing moisture, appearance such as warpage, heat resistance when absorbing moisture, retention of mechanical strength when absorbing moisture, electrical insulation properties when absorbing moisture, etc. are significantly improved. In the present invention, a copper-clad laminate can be made by laminating copper foil at the same time when manufacturing a laminate, with or without using an adhesive, or by using an adhesive after manufacturing a laminate. It is also possible to form a copper-clad laminate by bonding copper foil. The copper-clad laminate may optionally be copper-clad on one or both sides.
また、本発明における印刷回路用銅張り積層板を製造す
るにおいて用いる不飽和ポリエステル樹脂液の粘度も重
要な要因の一つであって、本発明においてはその粘度が
０．１〜１０ポイズである時、より望ましくは０．５〜
８ボ”イズである時、良好な結果を得る。粘度の調整は
用いるスチレン等の単官能性ｉ量体および多官能性ビニ
ル単量体の種類および量によっても可能である。またこ
れら単量体よりも易揮発性である溶剤の添加によっても
可能であるが、特に本発明においては何らの溶剤を用い
ることなくして、不飽和ポリエステル鎖の分子量の減少
、架橋用液状上ツマー配合量の増加等によって望ましい
粘度の調整が可能である。In addition, the viscosity of the unsaturated polyester resin liquid used in manufacturing the copper-clad laminate for printed circuits in the present invention is also an important factor, and in the present invention, the viscosity is 0.1 to 10 poise. time, more preferably 0.5~
Good results are obtained when the number of 8-bodies is 8". The viscosity can also be adjusted by adjusting the type and amount of the monofunctional i-mer such as styrene and the polyfunctional vinyl monomer used. Although this is possible by adding a solvent that is more volatile than the polymer, in particular, in the present invention, it is possible to reduce the molecular weight of the unsaturated polyester chain and increase the amount of liquid upper binder for crosslinking without using any solvent. It is possible to adjust the desired viscosity by, for example,
実施例
プロピレングリコール、イソフタル酸およびフマル酸の
原料成分のモル比がそれぞれ３：Ｌ：２であって、平均
分子量が４０００である不飽和ポリエステル鎖を用いて
、不飽和ポリエステル鎖が５９重ｆＪ％、スチレン２８
重量％、ジビニルヘンゼン１３重量％であって、室温に
おける粘度が４゜５ポイズである不飽和ポリエステル樹
脂液を得、さらに硬化用触媒としてクメンハイドロパー
オキサイド１部、および促進剤として５％ナフテン酸コ
バルｌ−０，２部配合した。坪量が１５０ ｇ／ｍであ
って、厚みが２８５μｍであるクラフト紙に含浸せしめ
、この含浸紙を６枚積層し、同時に、厚さが３５μｍで
ある電解銅箔をラミネートし、そのまま１００℃×２０
分、ついで８５°Ｃ×１３時間の条件で硬化せしめ、厚
さが１．６ 鶴である銅張り積層板を得た。Example Using an unsaturated polyester chain having a molar ratio of propylene glycol, isophthalic acid, and fumaric acid as raw materials, each having a molar ratio of 3:L:2 and an average molecular weight of 4000, the unsaturated polyester chain was 59% by weight/fJ%. , styrene 28
An unsaturated polyester resin solution containing 13% by weight of divinylhenzene and a viscosity of 4.5 poise at room temperature was obtained, in addition to 1 part of cumene hydroperoxide as a curing catalyst and 5% naphthene as an accelerator. 0.2 parts of acid cobalt was added. Kraft paper with a basis weight of 150 g/m and a thickness of 285 μm was impregnated, six sheets of this impregnated paper were laminated, and at the same time, an electrolytic copper foil with a thickness of 35 μm was laminated, and as it was heated at 100 ° C. 20
It was then cured at 85° C. for 13 hours to obtain a copper-clad laminate having a thickness of 1.6 mm.
比較例
実施例において、ジビニルベンゼンを混合せず、ポリマ
ー鎖成分５９重量％、スチレン４１重量％であって、室
温における粘度が４．５ポイズの樹脂液を得、実施例と
同様にして、銅張り積層板を得た。Comparative Example In the example, divinylbenzene was not mixed, a resin liquid containing 59% by weight of the polymer chain component, 41% by weight of styrene, and a viscosity of 4.5 poise at room temperature was obtained, and copper was added in the same manner as in the example. A stretched laminate was obtained.
以上の実施例および比較例の特性を第１表に示す。試験
はＪＩＳ−Ｃ−６４８１によった。Table 1 shows the characteristics of the above examples and comparative examples. The test was based on JIS-C-6481.
（以下余白） 第 １ 表(Margin below) Table 1
Claims (1)
０重量％の配合比率で多官能性炭化水素系ビニル単量体
を併用してなる架橋剤を２０〜６０重量％含有せしめた
、室温において液状である不飽和ポリエステル樹脂をセ
ルロース繊維を主成分とした基材に含浸せしため後、基
材を積層して硬化させると共に銅箔を接合することを特
徴とする銅張り積層板の製造法。5 to 6 for styrene and/or its monofunctional derivatives
An unsaturated polyester resin, which is liquid at room temperature and contains 20 to 60 weight % of a crosslinking agent combined with a polyfunctional hydrocarbon vinyl monomer at a blending ratio of 0 weight %, is made of cellulose fiber as the main component. 1. A method for manufacturing a copper-clad laminate, which comprises impregnating the base material, then laminating and curing the base materials, and bonding the copper foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11988387A JPS62283132A (en) | 1987-05-15 | 1987-05-15 | Production of laminate for electricity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11988387A JPS62283132A (en) | 1987-05-15 | 1987-05-15 | Production of laminate for electricity |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12009778A Division JPS5546970A (en) | 1978-09-28 | 1978-09-28 | Laminated plate for electricity and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62283132A true JPS62283132A (en) | 1987-12-09 |
Family
ID=14772594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11988387A Pending JPS62283132A (en) | 1987-05-15 | 1987-05-15 | Production of laminate for electricity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62283132A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6130904A (en) * | 1984-07-20 | 1986-02-13 | 動力炉・核燃料開発事業団 | Method of installing rotor unit in field |
-
1987
- 1987-05-15 JP JP11988387A patent/JPS62283132A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6130904A (en) * | 1984-07-20 | 1986-02-13 | 動力炉・核燃料開発事業団 | Method of installing rotor unit in field |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4954304A (en) | Process for producing prepreg and laminated sheet | |
| JPS61243844A (en) | Thermosetting resin composition, laminated sheet and production thereof | |
| US4866134A (en) | Laminate with layer of rubber-modified vinyl ester and unsaturated polyester | |
| KR910000076B1 (en) | Fire retardant electrical laminated sheet | |
| JPS6130904B2 (en) | ||
| US5270104A (en) | Unsaturated polyester resin composition and laminates | |
| JPS62283132A (en) | Production of laminate for electricity | |
| US4159371A (en) | Flame-retardant resin compositions | |
| JPH0477006B2 (en) | ||
| JPS6356548A (en) | Thermosetting resin composition, laminated sheet produced by using same and production thereof | |
| US5238730A (en) | Electrical laminate with dibasic acid-modified epoxy (meth)acrylate | |
| JPS6128545A (en) | Resin composition, laminate, and their preparation | |
| JPS6334020B2 (en) | ||
| JPS63117053A (en) | Thermosetting resin composition and laminated sheet | |
| JPS6059932B2 (en) | Method for improving processability of unsaturated polyester resin laminates for electrical applications | |
| EP0336266B1 (en) | Electrical laminate produced by using special thermosetting resin compostions | |
| JPH032057B2 (en) | ||
| JPH04107978A (en) | Laminated plate for electricity | |
| JPH07173251A (en) | Laminate and its production | |
| JPH07247417A (en) | New toughened curable polyphenylene ethereal resin composition | |
| JPH02127415A (en) | Epoxy resin composition and production of prepreg and laminated sheet | |
| JPS6045061B2 (en) | Manufacturing method for copper-clad laminates | |
| JPH04141413A (en) | Electric laminate | |
| JPS58196222A (en) | Flame-retardant unsaturated polyester resin composition and laminated board | |
| JPS6310652A (en) | Unsaturated polyester resin composition and laminated sheet for electrical use |