JP4314543B2 - Phosphorus-containing triazine-modified phenolic resin composition and flame retardant - Google Patents
Phosphorus-containing triazine-modified phenolic resin composition and flame retardant Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、りん含有トリアジン変性フェノール樹脂組成物及び難燃剤に関するものである。
【０００２】
【従来の技術】
積層板用樹脂の難燃化方法として、従来は、臭素系難燃剤、窒素系難燃化剤とリン系難燃剤の単独または組み合わせ及び前記難燃剤の単独または組み合わせに無機系難燃助剤を併用する難燃システムが主流であった。しかし、近年、環境問題から、臭素系難燃剤の使用が敬遠されつつあり、窒素系難燃剤とリン系難燃剤との組み合わせが注目されつつある。しかし、リン系難燃剤の使用においては、以下のような問題点があった。赤りんを使用する場合、安全性が不十分である。りん酸系化合物を使用する場合、１７０℃前後の成形温度により、樹脂および有機基材が炭化して、積層板の強度が低下する。りん酸エステル類を使用すると、耐熱性、耐溶剤性が低下する。
【０００３】
【発明が解決しようとする課題】
本発明はトリアジン変性フェノール樹脂にりん化合物を反応させて得られ、耐熱性、耐溶剤性が良好な積層板用りん含有トリアジン変性フェノール樹脂組成物及び難燃剤を提供するものである。
【０００４】
【課題を解決するための手段】
本発明は、次のものに関する。
１． トリアジン変性フェノール樹脂にりん化合物を反応させて得られるりん含有トリアジン変性フェノール樹脂組成物であって、前記トリアジンが、ベンゾグアナミン、あるいは、ベンゾグアナミンとメラミンとの併用のいずれかであり、前記りん化合物が、トリフェニルフォスフェート、トリクレジルフォスフェート、クレジルジフェニルフォスフェート、トリブチルフォスフェート、トリ−２−エチルヘキシルフォスフェートのいずれかである、りん含有トリアジン変性フェノール樹脂組成物。
２． トリアジン変性フェノール樹脂がトリアジン化合物とフェノール類とホルムアルデヒド類からなり、１００℃以上で１時間以上の縮合反応させて得たものである項１項記載のりん含有トリアジン変性フェノール樹脂組成物。
３． りん化合物がトリフェニルフォスフェートである項１又は項２記載のりん含有トリアジン変性フェノール樹脂組成物。
４． 項１〜３のいずれかに記載のりん含有トリアジン変性フェノール樹脂組成物を主成分としてなる紙フェノール樹脂積層板用難燃剤。
５． 項１〜３のいずれかに記載のりん含有トリアジン変性フェノール樹脂組成物を含んでなるガラスエポキシ樹脂積層板用難燃剤。
【０００５】
【発明の実施の形態】
本発明に用いるトリアジン化合物としては、特に限定するものではないが、メラミン、ベンゾグアナミン、アセトグアナミン等があり、窒素含有量が多いことからメラミンが特に好ましい。
【０００６】
フェノール類としては、フェノール、クレゾール、キシレノール、ブチルフェノールなどのアルキルフェノール、カテコール、レゾルシン、ビスフェノールＡ、ビスフェノールＦなどの多価フェノール等がある。これらの単独使用又は２種類以上の併用も可能であり、特に限定される物ではない。
【０００７】
アルデヒド類としては、ホルマリン（通常３７％であるが、３７％以上の高濃度品の使用も可）、パラホルムアルデヒド（ホルムアルデヒド含量について限定する物ではなく、工業品の含量である８０〜９６％品の使用が可）等の単独及び併用が可能である。
【０００８】
トリアジン化合物とフェノール類との合計に対するトリアジン化合物のモル比率は２％〜５０％が好ましい。２％未満であると難燃性に乏しくなる傾向があり、５０％を超えると樹脂化が困難となる。
【０００９】
トリアジン化合物とフェノール類との合計１モルに対してアルデヒド類のモル比率は０．０３〜２．０が好ましい。０．０３未満であると未反応フェノールが多くなりやすく、２．０を超えると分子量が大きくなり、ゲルが発生することがある。
【００１０】
トリアジン化合物とフェノール類とアルデヒド類との反応において、触媒の使用及び種類を限定するものではない。無触媒でも反応は進む。触媒を使用する際にも、しゅう酸、酢酸、トルエンスルフォン酸、パラトルエンスルフォン酸等の有機酸、塩酸、硫酸、燐酸等の無機酸等の酸性触媒、トリメチルアミン、トリエチルアミン、アンモニア水、ジエチルアミン、アニリン等のアミン系触媒、炭酸グアニジン等の炭酸塩、水酸化ナトリウム、水酸化カリウム、酢酸亜鉛、塩化亜鉛等の金属化合物の使用が可能である。触媒は、
【００１１】
トリアジン化合物とフェノール類とアルデヒド類との反応の方法、順序は特に限定するものではない。すなわち、トリアジン化合物とフェノール類とアルデヒド類を同時に反応させること、予め、フェノール類とアルデヒド類を反応させて、次いでトリアジン化合物、必要に応じて更にアルデヒド類を添加して反応させること、逆に、予め、トリアジン化合物とアルデヒド類を反応させて、次いでフェノール類、必要に応じて更にアルデヒド類を添加して反応させること等任意である。
【００１２】
トリアジン化合物とフェノール類とアルデヒド類との反応は１００℃以下の付加反応、１００℃以上の縮合反応と別々に進めることが好ましい。しかし、トリアジン化合物とフェノール類とアルデヒド類との反応を同時に行う場合は、反応温度１００℃以下の付加反応の工程を設けずに、１００℃以上で付加反応と縮合反応を同時の行ってもよい。１００℃以上の縮合反応は必ず必要であり、１００℃以下の付加反応だけであると、りん含有トリアジン変性フェノール樹脂組成物の相分離、溶剤への溶解性または保存安定性の低下をきたす。
【００１３】
トリアジン化合物とフェノール類とホルムアルデヒド類と反応において、未反応フェノールの除去については、特に限定するものではないが、合成釜の有効活用より、未反応フェノールを除去した方が好ましい。
【００１４】
トリアジン変性フェノール樹脂と反応させるりん化合物としては、トリフェニルフォスフェート、トリクレジルフォスフェート、クレジルジフェニルフォスフェート、トリブチルフォスフェート、トリ−２−エチルヘキシルフォスフェートなどの使用が可能であるが、供給安定性、反応生成物であるフェノールの再利用からトリフェニルフォスフェートが好ましい。
【００１５】
トリアジン変性フェノール樹脂とりん化合物の重量比率は、トリアジン変性フェノール樹脂／りん化合物が５／１００〜１００／５が好ましい。５／１００未満であると未反応りん化合物含量が多くなり、耐薬品性が低下する傾向がある。一方、１００／５を越えると、りん含有トリアジン変性フェノール樹脂のりん含量が少なくなり、難燃性が低下する傾向がある。
【００１６】
トリアジン変性フェノール樹脂とりん化合物の反応で使用する触媒として、炭酸ナトリウム、炭酸カリウム等の炭酸塩、水酸化ナトリウム、水酸化カリウム等の水酸化物、トリエチルアミン、ジエチルアミン、トリメチルアミン等のアミン類、アンモニア水及び硫酸、塩酸等の酸類などエステル交換反応で使用する触媒を用いることができる。触媒の使用量は、トリアジン変性フェノール樹脂とりん化合物の総量に対して、０．０１〜５重量％が好ましい。
【００１７】
トリアジン変性フェノール樹脂とりん化合物の反応温度は特に限定するものではないが１００〜２００℃が好ましい。１００℃未満であると反応が遅くなり、２００℃を越えると反応物が著しく着色する傾向がある。
【００１８】
トリアジン変性フェノール樹脂とりん化合物の反応では、反応生成物を除去し、反応を生成系に進めるため減圧下で行うことが好ましい。
トリアジン変性フェノール樹脂とりん化合物との反応物の残存フェノール類及びアルコール類の合計量は５重量％以下が好ましい。５％を越えると、積層板に適用した場合、積層板の耐熱性が低下する。
【００１９】
該りん含有トリアジン変性フェノール樹脂を適用する積層板の樹脂系としては、フェノール樹脂及び植物油等の可とう化剤で変性した変性フェノール樹脂等の積層板に使用されるフェノール樹脂系、エポキシ樹脂として、エピビス型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、多官能型のエポキシ樹脂等（これらのエポキシ樹脂は臭素化されていてもよい）、硬化剤として、ジシアンジアミド、ノボラック型フェノール樹脂、ビスフェノールＡノボラック型フェノール樹脂に促進剤を添加したエポキシ樹脂系等積層板に使用されるエポキシ樹脂系等があり、適用に対しては特に限定するものではない。
【００２０】
積層板に適用した場合使用する基材は特に限定されるものではなく、クラフト紙やリンタ紙などの紙基材、ガラス繊維織布やガラス繊維不織布などのガラス基材などの基材の使用が可能である。
【００２１】
【実施例】
参考例１
（１）りん含有トリアジン変性フェノール樹脂（Ｔ１）の合成
温度計、冷却管、攪拌装置付き４ツ口セパラブルフラスコにフェノール ９４０ｇ、メラミン ４４ｇ、９２％パラホルムアルデヒド９８ｇ、トリエチルアミン０．８ｇを配合して、８０℃で３時間反応させた。さらに、還流温度まで昇温させ還流温度で１０時間反応させた。その後、フラスコ内温度１７０℃、減圧度７００ｍｍＨｇで濃縮物が出なくなるまで減圧濃縮を行った。ついで、減圧開放後、トリフェニルフォスフェート １０００ｇ、炭酸カリウム １ｇを添加して、フラスコ内温度１８０℃、減圧度７００ｍｍＨｇで１０時間反応させて、りん含有トリアジン変性フェノール樹脂（Ｔ１）を得た。未反応フェノールは２％であった。
【００２２】
（２）積層板用フェノール樹脂（Ａ１）の合成
温度計、冷却管、攪拌装置付き４ツ口セパラブルフラスコに桐油 ７２０ｇ、ｍ−クレゾール ５８０ｇ、パラトルエンスルフォン酸 ０．７４ｇを配合して、８０℃で１時間反応させ冷却した。次いで、フェノール５００ｇ、９２％パラホルムアルデヒド ４２０ｇ、２５％アンモニア水 ３５ｇを添加して、８０℃で１６０℃熱板上でのゲルタイムが６分になるまで常圧で反応を進めた。さらに、ゲルタイムが３分になるまで、８０℃以下で減圧濃縮を行った。その後、樹脂分が５０％になるようにメタノールとトルエンの混合溶剤を添加して、積層板用フェノール樹脂（Ａ１）を得た。
【００２３】
（３）積層板（Ｌ１）の作製
積層板用フェノール樹脂（Ａ１）とりん含有トリアジン変性フェノール樹脂（Ｔ１）とを、Ａ１（固形重量）／Ｔ１が８０／２０になるように混合して樹脂ワニスを調整した。これを、坪量１３５ｇ／ｍ2のクラフト紙に付着樹脂量が５０重量％になるように、含浸塗工した後、乾燥して塗工紙を得た。接着剤付き銅箔１枚とこの塗工紙８枚を銅箔が最外層になるように重ね合わせ、加熱加圧して、厚さ１．６ｍｍの紙基材積層板（Ｌ１）を得た。
【００２４】
実施例１
（１）りん含有トリアジン変性フェノール樹脂（Ｔ２）の合成
温度計、冷却管、攪拌装置付き４ツ口セパラブルフラスコにフェノール ９００ｇ、ベンゾグアナミン９０ｇ、メラミン９０ｇ、９２％パラホルムアルデヒド１５６ｇ、しゅう酸２１ｇを配合して、還流温度まで昇温させ還流温度で１０時間反応させた後、減圧度７００ｍｍＨｇで１６０℃まで昇温して濃縮した。減圧解放後、トリクレジルフォスフェートを１０００ｇ、炭酸ナトリウム １ｇを添加して、フラスコ内温度を１８０℃にして、減圧度７００ｍｍＨｇで１０時間反応を進め、さらに、この反応条件で減圧水蒸気蒸留を１０時間行い、りん含有トリアジン変性フェノール樹脂（Ｔ２）を得た。Ｔ２の残存フェノールと残存クレゾールの合計量は４％であった。
【００２５】
（２）積層板用エポキシ樹脂（Ａ２）の配合
冷却管、攪拌装置付き４ツ口セパラブルフラスコに エポキシ樹脂としてエピビス型エポキシ樹脂（油化シェルエポキシ（株）製 商品名エピコート８２８）５７０ｇ、硬化剤としてノボラック型フェノール樹脂（日立化成工業(株) 商品名ＨＰ８５０Ｎ）３１５ｇ、促進剤としてイミダゾール ８．５ｇ 溶剤としてメチルエチルケトン ５００ｇを配合して積層板用エポキシ樹脂組成物（Ａ２）を得た。
【００２６】
（３）積層板（Ｌ２）の作製
積層板用エポキシ樹脂組成物（Ａ２）にりん含有トリアジン変性フェノール樹脂（Ｔ２）を固形重量比でＡ２／Ｔ２＝８０／２０になるように混合し、樹脂ワニスを調整した。これを、ＭＩＬ７６２８タイプのガラス織布に付着樹脂量が４２重量％になるように、含浸塗工した後、乾燥して塗工布を得た。該塗工布８枚を組み合わせ、加熱加圧して、厚さ１．６ｍｍのガラス基材積層板（Ｌ２）を得た。
【００２７】
比較例１〔積層板（Ｌ３）の作製〕
積層板用フェノール樹脂（Ａ１）を、Ａ１（固形重量）／トリフェニルフォスフェート＝８０／２０になるように混合して樹脂ワニスを調整した。これを、坪量１３５ｇ／ｍ2のクラフト紙に付着樹脂量が５０重量％になるように、含浸塗工させた後、乾燥させ塗工紙を得た。接着剤付き銅箔１枚と該塗工紙８枚を組み合わせ、加熱加圧して、厚さ１．６ｍｍの紙基材積層板（Ｌ３）を得た。
【００２８】
比較例２〔積層板（Ｌ４）の作製〕
積層板用エポキシ樹脂（Ａ２）にトリクレジルフォスフェートを固形重量比でＡ２／トリクレジルフォスフェート＝８０／２０になるように混合して樹脂ワニスを調整した。これを、ＭＩＬ７６２８タイプのガラス織布に付着樹脂量が４２重量％になるように、含浸塗工させた後、乾燥させ塗工布を得た。該塗工布８枚を組み合わせ、加熱加圧して、厚さ１．６ｍｍのガラス基材積層板（Ｌ４）を得た。
【００２９】
以上得られた積層板の特性を表１に示す。
【表１】
耐溶剤性：銅箔を全面除去した積層板を２０ｍｍ×５０ｍｍに切断して、試験片とした。この試験片をアセトンで１０分煮沸した後、試験片の外観を評価した。外観に異常なしを○、端部または表面に若干の異常ありを△とし、端部または表面に異常ありを×とした。
耐熱性：紙基材積層板の場合は銅箔付き積層板を２５ｍｍ×２５ｍｍに切断して、試験片とした。この試験片を２６０℃のはんだ浴に浮かべ、膨れるまでの時間（秒）により耐熱性（はんだ耐熱性）の評価基準とした。また、ガラス基材積層板の場合は積層板のガラス転移温度（Ｔｇ）を耐熱性の評価基準とした。
【００３１】
【発明の効果】
本発明によるりん含有トリアジン変性フェノール樹脂を用いることにより、耐溶剤性、耐熱性に優れた積層板を得ることが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a phosphorus-containing triazine-modified phenol resin composition and a flame retardant.
[0002]
[Prior art]
Conventionally, as a flame retardant method for a resin for laminates, an inorganic flame retardant aid is used in a brominated flame retardant, a nitrogen flame retardant and a phosphorus flame retardant alone or in combination, and the flame retardant alone or in combination. The flame retardant system used together was the mainstream. However, in recent years, the use of brominated flame retardants has been avoided due to environmental problems, and the combination of nitrogen-based flame retardants and phosphorus-based flame retardants has been attracting attention. However, the use of phosphorus flame retardants has the following problems. When red phosphorus is used, safety is insufficient. When a phosphoric acid compound is used, the resin and the organic base material are carbonized at a molding temperature of around 170 ° C., and the strength of the laminate is lowered. When phosphoric acid esters are used, heat resistance and solvent resistance are lowered.
[0003]
[Problems to be solved by the invention]
The present invention provides a phosphorus-containing triazine-modified phenolic resin composition for a laminated board and a flame retardant which are obtained by reacting a triazine-modified phenolic resin with a phosphorus compound and have good heat resistance and solvent resistance.
[0004]
[Means for Solving the Problems]
The present invention relates to the following.
1. A phosphorus-containing triazine-modified phenol resin composition obtained by reacting a triazine-modified phenol resin with a phosphorus compound, wherein the triazine is either benzoguanamine or a combination of benzoguanamine and melamine, and the phosphorus compound is A phosphorus-containing triazine-modified phenol resin composition which is any one of triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, and tri-2-ethylhexyl phosphate.
2. Item 2. The phosphorus-containing triazine-modified phenolic resin composition according to item 1, wherein the triazine-modified phenolic resin comprises a triazine compound, phenols and formaldehyde, and is obtained by a condensation reaction at 100 ° C or higher for 1 hour or longer.
3. Item 3. The phosphorus-containing triazine-modified phenol resin composition according to Item 1 or 2, wherein the phosphorus compound is triphenyl phosphate.
4). Item 4. A flame retardant for a paper phenolic resin laminate comprising the phosphorus-containing triazine-modified phenolic resin composition according to any one of Items 1 to 3 as a main component.
5 . Item 5. A flame retardant for a glass epoxy resin laminate comprising the phosphorus-containing triazine-modified phenol resin composition according to any one of Items 1 to 3 .
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Although it does not specifically limit as a triazine compound used for this invention, There exist melamine, a benzoguanamine, an acetoguanamine, etc., and melamine is especially preferable from there being much nitrogen content.
[0006]
Examples of phenols include alkylphenols such as phenol, cresol, xylenol, and butylphenol, polyhydric phenols such as catechol, resorcin, bisphenol A, and bisphenol F. These can be used alone or in combination of two or more, and are not particularly limited.
[0007]
As aldehydes, formalin (usually 37%, but high-concentration products of 37% or more can be used), paraformaldehyde (not limited to formaldehyde content, but 80-96% product of industrial product content) Can be used alone or in combination.
[0008]
The molar ratio of the triazine compound to the total of the triazine compound and the phenol is preferably 2% to 50%. If it is less than 2%, the flame retardancy tends to be poor, and if it exceeds 50%, it becomes difficult to form a resin.
[0009]
The molar ratio of the aldehydes is preferably 0.03 to 2.0 with respect to 1 mol in total of the triazine compound and the phenols. If it is less than 0.03, the amount of unreacted phenol tends to increase, and if it exceeds 2.0, the molecular weight increases and a gel may be generated.
[0010]
In the reaction of the triazine compound, phenols and aldehydes, the use and type of the catalyst are not limited. The reaction proceeds even without catalyst. Even when using the catalyst, acidic catalysts such as organic acids such as oxalic acid, acetic acid, toluenesulfonic acid, paratoluenesulfonic acid, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, trimethylamine, triethylamine, aqueous ammonia, diethylamine, aniline It is possible to use amine catalysts such as carbonates, carbonates such as guanidine carbonate, and metal compounds such as sodium hydroxide, potassium hydroxide, zinc acetate, and zinc chloride. The catalyst
[0011]
The method and order of the reaction of the triazine compound, phenols and aldehydes are not particularly limited. That is, reacting triazine compound, phenols and aldehydes simultaneously, reacting phenols and aldehydes in advance, then adding triazine compound and further adding aldehydes as necessary, and conversely, It is optional to react the triazine compound with aldehydes in advance, and then add phenols and further aldehydes as necessary.
[0012]
The reaction of the triazine compound, the phenols, and the aldehydes preferably proceeds separately from the addition reaction at 100 ° C. or lower and the condensation reaction at 100 ° C. or higher. However, when the reaction of the triazine compound, the phenol and the aldehyde is performed simultaneously, the addition reaction and the condensation reaction may be performed simultaneously at 100 ° C. or higher without providing an addition reaction step at a reaction temperature of 100 ° C. or lower. . The condensation reaction at 100 ° C. or higher is absolutely necessary. If only the addition reaction at 100 ° C. or lower, the phase separation of the phosphorus-containing triazine-modified phenol resin composition, the solubility in a solvent or the storage stability is lowered.
[0013]
In the reaction between the triazine compound, the phenols and the formaldehyde, the removal of the unreacted phenol is not particularly limited, but it is preferable to remove the unreacted phenol from the effective utilization of the synthetic kettle.
[0014]
As the phosphorus compound to be reacted with the triazine-modified phenolic resin, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, etc. can be used. Triphenyl phosphate is preferable because of stability and reuse of the reaction product phenol.
[0015]
The weight ratio of the triazine-modified phenol resin to the phosphorus compound is preferably 5/100 to 100/5 for the triazine-modified phenol resin / phosphorus compound. If it is less than 5/100, the unreacted phosphorus compound content increases and the chemical resistance tends to decrease. On the other hand, when it exceeds 100/5, the phosphorus content of the phosphorus-containing triazine-modified phenol resin is decreased, and the flame retardancy tends to be lowered.
[0016]
Catalysts used in the reaction of triazine-modified phenolic resin with phosphorus compounds include carbonates such as sodium carbonate and potassium carbonate, hydroxides such as sodium hydroxide and potassium hydroxide, amines such as triethylamine, diethylamine and trimethylamine, aqueous ammonia In addition, a catalyst used in a transesterification reaction such as acids such as sulfuric acid and hydrochloric acid can be used. The amount of the catalyst used is preferably 0.01 to 5% by weight based on the total amount of the triazine-modified phenolic resin and the phosphorus compound.
[0017]
The reaction temperature of the triazine-modified phenol resin and the phosphorus compound is not particularly limited, but is preferably 100 to 200 ° C. When the temperature is lower than 100 ° C., the reaction becomes slow, and when the temperature exceeds 200 ° C., the reaction product tends to be markedly colored.
[0018]
The reaction between the triazine-modified phenol resin and the phosphorus compound is preferably carried out under reduced pressure in order to remove the reaction product and advance the reaction to the production system.
The total amount of residual phenols and alcohols in the reaction product of the triazine-modified phenol resin and the phosphorus compound is preferably 5% by weight or less. If it exceeds 5%, the heat resistance of the laminate is reduced when applied to the laminate.
[0019]
As a resin system of a laminated board to which the phosphorus-containing triazine-modified phenol resin is applied, as a phenol resin type used in a laminated board such as a modified phenol resin modified with a flexible agent such as a phenol resin and vegetable oil, an epoxy resin, Epibis type epoxy resin, phenol novolac type epoxy resin, polyfunctional type epoxy resin, etc. (these epoxy resins may be brominated), dicyandiamide, novolac type phenol resin, bisphenol A novolac type phenol resin as curing agent There are epoxy resin-based materials used for laminates such as epoxy resin-based materials to which an accelerator is added, and the application is not particularly limited.
[0020]
The substrate to be used when applied to the laminate is not particularly limited, and it is possible to use a substrate such as a paper substrate such as craft paper or linter paper, or a glass substrate such as glass fiber woven fabric or glass fiber nonwoven fabric. Is possible.
[0021]
【Example】
Reference example 1
(1) Synthesis of phosphorus-containing triazine-modified phenolic resin (T1) A thermometer, a condenser tube, and a four-necked separable flask with a stirrer were mixed with 940 g of phenol, 44 g of melamine, 98 g of 92% paraformaldehyde, and 0.8 g of triethylamine. And reacted at 80 ° C. for 3 hours. Furthermore, the temperature was raised to the reflux temperature and the reaction was carried out at the reflux temperature for 10 hours. Thereafter, vacuum concentration was performed at a flask internal temperature of 170 ° C. and a degree of vacuum of 700 mmHg until no concentrate was produced. Next, after releasing the vacuum, 1000 g of triphenyl phosphate and 1 g of potassium carbonate were added and reacted for 10 hours at a temperature in the flask of 180 ° C. and a reduced pressure of 700 mmHg to obtain a phosphorus-containing triazine-modified phenol resin (T1). Unreacted phenol was 2%.
[0022]
(2) Synthesis of a phenolic resin (A1) for laminated plate (A1), blending 720 g of tung oil, 580 g of m-cresol, and 0.74 g of paratoluenesulfonic acid into a 4-neck separable flask equipped with a condenser and a stirrer, The reaction was carried out at 1 ° C. for 1 hour and cooled. Subsequently, 500 g of phenol, 420 g of 92% paraformaldehyde, and 35 g of 25% aqueous ammonia were added, and the reaction was allowed to proceed at normal pressure at 80 ° C. until the gel time on a 160 ° C. hot plate reached 6 minutes. Furthermore, it concentrated under reduced pressure at 80 degrees C or less until the gel time became 3 minutes. Thereafter, a mixed solvent of methanol and toluene was added so that the resin content was 50% to obtain a phenolic resin for laminate (A1).
[0023]
(3) Production of Laminate (L1) Phenol resin (A1) for laminate and phosphorus-containing triazine-modified phenol resin (T1) are mixed so that A1 (solid weight) / T1 is 80/20. The varnish was adjusted. This was impregnated and coated on a kraft paper having a basis weight of 135 g / m 2 so that the amount of the adhered resin was 50% by weight and then dried to obtain a coated paper. One sheet of copper foil with adhesive and 8 sheets of this coated paper were overlapped so that the copper foil would be the outermost layer and heated and pressed to obtain a 1.6 mm thick paper base laminate (L1).
[0024]
Example 1
(1) Synthesis of phosphorus-containing triazine-modified phenol resin (T2) A 4-meter separable flask equipped with a thermometer, a condenser tube, and a stirrer was mixed with 900 g of phenol, 90 g of benzoguanamine, 90 g of melamine, 156 g of 92% paraformaldehyde, and 21 g of oxalic acid. The mixture was heated up to the reflux temperature and reacted at the reflux temperature for 10 hours, and then heated up to 160 ° C. at a reduced pressure of 700 mmHg and concentrated. After release under reduced pressure, 1000 g of tricresyl phosphate and 1 g of sodium carbonate were added, the temperature in the flask was raised to 180 ° C., and the reaction was allowed to proceed for 10 hours at a reduced pressure of 700 mmHg. This was carried out for a time to obtain a phosphorus-containing triazine-modified phenol resin (T2). The total amount of residual phenol and residual cresol of T2 was 4%.
[0025]
(2) Mixing cooling pipe of epoxy resin (A2) for laminated plate, 4-neck separable flask with stirrer 570 g of epibis type epoxy resin (trade name Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) as epoxy resin, curing An epoxy resin composition (A2) for laminates was obtained by blending 315 g of novolak type phenol resin (trade name HP850N, Hitachi Chemical Co., Ltd.) as an agent, 8.5 g of imidazole as an accelerator, and 500 g of methyl ethyl ketone as a solvent.
[0026]
(3) Production of Laminate (L2) Phosphorus-containing triazine-modified phenol resin (T2) is mixed with epoxy resin composition (A2) for laminate so that the solid weight ratio is A2 / T2 = 80/20. The varnish was adjusted. This was impregnated and coated on a MIL7628 type glass woven fabric so that the amount of the adhered resin was 42% by weight and then dried to obtain a coated fabric. The eight coated cloths were combined and heated and pressed to obtain a glass substrate laminate (L2) having a thickness of 1.6 mm.
[0027]
Comparative Example 1 [Production of Laminated Plate (L3)]
The phenolic resin for laminate (A1) was mixed so that A1 (solid weight) / triphenyl phosphate = 80/20 to prepare a resin varnish. This was impregnated and coated on a kraft paper having a basis weight of 135 g / m 2 so that the amount of the adhered resin was 50% by weight and then dried to obtain a coated paper. One copper foil with adhesive and 8 coated papers were combined and heated and pressurized to obtain a paper base laminate (L3) having a thickness of 1.6 mm.
[0028]
Comparative Example 2 [Production of Laminated Plate (L4)]
The resin varnish was prepared by mixing tricresyl phosphate with the epoxy resin (A2) for laminate so that the solid weight ratio was A2 / tricresyl phosphate = 80/20. This was impregnated and coated on a MIL7628 type glass woven fabric so that the amount of the adhered resin was 42% by weight and then dried to obtain a coated fabric. The eight coated cloths were combined and heated and pressed to obtain a glass substrate laminate (L4) having a thickness of 1.6 mm.
[0029]
Table 1 shows the characteristics of the obtained laminate.
[Table 1]
Solvent resistance: A laminate from which the copper foil had been completely removed was cut into 20 mm × 50 mm to obtain test pieces. After boiling this test piece with acetone for 10 minutes, the appearance of the test piece was evaluated. “O” indicates that there is no abnormality in the appearance, “Δ” indicates that there is a slight abnormality in the end or the surface, and “X” indicates that there is an abnormality in the end or the surface.
Heat resistance: In the case of a paper base laminate, the laminate with copper foil was cut into 25 mm x 25 mm to obtain test pieces. This test piece was floated on a solder bath at 260 ° C., and the evaluation time of heat resistance (solder heat resistance) was determined by the time (seconds) until swelling. In the case of a glass substrate laminate, the glass transition temperature (Tg) of the laminate was used as the heat resistance evaluation standard.
[0031]
【The invention's effect】
By using the phosphorus-containing triazine-modified phenol resin according to the present invention, a laminate having excellent solvent resistance and heat resistance can be obtained.
Claims (5)
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