JPH01118522A - Preparation of flame-retardant resin composition for laminate - Google Patents
Preparation of flame-retardant resin composition for laminateInfo
- Publication number
- JPH01118522A JPH01118522A JP27695687A JP27695687A JPH01118522A JP H01118522 A JPH01118522 A JP H01118522A JP 27695687 A JP27695687 A JP 27695687A JP 27695687 A JP27695687 A JP 27695687A JP H01118522 A JPH01118522 A JP H01118522A
- Authority
- JP
- Japan
- Prior art keywords
- diglycidyl ether
- brominated bisphenol
- flame
- triphenyl phosphite
- laminate
- 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
- 239000003063 flame retardant Substances 0.000 title claims description 32
- 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 title claims description 24
- 239000011342 resin composition Substances 0.000 title claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims abstract description 30
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 229910052794 bromium Inorganic materials 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000004080 punching Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 4
- 240000002834 Paulownia tomentosa Species 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000002383 tung oil Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- -1 pro-brominated bisphenol A diglycidyl ether Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000015107 ale Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Landscapes
- Epoxy Resins (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、難燃性、耐熱性の優れた積層板を提供でき貯
蔵安定性に優れた積層板用難燃性樹脂組成物の製造法に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a flame-retardant resin composition for a laminate, which can provide a laminate with excellent flame retardancy and heat resistance and has excellent storage stability.
従来の技術
近年、家庭用電気機器の安全性の面から、それに使用さ
れるプリント回路基板（（積層板で構成される）の難燃
化の要求が高まって来た。同時に、多岐にわたる要求特
性項目の中でも、寸法精度の要求から低温打抜き加工性
、あるいは無加熱打抜き加工性及び耐熱性に対する要求
が年々厳しくなっている。Conventional technology In recent years, from the standpoint of safety in household electrical equipment, there has been an increasing demand for flame retardant printed circuit boards (composed of laminated boards) used in them.At the same time, a wide variety of required characteristics have been Among these items, demands for low-temperature punching workability, non-heating punching workability, and heat resistance are becoming stricter year by year due to demands for dimensional accuracy.
これに対し、従来の難燃樹脂、あるいは難燃剤の使用で
は、これらの要求を完全に満足することは困難であった
。On the other hand, it has been difficult to completely satisfy these requirements using conventional flame retardant resins or flame retardants.
即ち、従来の難燃剤として、反応性を持たない低分子量
の添加型難燃剤と反応性を持つ反応型難燃剤が知られて
いる。That is, as conventional flame retardants, there are known low molecular weight additive flame retardants that are not reactive and reactive flame retardants that are reactive.
添加型難燃剤を使用した場合、これを配合した樹脂の耐
熱性、耐薬品性、電気特性が低下し、さらに、架橋密度
の低下により層間密着性が著しく低下する。特に、打抜
き加工性については、層間は（離、打抜き時の粉落ち、
ダイスの穴詰り等の欠点が現われやすくなる。When an additive flame retardant is used, the heat resistance, chemical resistance, and electrical properties of the resin blended with the flame retardant are reduced, and furthermore, the interlayer adhesion is significantly reduced due to a reduction in crosslinking density. In particular, regarding punching workability, the difference between layers (distance, powder falling during punching,
Defects such as die hole clogging are more likely to appear.
反応型難燃剤を配合して使用した場合、前記の欠点は少
ないものの、積層板とした時の樹脂の架橋密度の増加に
より、積層板の軟化温度を高温側に移動させ、低温ある
いは無加熱の打抜きに適さなくなり、また、その反応性
のため、配合樹脂、塗工基材の貯蔵安定性が悪くなる。When used in combination with reactive flame retardants, although the above-mentioned disadvantages are small, the increased crosslinking density of the resin when used as a laminate moves the softening temperature of the laminate to a higher temperature side, making it easier to use at low temperatures or without heating. It becomes unsuitable for punching, and due to its reactivity, the storage stability of the compounded resin and coated substrate deteriorates.
前者の代表的な例として、ブロム化ビスフェノールＡ、
ブロム化ジフェニルエール類、トリド
フェニルフォスフエ−！及びそのアルキル誘導体があり
、また、後者の代表例として、ブロム化エポキシ樹脂が
ある。Representative examples of the former include brominated bisphenol A,
Brominated diphenyl ales, tridophenyl phosphate! and its alkyl derivatives, and a representative example of the latter is brominated epoxy resin.
実際には、多岐にわたる特性上の要求から、添加型と反
応型難燃剤の両者それぞれの長所短所を考慮しつつ、両
者が併用されている。In reality, due to a wide variety of property requirements, additive type flame retardants and reactive type flame retardants are used in combination, taking into consideration their respective advantages and disadvantages.
また、両者の併用、特にハロゲン（実用上Ｂｒが多用さ
れている）、リンの併用は別の側面からも利点がある。In addition, the combination of both, particularly halogen (Br is often used in practice) and phosphorus, has advantages from other aspects as well.
即ち、難燃効果を持つ元素（ハロゲン、リン、窒素、ホ
ウ素等）を単独で使用する場合より、それらを複数併用
した場合の方が、相乗効果により難燃効果が増大し、結
果的に難燃剤の総使用短を減少することができる。また
、添加型難燃剤は、優れた可塑効果を持つため、その併
用により積層板の可撓性、打抜き加工性の向上を行うこ
とができる。In other words, rather than using elements that have flame retardant effects (halogen, phosphorus, nitrogen, boron, etc.) alone, when multiple of them are used together, the flame retardant effect increases due to the synergistic effect, and as a result, the flame retardant effect increases. The total usage of fuel can be reduced. Further, since the additive flame retardant has an excellent plasticizing effect, the flexibility and punching workability of the laminate can be improved by using it in combination.
しかし、例を最も使用頻度の高いＢｒ、Ｐの複合系につ
いて挙げると、Ｂｒ系のものは、添加型と反応型の両方
が実用化されているが、Ｐ系のものについては添加型し
か実用化されていない。However, to give an example of the most frequently used composite system of Br and P, both the additive type and the reactive type are in practical use for the Br type, but only the additive type is in practical use for the P type. has not been standardized.
従って、Ｂｒ、Ｐの複合系において、最適難燃効果を示
す配合比を探し得たとしても、前述の添加型難燃剤の持
つ欠点のため、簡単に使用量を増加することができなか
った。Therefore, even if it were possible to find a blending ratio that exhibits the optimum flame retardant effect in a composite system of Br and P, it was not possible to easily increase the amount used due to the drawbacks of the additive type flame retardant described above.
発明が解決しようとする問題点
以上から、従来Ｐ系化合物を使用する難燃性樹脂及び難
燃剤は、積層板特性上での様々な制約から、最適な難燃
効果を得るための配合比率の自由度が非常に狡く、必ず
しも最も難燃効果の高い配合系が選択されているとは言
えなかった。Problems to be Solved by the Invention From the above, flame retardant resins and flame retardants that conventionally use P-based compounds have been difficult to adjust the blending ratio to obtain the optimal flame retardant effect due to various constraints on the properties of laminates. The degree of freedom was very flexible, and it could not be said that the combination system with the highest flame retardant effect was necessarily selected.
本発明は、上記の点に鑑み、これを配合使用して難燃性
、耐熱性に優れた積層板を得られ、また、貯蔵安定性に
優れた積層板用難燃性樹脂組成物を提供することを目的
とする。In view of the above points, the present invention provides a flame-retardant resin composition for laminates that can be blended and used to obtain laminates with excellent flame retardancy and heat resistance, and also has excellent storage stability. The purpose is to
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、
ブロム化ビスフェノールＡジグリシジルエーテルとトリ
フェニルフォスファイト（（Ｃ，Ｈ，Ｏ）、Ｐ）を反応
させることを特徴とする積層板用難燃性樹脂組成物の製
造法である。Means for Solving the Problems The present invention has been made to achieve the above objects.
This is a method for producing a flame-retardant resin composition for a laminate, which is characterized by reacting brominated bisphenol A diglycidyl ether with triphenylphosphite ((C,H,O), P).
作用
トリフェニルフォスファイトは、プロふ化ビスフェノー
ルＡジグリシジルエーテルの持つ水酸基とエステル反応
を起こし、フェノールを放出しながらブロム化ビスフェ
ノールＡジグリシジルエーテル分子に化学的に結合する
（式（１）を参照）。Action Triphenylphosphite causes an ester reaction with the hydroxyl group of pro-brominated bisphenol A diglycidyl ether, and chemically bonds to the brominated bisphenol A diglycidyl ether molecule while releasing phenol (see formula (1)). .
トリフェニルフォスファイトは、三官能のためそれ自身
が架橋形成の中心となり得る。この反応により、トリフ
ェニルフォスファイトは、ブロム化ジフェニルエーテル
の架橋に関与シ、その骨格に取り込まれて行くため、従
来の添加型リン酸エステル類の持つ諸欠点を顕在化させ
ずに、従来より高いリン含有量を持たせる事が可能であ
り、Ｂｒ、Ｐの難燃性に対する相乗効果が最も効果的な
所まで使用量を増加することができる。Since triphenylphosphite is trifunctional, it can itself become the center of crosslink formation. Through this reaction, triphenyl phosphite participates in the crosslinking of brominated diphenyl ether and is incorporated into its skeleton. It is possible to increase the phosphorus content, and the amount used can be increased to the point where the synergistic effect of Br and P on flame retardancy is most effective.
式（１）に示した様に、トリフェニルフォスファイトが
水酸基１モルとエステル反応を行うと、１モルのフェノ
ールが生成する。生成フェノールは、エポキシ基と反応
することにより若干架橋密度を低下させる事により、可
撓性を向上させる。As shown in formula (1), when triphenylphosphite undergoes an ester reaction with 1 mole of hydroxyl group, 1 mole of phenol is produced. The generated phenol improves flexibility by slightly lowering the crosslinking density by reacting with epoxy groups.
実施例
本発明を実施するに当り、ブロム化ビスフェノールＡジ
グリシジルエーテルとトリフェニルフォスファイトの使
用比率については、未反応のトリフェニルファイトが残
存することを避けるため、〔プロふ化ビスフェノールＡ
ジグリシジルエーテルの水酸基当量〕≧〔トリフェニル
フォスファイトの分子量×偽〕となる様にした方が良い
。プロふ化ビスフェノールＡジグリシジルエーテルとト
リフェニルフォスファイトの反応の際に使用する触媒と
しては、ブロム化ビスフェノールＡジグリシジルエーテ
ル単独での高分子化、三次元の架橋を防止するため、並
びニ耐熱性の点から、ベンジルジメチルアミン、２−（
ジメチルアミノメチル）フェノール、２，４゜６−トリ
ス（ジメチルアミノメチル）フェノール等の芳香族三級
アミンが好ましい。添加量としては、ブロム化ビスフェ
ノールＡジグリシジルエーテルとトリフェニル７オスフ
アイトの固型総重量１００に対し、０．５〜５重量部が
望ましい。EXAMPLE In carrying out the present invention, the ratio of brominated bisphenol A diglycidyl ether and triphenyl phosphite to be used is determined to avoid residual unreacted triphenyl phosphite.
It is better to set it so that the hydroxyl group equivalent of diglycidyl ether]≧[molecular weight of triphenylphosphite x false]. The catalyst used in the reaction of pro-brominated bisphenol A diglycidyl ether and triphenyl phosphite has the following properties: From the point of view, benzyldimethylamine, 2-(
Aromatic tertiary amines such as dimethylaminomethyl)phenol and 2,4°6-tris(dimethylaminomethyl)phenol are preferred. The amount added is desirably 0.5 to 5 parts by weight based on 100 parts of the total solid weight of brominated bisphenol A diglycidyl ether and triphenyl 7-osphite.
本発明の難燃性樹脂は、これを配合して使用するとき、
単独で使用しても、あるいは比較的少量のトリフェニル
ホスフェート、ブロム化ジフェニルエーテル等の添加型
難燃剤と併用する事も可能であるが、いずれの場合も難
燃性樹脂及び難燃剤の総使用量を減少することができる
。When the flame retardant resin of the present invention is blended and used,
It can be used alone or in combination with a relatively small amount of additive flame retardant such as triphenyl phosphate or brominated diphenyl ether, but in either case, the total amount of flame retardant resin and flame retardant used can be reduced.
本発明の一実施例を説明する。An embodiment of the present invention will be described.
実施例１
ブロム含有率４８９６、エポキシ当量４００、水酸基当
ｆｆ１２，５００のブロム化ビスフェノールＡジグリシ
ジルエーテルの６０９６）ルエン溶液１．３３３ ｙト
、トリフェニルフォスファイト３１Ｆと、ベンジルメチ
ルアミン２．７ｆを三ツロフラスコに投入し、９０℃で
３時間反応させた（反応物１）。Example 1 A 6096) toluene solution of brominated bisphenol A diglycidyl ether with a bromine content of 4896, an epoxy equivalent of 400, and a ff of 12,500 per hydroxyl group, triphenylphosphite 31F, and benzylmethylamine 2.7f. The mixture was poured into a Mitsuro flask and reacted at 90°C for 3 hours (Reactant 1).
また、別途、桐油変性フェノール樹脂を次の様にして得
た。Separately, a tung oil-modified phenol resin was obtained as follows.
三ツロフラスコに桐油７２０ ｆ！、ｍ−クレゾール５
８０Ｆ、パラトルエンスルホン酸０．７４ｇヲ投・入し
、８０℃で１時間反応後、フェノール５００ Ｆ、８６
％パラホルムアルデヒド４５０ ｆ 、 ２５％アンモ
ニア水３５ｇを投入し、８０℃で反応を進めて、反応生
成物の１６０℃熱盤上での硬化時間が６分になった時点
で脱水濃縮し、後にメタノールを加え樹脂分５０９６に
調整した。Tung oil 720 f in a Mitsuro flask! , m-cresol 5
80F, add 0.74g of para-toluenesulfonic acid, react at 80℃ for 1 hour, then phenol 500F, 86
Add 450 f% paraformaldehyde and 35 g of 25% ammonia water, proceed with the reaction at 80°C, and when the reaction product hardens on a 160°C hot plate for 6 minutes, dehydrate and concentrate, and then add methanol. was added to adjust the resin content to 5096.
この桐油変性フェノール樹脂と前記反応物１を固形分比
率で〔桐油変性フェノール樹脂〕／〔反応物１ ） ＝
８０／２０の割合で混合溶解し１１ミルスのクラフト紙
基材に樹脂付着ｆｆｔ５０９６となるよう塗工乾燥した
。The solid content ratio of this tung oil-modified phenolic resin and the reactant 1 is [tung oil-modified phenolic resin]/[reactant 1] =
The mixture was mixed and dissolved in a ratio of 80/20, coated on an 11 mils kraft paper base material, and dried to give a resin adhesion of fft5096.
接着剤付き３５μ厚銅箔１枚と前記塗工紙基材８枚を組
合せ積層し、加熱加圧して厚さ１．６ｍの片面銅張り積
層板を得た。One sheet of 35μ thick copper foil with adhesive and eight sheets of the coated paper base material were combined and laminated, and heated and pressed to obtain a single-sided copper-clad laminate having a thickness of 1.6 m.
実施例２
実施例１と同様のブロム化ビスフェノールＡジグリシジ
ルエーテルトルエン溶液１．３３３ ｆ 、！ニトリフ
ェニルフォスファイト３１９ ト）リエチルアミン２．
Ｏｆを三ツロフラスコに投入し、９０℃で３時間反応さ
せた（反応物２）。Example 2 Brominated bisphenol A diglycidyl ether toluene solution similar to Example 1 1.333 f,! Nitriphenylphosphite 319 t) Ethylamine2.
Of was charged into a Mitsuro flask and reacted at 90°C for 3 hours (Reactant 2).
反応物２を用い、以下、実施例１と同様の配合量、方法
により厚さ１．６ｎ＋の片面銅張り積層板を得た。Using Reactant 2, a single-sided copper-clad laminate having a thickness of 1.6n+ was obtained using the same blending amount and method as in Example 1.
比較例１
実施例１で使用した桐油変性フェノール樹脂とブロム含
有率４８９６、エポキシ当ｍ ４００のプ慢ム化ビ不フ
エ、ノールＡジグリシジルエーテルの６０％トルエン溶
液を固形分比率で〔桐油変性フェノールｔａＪ脂） ／
（ブロム化ビスフェノールＡジグリシジルエーテル）
＝８０／２０の割合で混合溶解し、これを１１ミルス
のクラフト紙に塗工乾燥して、以下、実施例１と同様の
方法で厚さ１．６輪の片面銅張り積層板を得た。Comparative Example 1 A 60% toluene solution of tung oil-modified phenolic resin used in Example 1, a bromine content of 4896, an epoxy equivalent of 400 m, and a 60% toluene solution of Nol A diglycidyl ether was added to the solid content ratio [tung oil modified]. Phenol taJ fat) /
(Brominated bisphenol A diglycidyl ether)
= Mixed and dissolved in a ratio of 80/20, coated on 11 mils kraft paper and dried. Hereinafter, in the same manner as in Example 1, a single-sided copper-clad laminate with a thickness of 1.6 wheels was obtained. .
比較例２
実施例１で使用した桐油変性フェノール樹脂と比較例１
で使用したブロム化ビスフェノールＡジグリシジルエー
テルと、トリフェニルホスフェートを固形分世率で〔桐
油変性フェノール樹脂） ／ （ブロム化ビスフェノー
ルＡジグリシジルエーテル）／（）リフェニルホスフエ
ート〕＝６０／３０／１０の割合で混合溶解し、これを
１１ミルスのクラフト紙に塗工乾燥して、以下、実施例
１と同様の方法で厚さ１．６−の片面銅張り積層板を得
た。Comparative Example 2 Tung oil modified phenolic resin used in Example 1 and Comparative Example 1
Brominated bisphenol A diglycidyl ether and triphenyl phosphate used in solid fraction [tung oil modified phenol resin] / (brominated bisphenol A diglycidyl ether) / () triphenyl phosphate] = 60/30/ The mixture was mixed and dissolved in a ratio of 10:1, and then coated on 11 mils kraft paper and dried. A single-sided copper-clad laminate with a thickness of 1.6 mm was obtained in the same manner as in Example 1.
実施例、比較例で得た積層板の試験結果を第第 １
表
発明の効果
以上の試験結果から明らかなように、本発明により難燃
効果が向上し、可撓性、耐熱性に優れた積層板のための
難燃性樹脂組成物を製造でき、樹脂溶液及び塗工基材の
貯蔵安定性も向上する。The test results of the laminates obtained in Examples and Comparative Examples are
As is clear from the test results described above, the present invention improves the flame retardant effect, makes it possible to produce a flame retardant resin composition for laminates with excellent flexibility and heat resistance, and And the storage stability of the coated substrate is also improved.
Claims (1)
フェニルフォスファイトを反応させることを特徴とする
積層板用難燃性樹脂組成物の製造法。A method for producing a flame-retardant resin composition for laminates, which comprises reacting brominated bisphenol A diglycidyl ether with triphenyl phosphite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27695687A JPH01118522A (en) | 1987-10-30 | 1987-10-30 | Preparation of flame-retardant resin composition for laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27695687A JPH01118522A (en) | 1987-10-30 | 1987-10-30 | Preparation of flame-retardant resin composition for laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01118522A true JPH01118522A (en) | 1989-05-11 |
Family
ID=17576754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27695687A Pending JPH01118522A (en) | 1987-10-30 | 1987-10-30 | Preparation of flame-retardant resin composition for laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01118522A (en) |
-
1987
- 1987-10-30 JP JP27695687A patent/JPH01118522A/en active Pending
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