JPH093302A - Phenolic resin composition, prepreg produced using same and laminate - Google Patents
Phenolic resin composition, prepreg produced using same and laminateInfo
- Publication number
- JPH093302A JPH093302A JP15163395A JP15163395A JPH093302A JP H093302 A JPH093302 A JP H093302A JP 15163395 A JP15163395 A JP 15163395A JP 15163395 A JP15163395 A JP 15163395A JP H093302 A JPH093302 A JP H093302A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- phenol resin
- compound
- prepreg
- 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.)
- Withdrawn
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はフェノール樹脂組成物、
そのフェノール樹脂組成物を用いたプリプレグ、及び積
層板に関し、一例をあげれば、電気機器・電子機器、産
業機器等に搭載される紙基材積層板に有用なものであ
る。The present invention relates to a phenol resin composition,
Regarding the prepreg and the laminated board using the phenolic resin composition, for example, they are useful for a paper base laminated board to be mounted on electric equipment / electronic equipment, industrial equipment and the like.
【０００２】[0002]
【従来の技術】電子機器等に搭載される紙基材フェノー
ル樹脂積層板は難燃性が要求されている。例えば、難燃
性水準としてＵＬ試験法において、最大燃焼時間が１０
秒以下が求められている。上記高水準の難燃性を付与す
るために、ブロム系難燃剤を汎用しているが、近年公害
上の問題から、上記ブロム系難燃剤の不使用が求められ
ている。そのため、ブロム系難燃剤に代わり、リン系難
燃剤の使用が検討されているが、リン系難燃剤は含有量
を増加すると難燃性は向上するものの耐熱性、特に半田
耐熱性が劣化する問題がある。従って、耐熱性の水準を
維持しつつ、難燃性の優れた積層板を得ることのできる
リン系難燃剤を用いたフェノール樹脂組成物が求められ
ている。2. Description of the Related Art A paper-based phenolic resin laminated plate mounted on electronic equipment is required to have flame retardancy. For example, in the UL test method as the flame retardancy level, the maximum burning time is 10
Less than a second is required. In order to impart the above-mentioned high level of flame retardancy, a brominated flame retardant is generally used, but in recent years, due to pollution problems, it is required that the brominated flame retardant is not used. Therefore, the use of a phosphorus-based flame retardant instead of a bromine-based flame retardant is being considered, but the phosphorus-based flame retardant improves the flame retardancy when the content is increased, but the heat resistance, especially the solder heat resistance deteriorates. There is. Therefore, there is a demand for a phenolic resin composition using a phosphorus-based flame retardant that can obtain a laminated board having excellent flame retardancy while maintaining the level of heat resistance.
【０００３】[0003]
【発明が解決しようとする課題】本発明は上記の事実に
鑑みてなされたもので、その目的とするところは、耐熱
性の水準を維持しつつ、難燃性の優れた、リン系化合物
を含有するフェノール樹脂組成物、このフェノール樹脂
組成物を用いたプリプレグ、及び積層板を提供すること
にある。The present invention has been made in view of the above facts, and an object of the present invention is to provide a phosphorus compound having excellent flame retardancy while maintaining a heat resistance level. It is intended to provide a phenol resin composition containing, a prepreg using the phenol resin composition, and a laminated board.
【０００４】[0004]
【課題を解決するための手段】本発明の請求項１に係る
フェノール樹脂組成物は、リン系化合物を含有するフェ
ノール樹脂組成物であって、さらに、上記組成物中に、
メラミン樹脂、ユリア樹脂、ウレタン樹脂の単独、変
性物、これら樹脂含有化合物、及び、ジシアンジアミ
ド、アニリンからなる群から選ばれた少なくとも１種以
上の窒素含有化合物、下記構造式〔１〕で表されるシ
アヌレート化合物、並びに、ハイドロキノンを成分と
して含有することを特徴とする。The phenol resin composition according to claim 1 of the present invention is a phenol resin composition containing a phosphorus compound, and further, in the above composition,
Melamine resin, urea resin, urethane resin alone or modified product, these resin-containing compounds, and at least one nitrogen-containing compound selected from the group consisting of dicyandiamide and aniline, represented by the following structural formula [1] It is characterized by containing a cyanurate compound and hydroquinone as components.
【０００５】[0005]
【化２】 Embedded image
【０００６】〔式中Ｒ1 , Ｒ2 , Ｒ3 はアルキル基を示
す。〕 本発明の請求項２に係るプリプレグは、請求項１記載の
フェノール樹脂組成物を基材に含浸し、この含浸したフ
ェノール樹脂組成物の樹脂が半硬化した状態にあること
を特徴とする。[In the formula, R 1, R 2 and R 3 represent an alkyl group. A prepreg according to claim 2 of the present invention is characterized in that a substrate is impregnated with the phenol resin composition according to claim 1, and the resin of the impregnated phenol resin composition is in a semi-cured state.
【０００７】本発明の請求項３に係る積層板は、請求項
２記載のプリプレグを用いて、樹脂が完全に硬化した状
態にあることを特徴とする。The laminated plate according to claim 3 of the present invention is characterized in that the resin is completely cured by using the prepreg according to claim 2.
【０００８】以下、本発明を詳細に説明する。本発明の
フェノール樹脂組成物を構成するフェノール樹脂として
は、各種のものが使用でき、フェノール樹脂の単独、変
性物、混合物等が用いられる。Hereinafter, the present invention will be described in detail. As the phenol resin constituting the phenol resin composition of the present invention, various ones can be used, and a phenol resin alone, a modified product or a mixture thereof can be used.
【０００９】本発明のフェノール樹脂組成物を構成する
リン系化合物は、得られる積層板に難燃性を付与するも
のであって、例えば、トリフェニルホスフェイト、トリ
クレジルホスフェイト、キシレニルジフェニルホスフェ
イト、クレジルジフェニルホスフェイト、及び、これら
の誘導体が挙げられる。このリン系化合物のリン成分の
含有量は、得られる積層板の樹脂組成物の固形量と基材
の構成比率等によって適宜決定されるが、例えば、積層
板中の樹脂組成物の固形量が略５０重量％の場合、上記
樹脂組成物の固形量に対し、リン成分の含有量が０．５
〜３重量％が好ましく、なかでも２重量％程度が適して
いる。上記リン系化合物のリン成分の含有量が少ないと
難燃性が劣り、多すぎると耐熱性が低下する。The phosphorus-based compound constituting the phenol resin composition of the present invention imparts flame retardancy to the resulting laminate, and examples thereof include triphenyl phosphate, tricresyl phosphate and xylenyl. Examples include diphenyl phosphate, cresyl diphenyl phosphate, and derivatives thereof. The content of the phosphorus component of the phosphorus-based compound is appropriately determined by the solid content of the resin composition of the resulting laminate and the composition ratio of the base material, for example, the solid content of the resin composition in the laminate is In the case of about 50% by weight, the phosphorus content is 0.5 with respect to the solid amount of the resin composition.
-3 wt% is preferable, and about 2 wt% is suitable. If the content of the phosphorus component in the phosphorus-based compound is small, the flame retardancy is poor, and if it is too large, the heat resistance is reduced.
【００１０】本発明のフェノール樹脂組成物は、特徴的
な構成材料として、窒素含有化合物、前記構造式〔１〕
で表されるシアヌレート化合物、及び、ハイドロキノン
を成分として含有する。The phenol resin composition of the present invention has a nitrogen-containing compound and the above structural formula [1] as a characteristic constituent material.
The cyanurate compound represented by and hydroquinone are contained as components.
【００１１】本発明のフェノール樹脂組成物は、上記窒
素含有化合物として、メラミン樹脂、ユリア樹脂、ウレ
タン樹脂の樹脂の単独、変性物、これらの樹脂含有化合
物、及び、ジシアンジアミド、アニリンからなる群から
選ばれた少なくとも１種以上を含有する。上記窒素含有
化合物は難燃補助剤として機能するものである。In the phenol resin composition of the present invention, the nitrogen-containing compound is selected from the group consisting of melamine resin, urea resin, urethane resin alone and modified, these resin-containing compounds, and dicyandiamide and aniline. At least one selected from the above is included. The nitrogen-containing compound functions as a flame retardant aid.
【００１２】本発明のフェノール樹脂組成物を構成する
シアヌレート化合物は、前記構造式〔１〕で表されるも
のである。式中Ｒ1 、Ｒ2 、Ｒ3 はアルキル基を示し、
全てが同一のアルキル基でも、異なったアルキル基でも
よい。上記シアヌレート化合物を含有すると難燃性のみ
ならず、耐熱性が向上する。上記シアヌレート化合物の
含有量は樹脂組成物の固形量に対し、１〜１０重量％が
好ましく、なかでも３〜５重量％程度が適している。The cyanurate compound constituting the phenol resin composition of the present invention is represented by the above structural formula [1]. In the formula, R 1 , R 2 and R 3 represent an alkyl group,
All may be the same alkyl group or different alkyl groups. When the above cyanurate compound is contained, not only flame retardancy but also heat resistance is improved. The content of the cyanurate compound is preferably 1 to 10% by weight, and more preferably about 3 to 5% by weight, based on the solid amount of the resin composition.
【００１３】本発明のフェノール樹脂組成物を構成する
ハイドロキノンは、難燃補助剤として機能するものであ
る。上記ハイドロキノンを含有すると、積層板を作製す
るまでの工程において、フェノール樹脂作製の際に残存
するホルムアルデヒドと反応し、可燃物を低減したり、
架橋密度を上げて積層板が熱分解するのを抑える。さら
に、上記ハイドロキノンは積層板が燃焼する際に生じる
ラジカルとハイドロキノンのラジカルが反応し、燃焼を
抑制する。その結果、積層板の難燃性が向上する。The hydroquinone constituting the phenol resin composition of the present invention functions as a flame retardant auxiliary agent. When the above-mentioned hydroquinone is contained, it reacts with the formaldehyde remaining during the production of the phenolic resin in the steps up to the production of the laminate, and reduces flammable substances,
Increase the crosslink density to prevent thermal decomposition of the laminate. Furthermore, the hydroquinone suppresses combustion by reacting the radicals generated when the laminate burns with the radicals of hydroquinone. As a result, the flame retardancy of the laminated plate is improved.
【００１４】上述の如く、上記窒素含有化合物、シアヌ
レート化合物、及び、ハイドロキノンは難燃補助剤とし
て機能するものであり、これら三成分を含有していると
リン系化合物の含有量が少量でも高水準の難燃性を付与
し、シアヌレート化合物は耐熱性の向上に効果を有す
る。また、リン系化合物の含有量が少量ですむため、耐
熱性の低下を防止する点からも有効である。As described above, the above-mentioned nitrogen-containing compound, cyanurate compound, and hydroquinone function as a flame retardant auxiliary agent. When these three components are contained, even if the content of the phosphorus compound is small, it is at a high level. And the cyanurate compound have an effect of improving heat resistance. Further, since the content of the phosphorus-based compound is small, it is effective from the viewpoint of preventing deterioration of heat resistance.
【００１５】上記フェノール樹脂組成物は、必要に応じ
てアンチモン等の他種の難燃剤を併用してもよい。さら
に、無機、有機の充填剤、溶剤及びその他水等の添加物
を適宜に配合してもよい。The above-mentioned phenol resin composition may be used in combination with other flame retardants such as antimony, if necessary. Further, an inorganic or organic filler, a solvent, and other additives such as water may be appropriately blended.
【００１６】上記フェノール樹脂組成物を用いてプリプ
レグを製造するにあたって、基材は、例えば、クラフト
紙、リンター紙、その他クラフト紙又はリンター紙に無
機物又は有機物を混入した紙基材が挙げられる。上述の
フェノール樹脂組成物をこれらの基材に含浸し、樹脂を
半硬化してプリプレグを得る。高度の電気特性を有する
積層板の場合、樹脂を多量に含有させる必要性から、含
浸する際に、上記フェノール樹脂組成物、又は、フェノ
ール樹脂組成物と別の樹脂組成物を用い一次含浸処理を
行い、次いで上記フェノール樹脂組成物を用いて二次含
浸処理を行うことが有効である。通常においては、上記
一次含浸用の樹脂組成物は溶剤又は水等で希釈された粘
度の低いものが用いられる。In producing a prepreg using the above-mentioned phenol resin composition, examples of the base material include kraft paper, linter paper, and other paper base materials in which kraft paper or linter paper is mixed with an inorganic substance or an organic substance. These substrates are impregnated with the above-mentioned phenol resin composition and the resin is semi-cured to obtain a prepreg. In the case of a laminated board having a high degree of electrical characteristics, since it is necessary to contain a large amount of resin, when impregnated, a primary impregnation treatment using the above-mentioned phenol resin composition or a resin composition different from the phenol resin composition. It is effective to carry out a secondary impregnation treatment using the above-mentioned phenol resin composition. In general, the resin composition for primary impregnation used has a low viscosity diluted with a solvent or water.
【００１７】本発明の積層板は、上述の製造方法で得ら
れたプリプレグ数枚と、必要により銅、アルミニウム、
ニッケル等の金属箔を重ね合わせ、加熱加圧すると、基
材中の樹脂が完全に硬化し、作製される。上記フェノー
ル樹脂組成物を用いるので、耐熱性が良好で、難燃性の
向上した積層板が得られる。上記積層板はブロム系難燃
剤の不使用を可能とするので、公害防止の点からも優れ
る。The laminated plate of the present invention comprises several prepregs obtained by the above-mentioned manufacturing method, and if necessary, copper, aluminum,
When metal foils such as nickel are superposed and heated and pressed, the resin in the base material is completely cured and is produced. Since the above-mentioned phenol resin composition is used, a laminate having good heat resistance and improved flame retardancy can be obtained. Since the above-mentioned laminated plate allows the use of no brominated flame retardant, it is also excellent in terms of pollution prevention.
【００１８】[0018]
実施例１ 一次含浸用の樹脂組成物、及び一次含浸は次の様に行っ
た。フェノール１００重量部（以下部と記す）、３７重
量％（以下単に％と記す）のホルマリン７０部を反応さ
せてレゾール型フェノール反応生成物Ａを得た。また、
メラミン１００部、ホルマリン（固形分３７％）１００
部を反応させてメラミン反応生成物Ｂを得た。このレゾ
ール型フェノール反応生成物Ａ５０部とメラミン反応生
成物Ｂ５０部の混合物を、水とメタノールを１対１で混
合したメタノール水溶液で希釈し、固形分１５％の一次
含浸用の樹脂組成物を得た。基材に重量１２６ｇ／ｍ2
のクラフト紙を用い、このクラフト紙に上記一次含浸用
の樹脂組成物を一次含浸した。その後、１３５℃の乾燥
機で３０秒乾燥し、樹脂が半硬化した状態である一次プ
リプレグＡを得た。この一次プリプレグＡは、一次ワニ
スＡの樹脂含有量がクラフト紙に対して１５％であっ
た。Example 1 The resin composition for primary impregnation and the primary impregnation were performed as follows. Resol type phenol reaction product A was obtained by reacting 100 parts by weight of phenol (hereinafter referred to as “part”) and 70 parts of 37% by weight (hereinafter referred to as “%”) formalin. Also,
Melamine 100 parts, formalin (solid content 37%) 100
Parts were reacted to obtain a melamine reaction product B. A mixture of 50 parts of this resol type phenol reaction product A and 50 parts of melamine reaction product B was diluted with an aqueous methanol solution in which water and methanol were mixed in a ratio of 1: 1 to obtain a resin composition for primary impregnation with a solid content of 15%. It was Weight of base material 126g / m 2
This kraft paper was first impregnated with the above resin composition for primary impregnation. Then, it was dried for 30 seconds in a dryer at 135 ° C. to obtain a primary prepreg A in which the resin was semi-cured. In this primary prepreg A, the resin content of the primary varnish A was 15% based on the kraft paper.
【００１９】二次含浸に用いたフェノール樹脂組成物の
調製は次の様に行った。フェノール１００部、３７％の
ホルマリン８０部、桐油３０部を反応させ、桐油変性レ
ゾール型フェノール樹脂を作製した。この桐油変性レゾ
ール型フェノール樹脂１００部に、リン系化合物として
トリフェニルホスフェイトを２０部、窒素含有化合物と
して上記メラミン反応生成物Ｂを１５部、前記構造式
〔１〕中のＲ1 、Ｒ2 、Ｒ3 がエチレン（−ＣＨ2 ＣＨ
2 −）で表されるシアヌレート化合物を５部、ハイドロ
キノンを５部混合し、フェノール樹脂組成物を作製し
た。The phenol resin composition used for the secondary impregnation was prepared as follows. 100 parts of phenol, 80 parts of 37% formalin and 30 parts of tung oil were reacted to produce a tung oil-modified resol type phenol resin. To 100 parts of this tung oil-modified resol-type phenolic resin, 20 parts of triphenyl phosphate as a phosphorus compound, 15 parts of the above melamine reaction product B as a nitrogen-containing compound, R 1 and R 2 in the structural formula [1] are used. , R 3 is ethylene (—CH 2 CH
2- ) 5 parts of the cyanurate compound represented by 2 ) and 5 parts of hydroquinone were mixed to prepare a phenol resin composition.
【００２０】二次含浸処理は次の様に行った。上記一次
プリプレグＡに上記フェノール樹脂組成物を含浸し、１
５５℃の乾燥機で１００秒間処理し、樹脂が半硬化した
状態であるプリプレグＢを製造した。このプリプレグＢ
中における、樹脂の含有量は５０％であった。The secondary impregnation treatment was performed as follows. The primary prepreg A is impregnated with the phenol resin composition, and 1
The resultant was treated with a drier at 55 ° C. for 100 seconds to produce prepreg B in which the resin was in a semi-cured state. This prepreg B
The content of the resin therein was 50%.
【００２１】次に、プリプレグＢを８枚重ね、最上層に
厚さ０．０３５ｍｍの銅箔を接着剤を介して配設し、こ
れを圧力１００ｋｇ／ｃｍ2 、温度１６０℃で６０分間
成形し、樹脂が完全に硬化した厚さ１．６ｍｍの積層板
を得た。Next, eight prepregs B were stacked, a copper foil having a thickness of 0.035 mm was arranged on the uppermost layer via an adhesive, and this was molded at a pressure of 100 kg / cm 2 and a temperature of 160 ° C. for 60 minutes. Thus, a 1.6 mm thick laminated plate in which the resin was completely cured was obtained.
【００２２】なお、上記一次含浸及び二次含浸の両方の
樹脂組成物の固形量に対し、上記リン系化合物のリン成
分の含有量は２重量％であり、上記シアヌレート化合物
は５重量％であった。The content of the phosphorus component of the phosphorus compound is 2% by weight and the content of the cyanurate compound is 5% by weight based on the solid amount of the resin composition in both the primary impregnation and the secondary impregnation. It was
【００２３】実施例２ 二次含浸に用いたフェノール樹脂組成物の窒素含有化合
物として上記メラミン反応生成物Ｂを１５部とアニリン
０．２部を用いた以外は実施例１と同様にして、一次プ
リプレグＡ及びプリプレグＢの作製を行い、積層板を得
た。なお、上記一次含浸及び二次含浸の両方の樹脂組成
物の固形量に対し、上記リン系化合物のリン成分の含有
量は２重量％であり、上記シアヌレート化合物は５重量
％であった。Example 2 A primary resin was prepared in the same manner as in Example 1 except that 15 parts of the melamine reaction product B and 0.2 part of aniline were used as the nitrogen-containing compound of the phenol resin composition used for the secondary impregnation. A prepreg A and a prepreg B were produced to obtain a laminated board. The content of the phosphorus component of the phosphorus compound was 2% by weight and the content of the cyanurate compound was 5% by weight based on the solid amount of the resin composition in both the primary and secondary impregnations.
【００２４】実施例３ ユリア１００部、ホルマリン（固形分３７％）１００部
を反応させてユリア樹脂Ｃを得た。二次含浸に用いたフ
ェノール樹脂組成物の窒素含有化合物として上記ユリア
樹脂Ｃを１５部用いた以外は実施例１と同様に、一次プ
リプレグＡ及びプリプレグＢの作製を行い、積層板を得
た。Example 3 Urea resin C was obtained by reacting 100 parts of urea with 100 parts of formalin (solid content 37%). A primary prepreg A and a prepreg B were produced in the same manner as in Example 1 except that 15 parts of the above urea resin C was used as the nitrogen-containing compound of the phenol resin composition used for the secondary impregnation to obtain a laminated plate.
【００２５】実施例４ メチレンビスパラフェニレンジイソシアネート（ＭＤ
Ｉ：三井東圧化学株式会社製）１００部とビスフェノー
ルＡ１００部を反応させてウレタン樹脂Ｄを得た。二次
含浸に用いたフェノール樹脂組成物の窒素含有化合物と
して上記ウレタン樹脂Ｄを１５部用いた以外は実施例１
と同様に、一次プリプレグＡ及びプリプレグＢの作製を
行い、積層板を得た。Example 4 Methylenebisparaphenylene diisocyanate (MD
I: manufactured by Mitsui Toatsu Chemicals, Inc.) 100 parts and bisphenol A 100 parts were reacted to obtain urethane resin D. Example 1 except that 15 parts of the urethane resin D was used as the nitrogen-containing compound of the phenol resin composition used for the secondary impregnation.
A primary prepreg A and a prepreg B were prepared in the same manner as in 1. to obtain a laminated plate.
【００２６】実施例５ 二次含浸に用いたフェノール樹脂組成物のリン系化合物
としてクレジルジフェニルホスフェイトを用いた以外は
実施例１と同様にして、一次プリプレグＡ及びプリプレ
グＢの作製を行い、積層板を得た。なお、上記一次含浸
及び二次含浸の両方の樹脂組成物の固形量に対し、上記
リン系化合物のリン成分の含有量は２重量％であり、上
記シアヌレート化合物は５重量％であった。Example 5 A primary prepreg A and a prepreg B were prepared in the same manner as in Example 1 except that cresyl diphenyl phosphate was used as the phosphorus compound of the phenol resin composition used for the secondary impregnation. A laminated board was obtained. The content of the phosphorus component of the phosphorus compound was 2% by weight and the content of the cyanurate compound was 5% by weight based on the solid amount of the resin composition in both the primary and secondary impregnations.
【００２７】比較例１ 二次含浸に用いたフェノール樹脂組成物の調製は次の様
に行った。フェノール１００部、３７％のホルマリン８
０部、桐油３０部を反応させ、桐油変性レゾール型フェ
ノール樹脂を作製した。この桐油変性レゾール型フェノ
ール樹脂１００部に、リン系化合物としてトリフェニル
ホスフェイトを２０部、窒素含有化合物として上記メラ
ミン反応生成物Ｂを１５部混合し、フェノール樹脂組成
物を作製した。このフェノール樹脂組成物を用いた以外
は実施例１と同様にして、一次プリプレグＡ及びプリプ
レグＢの作製を行い、積層板を得た。Comparative Example 1 The phenol resin composition used for the secondary impregnation was prepared as follows. Phenol 100 parts, 37% formalin 8
0 part and 30 parts of tung oil were reacted to prepare a tung oil-modified resol type phenol resin. To 100 parts of this tung oil-modified resol-type phenol resin, 20 parts of triphenyl phosphate as a phosphorus compound and 15 parts of the above melamine reaction product B as a nitrogen-containing compound were mixed to prepare a phenol resin composition. A primary prepreg A and a prepreg B were produced in the same manner as in Example 1 except that this phenol resin composition was used to obtain a laminated plate.
【００２８】比較例２ 二次含浸に用いたフェノール樹脂組成物の調製は次の様
に行った。フェノール１００部、３７％のホルマリン８
０部、桐油３０部を反応させ、桐油変性レゾール型フェ
ノール樹脂を作製した。この桐油変性レゾール型フェノ
ール樹脂１００部に、リン系化合物としてトリフェニル
ホスフェイトを４０部、窒素含有化合物として上記メラ
ミン反応生成物Ｂを１５部混合し、フェノール樹脂組成
物を作製した。このフェノール樹脂組成物を用いた以外
は実施例１と同様にして、一次プリプレグＡ及びプリプ
レグＢの作製を行い、積層板を得た。Comparative Example 2 The phenol resin composition used for the secondary impregnation was prepared as follows. Phenol 100 parts, 37% formalin 8
0 part and 30 parts of tung oil were reacted to prepare a tung oil-modified resol type phenol resin. To 100 parts of this tung oil-modified resol type phenol resin, 40 parts of triphenyl phosphate as a phosphorus compound and 15 parts of the above melamine reaction product B as a nitrogen-containing compound were mixed to prepare a phenol resin composition. A primary prepreg A and a prepreg B were produced in the same manner as in Example 1 except that this phenol resin composition was used to obtain a laminated plate.
【００２９】得られた実施例１〜５、及び比較例１〜２
の積層板の難燃性、及び耐熱性を評価した。難燃性は、
ＵＬ試験法に基づいて消炎時間を１０個測定し、平均値
と最大値を求めた。耐熱性は半田耐熱性とオーブン耐熱
性を測定した。上記半田耐熱性は２６０℃の半田にフロ
ートし、ふくれ発生までの時間を測定した。上記オーブ
ン耐熱性は所定の雰囲気温度のオーブンに３０分放置し
た後、外観を目視で観察し、ふくれが発生したものを不
合格、ふくれがないものを合格とし、合格する限界温度
を求めた。The obtained Examples 1-5 and Comparative Examples 1-2
The flame retardancy and heat resistance of the laminated plate of No. 1 were evaluated. Flame retardant,
Ten extinction times were measured based on the UL test method, and an average value and a maximum value were obtained. For heat resistance, solder heat resistance and oven heat resistance were measured. The solder heat resistance was measured by floating the solder at 260 ° C. and measuring the time until the occurrence of blistering. Regarding the above-mentioned oven heat resistance, after leaving it in an oven having a predetermined atmosphere temperature for 30 minutes, the appearance was visually observed, and those with blisters were rejected, those without blisters were accepted, and the limit temperature at which they passed was determined.
【００３０】結果は表１に示したとおり、実施例１〜５
はいずれも難燃性の水準として最大燃焼時間が１０秒以
下の高難燃性を達成し、且つ、耐熱性も良好であった。
比較例１は難燃性が劣り、比較例２は耐熱性が低下して
いた。The results, as shown in Table 1, are shown in Examples 1-5.
Each of them had high flame retardancy with a maximum combustion time of 10 seconds or less as a flame retardancy level, and also had good heat resistance.
Comparative Example 1 was inferior in flame retardancy, and Comparative Example 2 was inferior in heat resistance.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【発明の効果】本発明の請求項１記載のフェノール樹脂
組成物を用いると、半田耐熱性等の耐熱性が良好で、難
燃性の向上した積層板が得られる。When the phenol resin composition according to the first aspect of the present invention is used, a laminate having good heat resistance such as solder heat resistance and improved flame retardancy can be obtained.
【００３３】本発明の請求項２に係るプリプレグは上記
フェノール樹脂組成物を用いるので、このプリプレグを
用いるた積層板は、耐熱性が良好で、難燃性が向上す
る。Since the prepreg according to claim 2 of the present invention uses the above-mentioned phenol resin composition, the laminated board using this prepreg has good heat resistance and improved flame retardancy.
【００３４】本発明の請求項３に係る積層板は上記プリ
プレグを用いるので、半田耐熱性等の耐熱性が良好で、
難燃性が優れる。上記積層板はブロム系難燃剤の不使用
を可能とするので、公害防止の点からも優れる。Since the laminated board according to claim 3 of the present invention uses the above prepreg, it has good heat resistance such as solder heat resistance,
Excellent flame retardancy. Since the above-mentioned laminated plate allows the use of no brominated flame retardant, it is also excellent in terms of pollution prevention.
Claims (3)
組成物であって、さらに、上記組成物中に、メラミン樹
脂、ユリア樹脂、ウレタン樹脂の単独、変性物、これら
樹脂含有化合物、及び、ジシアンジアミド、アニリンか
らなる群から選ばれた少なくとも１種以上の窒素含有化
合物、下記構造式〔１〕で表されるシアヌレート化合
物、並びに、ハイドロキノンを成分として含有すること
を特徴とするフェノール樹脂組成物。 【化１】 〔式中Ｒ1 , Ｒ2 , Ｒ3 はアルキル基を示す。〕1. A phenolic resin composition containing a phosphorus-based compound, further comprising a melamine resin, a urea resin, a urethane resin alone or a modified product, a resin-containing compound and dicyandiamide in the composition. A phenol resin composition comprising at least one nitrogen-containing compound selected from the group consisting of aniline, a cyanurate compound represented by the following structural formula [1], and hydroquinone as components. Embedded image [In the formula, R 1, R 2 and R 3 represent an alkyl group. ]
基材に含浸し、この含浸したフェノール樹脂組成物の樹
脂が半硬化した状態にあることを特徴とするプリプレ
グ。2. A prepreg, wherein a base material is impregnated with the phenol resin composition according to claim 1, and the impregnated resin of the phenol resin composition is in a semi-cured state.
脂が完全に硬化した状態にあることを特徴とする積層
板。3. A laminate comprising the prepreg according to claim 2 and a resin in a completely cured state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15163395A JPH093302A (en) | 1995-06-19 | 1995-06-19 | Phenolic resin composition, prepreg produced using same and laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15163395A JPH093302A (en) | 1995-06-19 | 1995-06-19 | Phenolic resin composition, prepreg produced using same and laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH093302A true JPH093302A (en) | 1997-01-07 |
Family
ID=15522816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15163395A Withdrawn JPH093302A (en) | 1995-06-19 | 1995-06-19 | Phenolic resin composition, prepreg produced using same and laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH093302A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11192988B2 (en) | 2019-02-13 | 2021-12-07 | Kompozitor Kft. | Phenol-furan resin composition |
-
1995
- 1995-06-19 JP JP15163395A patent/JPH093302A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11192988B2 (en) | 2019-02-13 | 2021-12-07 | Kompozitor Kft. | Phenol-furan resin composition |
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| Date | Code | Title | Description |
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| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20020903 |