JPS63183938A - Production of laminated flame-retardant phenolic resin board - Google Patents
Production of laminated flame-retardant phenolic resin boardInfo
- Publication number
- JPS63183938A JPS63183938A JP1565987A JP1565987A JPS63183938A JP S63183938 A JPS63183938 A JP S63183938A JP 1565987 A JP1565987 A JP 1565987A JP 1565987 A JP1565987 A JP 1565987A JP S63183938 A JPS63183938 A JP S63183938A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- sheets
- phenolic resin
- flame
- dried
- 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.)
- Granted
Links
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 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 class 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 title claims abstract description 17
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 15
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 239000003063 flame retardant Substances 0.000 claims abstract description 20
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000004640 Melamine resin Substances 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 2
- 238000010030 laminating Methods 0.000 abstract 1
- 238000004080 punching Methods 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 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
- 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 1
- 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 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- WZPMZMCZAGFKOC-UHFFFAOYSA-N diisopropyl hydrogen phosphate Chemical compound CC(C)OP(O)(=O)OC(C)C WZPMZMCZAGFKOC-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 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 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、常温打抜き加工性、難燃性、耐熱性、電気特
性を高度に必要とする難燃性フェノール樹脂積層板の製
造法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing flame-retardant phenolic resin laminates that require high room-temperature punchability, flame retardancy, heat resistance, and electrical properties.
従来の技術
最近、民生機器に於いて、電気絶縁基板として難燃性フ
ェノール樹脂積層板を使用する率が増加する中で、高品
質、且す低価格の要求が益々高くなってきている。BACKGROUND OF THE INVENTION Recently, as the use of flame-retardant phenolic resin laminates as electric insulating substrates in consumer electronics has increased, the demand for high quality and low cost has become higher and higher.
高度な電気特性を持つ難燃性フェノール樹脂積層板を得
る為には、積層成形するプリプレグの作製段階に於いて
、基材への熱硬化性樹脂の含浸乾燥工程を下塗りと上塗
りの２度繰返す方法がある。従来、フェノール樹脂初期
縮合物とメラミン樹脂を混合した下塗り樹脂を基材に含
浸乾燥後、更に上塗り樹脂として難燃剤及び難燃樹脂を
配合した油変性フェノール樹脂ワニスを含浸乾燥してプ
リプレグを作製していた。In order to obtain a flame-retardant phenolic resin laminate with advanced electrical properties, the process of impregnating and drying the base material with a thermosetting resin is repeated twice, as an undercoat and a topcoat, during the prepreg manufacturing stage for lamination molding. There is a way. Conventionally, a prepreg is produced by impregnating and drying a base material with an undercoat resin that is a mixture of a phenolic resin initial condensate and a melamine resin, and then impregnating and drying an oil-modified phenolic resin varnish containing a flame retardant and a flame retardant resin as a top coat resin. was.
発明が解決しようとする問題点
従来法に於いては難燃性を確保（ＵＬ−９４−Ｖ−０）
する為に、下塗り樹脂はフェノール樹脂初期縮合物とメ
ラミン樹脂の混合樹脂を使用し、更に上塗り樹脂にはプ
ロふ化エポキシ樹脂等の難燃性樹脂とテトラブロモビス
フェノールＡ、）リフ二三ルホスフェート等のブロム化
合物やリン化合物等の難燃剤が多量に含有されていた為
、得られた積層板の層間密着性が弱く、常温打抜き加工
性、耐熱性が悪くなり、更に高価になっている。Problems to be solved by the invention Flame retardancy is ensured in the conventional method (UL-94-V-0)
In order to do this, the undercoat resin is a mixed resin of phenolic resin initial condensate and melamine resin, and the topcoat resin is a mixture of flame retardant resin such as pro-fluorinated epoxy resin and tetrabromobisphenol A,) rif-23-phosphate, etc. Because the laminates contained large amounts of flame retardants such as bromine compounds and phosphorus compounds, the resulting laminates had weak interlayer adhesion, poor room-temperature punching workability and heat resistance, and were more expensive.
従って、本発明は、常温打抜き性、耐熱性か良好で安価
な難燃性フェノール樹脂積層板を提供する事を目的とす
る。Therefore, an object of the present invention is to provide an inexpensive flame-retardant phenolic resin laminate that has good room-temperature punchability and heat resistance.
問題点を解決するための手段
本発明は、上記の目的を達成するためになされたもので
、フェノール樹脂初期縮合物とメラミン樹脂を混合した
下塗り樹脂を基材に含浸乾燥せしめる第１工程、難燃樹
脂を含有する油変性フェノール樹脂に固形分換算で五酸
化アンチモンゾルを２〜２０重量優含有する上塗り樹脂
を前記第１工程を経た基材に含浸乾燥せしめる第２工程
を経てプリプレグを作成し、これを積層成形する事を特
徴とするものである。Means for Solving the Problems The present invention has been made to achieve the above-mentioned object, and includes a difficult first step of impregnating and drying a base material with an undercoating resin that is a mixture of a phenolic resin initial condensate and a melamine resin. A prepreg is created through a second step of impregnating and drying the base material that has gone through the first step with a top coat resin containing 2 to 20 weight of antimony pentoxide sol in terms of solid content in an oil-modified phenolic resin containing a fuel resin. , which is characterized by being laminated and molded.
作用
本発明は、上記の特徴を有することにより、常温打抜き
加工性、難燃性、耐熱性、及び電気特性を高度に必要と
する難燃性フェノール樹脂積層板か得られる。即ち、従
来の方法では、上塗り樹脂中の難燃剤の含有率が多い為
、積層板の層間密着か弱く常温打抜き加工性及び耐熱性
を低下させる原因になっていた。従って、離燃効果の大
きい五酸化アンチモンゾルを添加することにより上絵り
樹脂中のブロム、リン系難燃剤と共に難燃樹脂をもその
使用を減少出来、且つ積層板の透明性も保持出来る。Function: The present invention has the above-mentioned characteristics, thereby providing a flame-retardant phenolic resin laminate that requires high room-temperature punching workability, flame retardancy, heat resistance, and electrical properties. That is, in the conventional method, since the content of flame retardant in the top coat resin is high, the adhesion between the layers of the laminate is weak, which causes a decrease in room temperature punching workability and heat resistance. Therefore, by adding antimony pentoxide sol, which has a large flame retardation effect, it is possible to reduce the use of flame retardant resin as well as bromine and phosphorus flame retardants in the overlay resin, and it is also possible to maintain the transparency of the laminate.
但し、五酸化アンチモンゾルが上塗り樹脂中の２重量幅
未満では、難燃性（ＵＬ−９４Ｖ−０）を確保し、ブロ
ム系、リン系の難燃剤の使用を減少出来る丈の効果は得
られなかった。又、上塗りの樹脂中の２０重重量幅越え
る量を添加すると積層板が不透明になり、品質上の間頭
がある。好ましい量としては、３〜１０重量幅で ゛あ
る。However, if the antimony pentoxide sol is less than 2% by weight in the top coat resin, the effect of ensuring flame retardancy (UL-94V-0) and reducing the use of bromine-based and phosphorus-based flame retardants cannot be achieved. There wasn't. Also, if it is added in an amount exceeding 20 weight range in the top coat resin, the laminate will become opaque and there will be problems in terms of quality. A preferable amount is 3 to 10 weight range.
実施例
次に、本発明の実施例を比較例、従来例と共に説明する
。Examples Next, examples of the present invention will be described together with comparative examples and conventional examples.
山桐油変性フェノール樹脂の製造
クレゾール３６６？、桐油４５ｏ？、パラトルエンスル
ホン酸０．４７）をコンデンサー付フラスコに仕込み攪
拌しなから８０°Ｃで９０分間反応し、更にフェノール
３ｏ７？、８６係パラホルム２８０）、２５％アンモニ
ア水２１ｐを投入し、４時間反応させた後、減圧下で約
１時間脱水を行い、メタノール３６２？、トルエン３５
６？を加え冷却した。Manufacture of Yamatou oil-modified phenolic resin Cresol 366? , Tung oil 45o? , p-toluenesulfonic acid 0.47) was charged into a flask with a condenser and reacted at 80°C for 90 minutes without stirring, and then phenol 3o7? , Section 86 paraform 280) and 21 p of 25% ammonia water were added, and after reacting for 4 hours, dehydration was performed under reduced pressure for about 1 hour, and methanol 362? , toluene 35
6? was added and cooled.
この樹脂の不揮発分は５０％であった。The nonvolatile content of this resin was 50%.
（Ｉｌ 難燃樹脂の製造
ブロム化エポキシ樹脂６２８？とジイソプロピルホスフ
ェ−）２３．２？をフラスコに仕込み８０°Ｃで３時間
反応後、更にジアミノジフェニルメタンを２４．８）投
入し８０″Ｃで１時間反応し冷却を行い、これにトリフ
ェニルホスフェートを１４２１添加溶解する。(Il Production of flame retardant resin Brominated epoxy resin 628? and diisopropyl phosphate) 23.2? was charged into a flask and reacted at 80°C for 3 hours, then 24.8) diaminodiphenylmethane was added and reacted at 80''C for 1 hour, cooled, and 1421ml of triphenyl phosphate was added and dissolved therein.
圓 積層板の製造
上記で得た樹脂を第１表に示す配合割合（重量幅）で五
酸化アンチモンゾル（有機溶媒分散）と混合して上塗り
樹脂を調製した。Manufacture of a laminate The resin obtained above was mixed with antimony pentoxide sol (organic solvent dispersion) in the proportions (weight range) shown in Table 1 to prepare a top coat resin.
まず、フェノール樹脂初期縮合物とメラミン樹脂を混合
した下塗り樹脂（フェノール樹脂初期縮合物／メラミン
樹脂−７０／３０）をｔｔミルスのクラフト紙に含浸乾
燥させ樹脂量１０〜１５重量パーセントの塗工紙を得た
。First, TT Mills kraft paper is impregnated with an undercoat resin (phenol resin initial condensate/melamine resin - 70/30), which is a mixture of a phenolic resin initial condensate and a melamine resin, and dried to coat paper with a resin content of 10 to 15 weight percent. I got it.
更にこの塗工紙に第１表の上塗り樹脂を含浸乾燥させ、
樹脂量４８〜５１重量パーセントのプリプレグを作製し
た。このプリプレグを所定枚数とプリプレグの片側表面
に銅箔を積層し、１６０°Ｃ１１００ｋｙ／ｃｙｙＥの
加熱加圧下で６０分間成形し、１．６ｆｉ厚の片面銅張
積層板を得た。Furthermore, this coated paper is impregnated with the top coating resin shown in Table 1 and dried.
A prepreg with a resin content of 48 to 51 weight percent was produced. A predetermined number of sheets of this prepreg were laminated with copper foil on one surface of the prepreg, and molded for 60 minutes under heating and pressure at 160° C. and 1100 ky/cyyE to obtain a single-sided copper-clad laminate with a thickness of 1.6 fi.
この銅張積層板の特性試験結果を第２表に示す。Table 2 shows the characteristics test results of this copper-clad laminate.
２・、４ 、（
第 １ 表
第 ２ 表
０ 絶縁抵抗、半田耐熱性の判定はＪＩＳ−に−６９１
１による。2, 4, (Table 1 Table 2 Table 0 Insulation resistance and soldering heat resistance are determined according to JIS-691
According to 1.
の 難燃性：ＵＬ法（垂直法による）
Ｖ−Ｏ規格（ＭＡＸ：、１０秒以下、マ：５秒以下）
３）打抜き加工性は密集孔パターンの実用金型を用い各
温度で打抜き目視にて判定した。Flame retardancy: UL method (perpendicular method) V-O standard (MAX: 10 seconds or less, MA: 5 seconds or less) 3) Punching workability was visually confirmed by punching at various temperatures using a practical mold with a dense hole pattern. Judgment was made.
◎：優、○：良、△：若若干自白Ｘ：層間剥離
発明の効果
上述したように、本発明によれば、第１表及び第２表か
ら明らかな様に難燃性を保持しながら上塗り樹脂中のブ
ロム系やリン系の急燃剤と共に難燃樹脂をも減少出来、
油変性フェノール樹脂を増加する事が可能となったので
、耐熱性、打抜加工性を改善出来た。また、上塗り樹脂
中に五酸化アンチモンゾルを添加する事により、高価な
ブロム、リン系難燃剤、難燃樹脂が減少出来るため、コ
ストダウンが出来、工業的価値は極めて大なるものであ
る。◎: Excellent, ○: Good, △: Slightly negative It can reduce the flame retardant resin as well as the bromine-based and phosphorus-based flame quickeners in the top coat resin.
Since it became possible to increase the amount of oil-modified phenolic resin, heat resistance and punching workability were improved. Furthermore, by adding antimony pentoxide sol to the top coat resin, the amount of expensive bromine, phosphorus flame retardants, and flame retardant resins can be reduced, resulting in cost reductions, which is of great industrial value.
Claims (1)
下塗り樹脂を基材に含浸乾燥せしめる第１工程、難燃樹
脂を含有する油変性フェノール樹脂に固形分換算で五酸
化アンチモンゾルを２〜２０重量％含有する上塗り樹脂
を前記第１工程を経た基材に含浸乾燥せしめる第２工程
を経てプリプレグを作製し、このプリプレグを積層成形
する事を特徴とする難燃性フェノール樹脂積層板の製造
法。The first step is to impregnate and dry the base material with an undercoating resin that is a mixture of a phenolic resin initial condensate and a melamine resin, and the oil-modified phenolic resin containing a flame-retardant resin contains 2 to 20% by weight of antimony pentoxide sol in terms of solid content. A method for producing a flame-retardant phenolic resin laminate, characterized in that a prepreg is produced through a second step of impregnating and drying the base material that has undergone the first step with a top coat resin, and the prepreg is laminated and molded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1565987A JPS63183938A (en) | 1987-01-26 | 1987-01-26 | Production of laminated flame-retardant phenolic resin board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1565987A JPS63183938A (en) | 1987-01-26 | 1987-01-26 | Production of laminated flame-retardant phenolic resin board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63183938A true JPS63183938A (en) | 1988-07-29 |
| JPH0360860B2 JPH0360860B2 (en) | 1991-09-18 |
Family
ID=11894861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1565987A Granted JPS63183938A (en) | 1987-01-26 | 1987-01-26 | Production of laminated flame-retardant phenolic resin board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63183938A (en) |
-
1987
- 1987-01-26 JP JP1565987A patent/JPS63183938A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0360860B2 (en) | 1991-09-18 |
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