JPS6386732A - Electric laminated board - Google Patents
Electric laminated boardInfo
- Publication number
- JPS6386732A JPS6386732A JP23138986A JP23138986A JPS6386732A JP S6386732 A JPS6386732 A JP S6386732A JP 23138986 A JP23138986 A JP 23138986A JP 23138986 A JP23138986 A JP 23138986A JP S6386732 A JPS6386732 A JP S6386732A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- acid
- substrates
- parts
- laminated board
- 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
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 9
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 9
- 239000003063 flame retardant Substances 0.000 claims abstract description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 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 claims abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 4
- 238000010030 laminating Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000004080 punching Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-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
- 239000005011 phenolic resin Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- TYQWYQKXBGUHCS-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(tribromomethyl)benzene Chemical compound BrC=1C(=C(C(=C(C(Br)(Br)Br)C=1)Br)Br)Br TYQWYQKXBGUHCS-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical class CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000132059 Carica parviflora Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 240000005250 Chrysanthemum indicum Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- -1 cadicol Chemical compound 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WPZJSWWEEJJSIZ-UHFFFAOYSA-N tetrabromobisphenol-F Natural products C1=C(Br)C(O)=C(Br)C=C1CC1=CC(Br)=C(O)C(Br)=C1 WPZJSWWEEJJSIZ-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009816 wet lamination Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
不発明に、難燃性、打抜加工性、電気特性にすぐｎた電
気用積層板（積層絶縁板、印刷回路用銅張積層板）に関
する。[Detailed Description of the Invention] (Industrial Application Field) An electrical laminate (laminated insulating board, copper-clad laminate for printed circuits) with excellent flame retardancy, punching workability, and electrical properties. Regarding.
（従来の技術）
電気用槓層舌には、プリプレグ化が容易で乾式積層によ
る大量生産が可能なフェノール樹脂及びエボキク樹脂さ
らに湿式積層による不飽和ポリエステル樹脂などが用い
らｎている。(Prior Art) Phenol resins and Evoki resins, which can be easily made into prepregs and can be mass-produced by dry lamination, as well as unsaturated polyester resins by wet lamination, are used for electric laminates.
近年の著しい電子機器工業の発展に伴ない、絶縁材料と
して使用さｎろ積層板及び印刷配嶽鈑の需要框増大して
いるが、安全性の面からこｎら電気量積ｆ−板の難燃化
が、部品実装の挿入自動化の面から寸法精度の向上と打
抜加工温度の低温化が図らｎている。With the remarkable development of the electronic equipment industry in recent years, the demand for laminated boards and printed packaging boards used as insulating materials has increased. In addition to flame retardancy, efforts are being made to improve dimensional accuracy and lower the temperature of the punching process in terms of automating the insertion of parts.
（発明が解決しようとする問題点）
難燃化のためには、ハロゲン元素の樹脂骨格への尋人及
び各種難燃剤を重加することを行うが、難燃性を十分に
与えようとすると耐熱性、耐薬品性、電気特性などを低
下する。(Problems to be Solved by the Invention) In order to make flame retardant, halogen elements are added to the resin skeleton and various flame retardants are added, but in order to provide sufficient flame retardancy, Decreases heat resistance, chemical resistance, electrical properties, etc.
低温での打抜き加工性を良くする１こめには、熱硬化性
樹脂に可塑剤を伶加するか、成るいに樹脂骨格に柔軟性
を待たせる等の方法をとるが、この場合も耐熱性、耐薬
品性、耐温性などが低下する。One way to improve punching workability at low temperatures is to add a plasticizer to the thermosetting resin, or to make the resin skeleton more flexible, but in this case, heat resistance is also improved. , chemical resistance, temperature resistance, etc. decrease.
したがって、従来の方法では良好なＭ燃性と低温での打
抜加工性の向上を満足することは非常にむつかしい。Therefore, it is very difficult to satisfy the requirements of good M flammability and improved punching workability at low temperatures using conventional methods.
（問題点を解決するための手段）
本発明者は、前述の問題点を解決し、良好な難燃性とａ
ｎた低温打抜加工ｅｔ有する電気用積層板を提供する。(Means for Solving the Problems) The present inventor has solved the above-mentioned problems, and achieved good flame retardancy and a
The present invention provides an electrical laminate having a low-temperature punching process.
本発明に、ハロゲン含有エポキシ樹脂と炭素数４−３６
の二塩基酸とを反応させ、さらにメタアクリル酸を反応
させて得らｎる可撓性に勝れたエポキシメタアクリレー
トを１ｍ燃剤として熱硬化性樹脂に僑加することに工つ
て、耐燃性を有しかつ低温打抜加工性を向上させるもの
である。In the present invention, a halogen-containing epoxy resin and a carbon number 4-36
By reacting the dibasic acid of and improves low-temperature punching workability.
本発明に便用する熱硬化性樹脂に、フェノール樹脂、エ
ポキシ樹脂、不飽和ポリエステル樹力旨、ビニルエステ
ル樹脂等いろいろあるが、特に不飽和ポリエステル樹脂
、ビニルエステル樹脂、熱硬化性１クリ／Ｌ−樹脂等の
ラジカル１甘系が好ましい。There are various thermosetting resins conveniently used in the present invention, such as phenolic resins, epoxy resins, unsaturated polyester resins, vinyl ester resins, etc., but in particular, unsaturated polyester resins, vinyl ester resins, thermosetting resins, etc. - Radical 1 sweet type such as resin is preferable.
本発明におけるハロゲン化エポキシ樹脂とに、１分子中
に少なくとも１個以上のエポキシ＆’を有し、ハロづ゛
ン含有量が３５重ｆ１ｔ％以上のものが好ましい。例え
ば、テトラブロモビスフェノールＡ１テトラブロムビス
フエノールＦ、ブロム化ノボラック樹脂等のブロム含有
多価フェノールとエピクロルヒドリンとの重縮合に工っ
て得らｎるエポキシ樹脂があるが、中でもテトラブロモ
ビスフェノールＡ型のものが好適である。The halogenated epoxy resin used in the present invention preferably has at least one epoxy &' in one molecule and has a halogen content of 35% by weight or more. For example, there are epoxy resins obtained by polycondensation of bromine-containing polyhydric phenols such as tetrabromobisphenol A1, tetrabromobisphenol F, and brominated novolac resins with epichlorohydrin. Preferably.
その市販品に、住友化学製スミエボキクＥＳＢ−６４０
、ＥＳＢ−４００、ＥＳＢ−５００゜ＥＳＢ−７００、
ダウケミカ／Ｌ−製ＤＥＲ−５４２、ＤＥＲ−５１１、
ＤＥＲ−５８０、油化シェル製１０４５．１０５０．１
０４６、ＤＸ−２４８等を挙げることができる。The commercially available product is Sumiebo Chrysanthemum ESB-640 manufactured by Sumitomo Chemical.
, ESB-400, ESB-500゜ESB-700,
Dow Chemical/L-manufactured DER-542, DER-511,
DER-580, manufactured by Yuka Shell 1045.1050.1
046, DX-248, and the like.
炭素数４〜３６の二塩基酸とは、マレイン酸、フタル酸
、アジピン酸、ダイマー酸等いろいろあるが、中でも柔
軟性を与えるという面からダイマー酸が好ヱしい。市販
品としては、エンボーｈ１０２２、エンボー／ｌ−１０
２４（エメリー社製）、第一ゼネラル社製バーサダイム
２１６、バーサグイム２８８等がある。There are various dibasic acids having 4 to 36 carbon atoms, such as maleic acid, phthalic acid, adipic acid, and dimer acid, among which dimer acid is preferred from the standpoint of imparting flexibility. Commercially available products include Enbow h1022 and Enbow/l-10.
24 (manufactured by Emery Co.), Versa Dime 216, Versa Dime 288, manufactured by Daiichi General Co., etc.
ブロム含有エポキシ樹脂と炭素数４〜３６の二塩基酸と
の反応は槙々の方法によって行うことができる。一般的
方法としては、ブロム含有ヱボキシ樹脂と二塩基酸とを
トリエチルアミン、ベンジルジメチルアミン、トリーｎ
−ブチルアミン、水酸化ナトリウム、水酸化リチウム等
の触媒存在下に７０〜１５０℃で反応させろ。このとき
必要によって、浴剤としてトルエン、スチレン、酢酸エ
チル、ＭＥＫ等を用いるが、特にスチレンを用いると反
応生成物′Ｉｔｉ！２！用するに白たりて溶剤を除去す
る必要がなく好ましい。The reaction between the bromine-containing epoxy resin and the dibasic acid having 4 to 36 carbon atoms can be carried out by Maki's method. A common method is to combine a bromine-containing epoxy resin and a dibasic acid with triethylamine, benzyldimethylamine, tri-n
- React at 70-150°C in the presence of a catalyst such as butylamine, sodium hydroxide, lithium hydroxide, etc. At this time, toluene, styrene, ethyl acetate, MEK, etc. may be used as a bath agent as required, but if styrene is used in particular, reaction products 'Iti! 2! This is preferable since it is not necessary to remove the solvent during use.
この反応を行った後、ハイドロキノン、カヂコール、ピ
クリン酸、分子状ｒ１！！累の安定剤とメタアクリル酸
を加える。このとき、反応を促進するために前記触媒を
さらに適賃加えてもよい。After carrying out this reaction, hydroquinone, cadicol, picric acid, molecular r1! ! Add the stabilizer and methacrylic acid. At this time, an appropriate amount of the catalyst may be further added to promote the reaction.
以上のようにして得た反応生成物を難燃剤として用いろ
ことができるが、さらに良好な難燃性を与えるために、
必要に応じて一般に慣用さｎる難燃市加剤を用いること
ができろ。代表的伽加剤の例に、ヘキ丈ブロモベンゼン
、ポリ臭化ビフェニルエーテル、ヘプタブロモトルエン
、２−４−６）リブロモフェノールメタアクリレ−）、
２−４−６）リブロモフェノールグリシジルコーラル等
の臭素系難燃剤、トリメチルホスフェート、トリフェニ
ルホスフェート等のリン酸エステル類、三酸化アンチそ
ン等がある。The reaction product obtained as described above can be used as a flame retardant, but in order to provide even better flame retardancy,
If necessary, commonly used flame retardant additives may be used. Examples of typical additives include hexabromobenzene, polybrominated biphenyl ether, heptabromotoluene, 2-4-6) ribomophenol methacrylate),
2-4-6) Brominated flame retardants such as ribomophenol glycidyl coral, phosphoric acid esters such as trimethyl phosphate and triphenyl phosphate, and antisodium trioxide.
こｎら難燃材を配合する基材含浸用熱硬化性樹脂として
は、不飽和ポリエステ／Ｉ−！ｌＩ脂、ビニルエステル
樹脂樹脂等のラジカル１甘系のものが工いが、中でも性
能、価格の面から不飽和ポリエステル樹脂が好適である
。この不飽和ポリエステルは一般に市販さｎるものを使
用することかでｆｋろ。The thermosetting resin for impregnating the base material with which these flame retardants are blended is unsaturated polyester/I-! Radically sweet type resins such as lI fats and vinyl ester resins are suitable, but unsaturated polyester resins are particularly suitable from the viewpoint of performance and cost. This unsaturated polyester is generally commercially available.
実施例１
（１） テトラブロモビスフェノールＡグリシジルエ
ーテル（エポキシ当量３９５〜４１０）１００部に対し
ダイマー酸５＆７部ベンジルジチルアミン１．３部スチ
レン６２部ハイドロキノン［Ｌ０５部を配合し、９０〜
１００℃で酸価が６以下になるまで反応を続け、さらに
メタアクリル酸９部を配付して反応を続け、酸価２．３
のダイマー酸変性エポキシメタアクリレート樹脂中を得
た。Example 1 (1) 5 and 7 parts of dimer acid to 100 parts of tetrabromobisphenol A glycidyl ether (epoxy equivalent 395-410) 1.3 parts of benzylditylamine 62 parts of styrene
The reaction was continued at 100°C until the acid value became 6 or less, and then 9 parts of methacrylic acid was added and the reaction was continued until the acid value reached 2.3.
A dimer acid-modified epoxy methacrylate resin was obtained.
（２）前記（１）において、メタアクリ／Ｌ−酸９部に
代えてアクリル酸９部とした他は（１）と同様にして酸
価五〇の樹脂（ＩＪ）を得た。(2) A resin (IJ) having an acid value of 50 was obtained in the same manner as in (1) above, except that 9 parts of acrylic acid was used instead of 9 parts of methacrylic/L-acid.
１３） ジエチレンクリコール８９１部、ｉ水マレイ
ン酸３７４部、インフタルｆｆ６３４ｍ、ハイドロキノ
ン０２部を配合し、窒素ガスを吹込みながら２１０℃に
昇温し、同温度で酸価２１．０となるまで加熱を進めて
不飽和ポリエステル樹り旨（助を得た。13) 891 parts of diethylene glycol, 374 parts of i-water maleic acid, 634 parts of Inftal FF, and 02 parts of hydroquinone were mixed, heated to 210°C while blowing nitrogen gas, and heated at the same temperature until the acid value reached 21.0. Proceeding with unsaturated polyester wood (help was obtained).
前記の樹脂中５０部、樹脂１１５０ｓ、スチレン１５部
、トリフェニルホスフェ−）１０部、ベンジルパーオキ
サイド１部を配合した樹脂溶液を基材として、予めメチ
ロールメラミン（日立化成製メラン６３０）樹脂溶液で
処理し樹脂分１２％とした厚さ［Ｌ２５ｆｆｌ！Ｈのク
ラフト紙に含浸させ全樹脂分６０％とした。こｎｋ６枚
積層積層接着剤を塗布した厚さ５５μｎ］のｔ解＠陥を
ラミネートし、１２０℃、１０ｋｇ／ａｎ’圧で２０分
間硬化させ、厚さ１．６市の銅張積層板を得た。A resin solution containing 50 parts of the above resin, 1150s resin, 15 parts of styrene, 10 parts of triphenyl phosphate, and 1 part of benzyl peroxide was used as a base material, and a methylolmelamine (Melan 630 manufactured by Hitachi Chemical Co., Ltd.) resin solution was prepared in advance. The thickness was treated with 12% resin [L25ffl! It was impregnated into No. H kraft paper to give a total resin content of 60%. This 6-layer laminate was laminated with a 55 μn thick T-type laminate coated with laminating adhesive and cured at 120°C and 10 kg/an' pressure for 20 minutes to obtain a copper-clad laminate with a thickness of 1.6 mm. Ta.
実施例２
実施例１において、樹脂中を樹脂ｔｉｌｌに代え、トリ
フェニルホスフェートの代わりに三酸化アンチモン４部
を加えた他は同様にして厚さ１．６ｉｒｅの銅張積層敬
全得た。Example 2 A copper-clad laminate with a thickness of 1.6 ire was obtained in the same manner as in Example 1, except that the resin was replaced with resin till, and 4 parts of antimony trioxide was added instead of triphenyl phosphate.
比較例
樹脂（ＪＩＤ１００部に対しベンゾイルパーオキサイド
１部、スチレン３０部を加え、実施例１と同様にして銅
張積層板を得た。Comparative Example Resin (1 part of benzoyl peroxide and 30 parts of styrene were added to 100 parts of JID, and a copper-clad laminate was obtained in the same manner as in Example 1.
（発明の効果）
実施例によって得た銅張積層板の試験成績を第１表に示
す。(Effects of the Invention) Table 1 shows the test results of the copper-clad laminates obtained in Examples.
表のデータから明らかであるが、本発明に工ろ電気用積
層板は、＃を熱性、耐湿性、電気特性を低下することな
く、難燃性が向上し、低温での打抜加工性が改善さｎた
。It is clear from the data in the table that the electrical laminate processed according to the present invention has improved flame retardancy and punching workability at low temperatures without reducing heat resistance, moisture resistance, and electrical properties. Improved.
４以下余白4 or less margins
Claims (1)
塩基酸と反応させた後さらにメタアクリル酸を反応させ
た反応生成物を、難燃剤として熱硬化性樹脂に配合し基
材に含浸して硬化積層することを特徴とする電気用積層
板。1. A reaction product obtained by reacting a halogen-containing epoxy resin with a dibasic acid having 4 to 36 carbon atoms and then reacting it with methacrylic acid is blended into a thermosetting resin as a flame retardant and impregnated into a base material. An electrical laminate board characterized by being cured and laminated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23138986A JPS6386732A (en) | 1986-09-30 | 1986-09-30 | Electric laminated board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23138986A JPS6386732A (en) | 1986-09-30 | 1986-09-30 | Electric laminated board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6386732A true JPS6386732A (en) | 1988-04-18 |
Family
ID=16922845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23138986A Pending JPS6386732A (en) | 1986-09-30 | 1986-09-30 | Electric laminated board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6386732A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0538777A (en) * | 1991-08-08 | 1993-02-19 | Hitachi Chem Co Ltd | Laminate and manufacture thereof |
-
1986
- 1986-09-30 JP JP23138986A patent/JPS6386732A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0538777A (en) * | 1991-08-08 | 1993-02-19 | Hitachi Chem Co Ltd | Laminate and manufacture thereof |
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