CN106626683A - 一种无卤、无磷、环保阻燃型纸基覆铜板的制备方法 - Google Patents

一种无卤、无磷、环保阻燃型纸基覆铜板的制备方法 Download PDF

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CN106626683A
CN106626683A CN201611057436.XA CN201611057436A CN106626683A CN 106626683 A CN106626683 A CN 106626683A CN 201611057436 A CN201611057436 A CN 201611057436A CN 106626683 A CN106626683 A CN 106626683A
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halogen
nitrogen
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CN106626683B (zh
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陈长浩
李宝东
朱义刚
秦伟峰
陈晓鹏
王卫兴
杨永亮
姜晓亮
朱琪琪
李洪学
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SHANDONG JINBAO ELECTRONICS CO Ltd
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Abstract

本发明属于覆铜板生产技术领域，尤其涉及一种无卤、无磷、环保阻燃型纸基覆铜板的制备方法。本发明利用全新的含氮酚醛树脂，协同其他填料，保证覆铜板的阻燃性、加工性及其它基本性能。本发明制得的覆铜板卤素含量氯≤0.09％、溴≤0.09％或氯加溴总量≤0.15％，满足无卤要求，并且不添加任何含磷化合物，磷含量≤0.1％。本发明制得的覆铜板阻燃性达到FV0级要求，做到无卤、无磷、环保，降低成本，耐热性大大提高。

Description

一种无卤、无磷、环保阻燃型纸基覆铜板的制备方法
技术领域
本发明属于覆铜板生产技术领域，尤其涉及一种无卤、无磷、环保阻燃型纸基覆铜板的制备方法。
背景技术
覆铜板广泛用于制造各类家用电器、电子信息产品及工业电子产品所用的印制电路板(简称PCB)。它作为印制电路板的基板材料，起着承载装联电子元器件、形成导电线路图形及在层间和线路间绝缘的三大功能，是一种重要的电子基础材料。
覆铜板的阻燃性是电子产品重要的安全性能之一。卤素类阻燃材料(含Cl、Br)以其经济性与可靠性，在印制电路基材产业中已应用多年，然而，随着全球性环境保护呼声的日益高涨，卤素类阻燃材料的环境负荷及对人体健康的影响正密切受到关注，已有许多国家的组织和机构相继在含卤产品的燃烧产物中检测出二噁英(Dioxin)、二苯并呋喃(Dibenzofuran)等致癌物质。含卤产品在燃烧过程中发烟量很大，会释放出剧毒物质卤化氢，严重威胁人体健康。因此研发和应用无卤型阻燃材料，生产环保型印制电路基材，已成为近年来覆铜板技术发展的新趋势。
目前无卤化覆铜板是利用氮磷协同阻燃，并添加无机填料，达到阻燃FV0级。但是，含磷化合物价格高，使用含磷化合物制造覆铜板易受潮，影响耐热性；氮磷协同阻燃，燃烧物含有大量含磷物质，对环境造成污染。
发明内容
本发明针对上述现有技术存在的不足，提供一种无卤、无磷、环保阻燃型纸基覆铜板的制备方法。
本发明解决上述技术问题的技术方案如下：一种无卤、无磷、环保阻燃型纸基覆铜板的制备方法，步骤如下：
(1)制备含氮酚醛树脂A：将20-50份尿素、140-260份三聚氰胺和300-500份浓度为32-42wt％的甲醛水溶液依次投入反应釜中，再加入1-3份浓度为25wt％的氢氧化钠溶液，在90-100℃条件下反应50-70min，继续加入70-100份浓度为98％的甲醇，降温至15-45℃，制得含氮酚醛树脂A；
(2)制备含氮酚醛树脂B：将100-150份苯酚、200-300份2,4-二氨基-6-苯基-1,3,5-三嗪和300-500份浓度为32-42wt％的甲醛水溶液投入反应釜，再加入10份浓度为10-15％的草酸水溶液，在90-100℃条件下反应30-50min，再加入300-600份环氧大豆油和2份胺类催化剂，在120-160℃条件下反应60-90min，减压脱水后，在155-165℃下测试胶化时间，控制胶化时间为110-160s，加入300-600份溶剂，制得含氮酚醛树脂B；
(3)制备漂白木浆纸第一次浸胶用树脂乳液：将30-50份步骤(1)制得的含氮酚醛树脂A、20-30份甲醇、20-40份软水和10-15份丙酮投入反应釜中，在10-45℃条件下搅拌均匀；
(4)制备漂白木浆纸第二次浸胶用树脂乳液：将5-10份无卤环氧树脂、60-80份步骤(2)制得的含氮酚醛树脂B、5-10份氢氧化铝、8-15份氰尿酸三聚氰胺和10-20份甲醇投入反应釜中，在10-45℃条件下搅拌均匀；
(5)取漂白木浆纸浸渍在步骤(3)的树脂乳液中，控制其含胶量为15-30％，自然晾干后，再浸渍在步骤(4)的树脂乳液中，在160℃条件下烘干1min，控制含胶量为50±3％，流动度为10-16％，制得漂白木浆纸浸胶料片；
(6)取若干张步骤(5)制得的漂白木浆纸浸胶料片叠加在一起，在其双面各覆有一张铜箔或者在单面覆有一张铜箔，在40-50MPa、150-160℃条件下热压100-130min，冷却，制得覆铜板。
本发明的有益效果是：本发明利用全新的含氮酚醛树脂，协同其他填料，保证覆铜板的阻燃性、加工性及其它基本性能。本发明制得的覆铜板卤素含量氯≤0.09％、溴≤0.09％或氯加溴总量≤0.15％，满足无卤要求，并且不添加任何含磷化合物，磷含量≤0.1％。本发明制得的覆铜板阻燃性达到FV0级要求，做到无卤、无磷、环保，降低成本，耐热性大大提高。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，步骤(1)制得的含氮酚醛树脂A的含氮量为20-35％。
进一步，步骤(2)中所述的胺类催化剂为氨水、三乙胺、三乙醇胺或苄胺中的一种或两种以上混合。
进一步，步骤(2)中所述的溶剂为甲醇、乙醇、丙酮、丁酮或水中的一种或两种以上混合。
进一步，步骤(4)中所述的无卤环氧树脂的环氧当量为200-300g/eq。
更进一步，步骤(4)中所述的无卤环氧树脂双官能、多官能酚醛型环氧树脂。
进一步，步骤(5)中所述的含胶量是指浸胶用树脂乳液纯固体占浸胶料片重量的百分比；所述的流动度是指浸胶用树脂乳液在50±5kg/cm2的压力、155±2℃下流出的重量占浸胶用树脂乳液总重量的百分比。
具体实施方式
以下结合实例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
一种无卤、无磷、环保阻燃型纸基覆铜板的制备方法，步骤如下：
(1)制备含氮酚醛树脂A：将20份尿素、140份三聚氰胺和300份浓度为37wt％的甲醛水溶液依次投入反应釜中，再加入1份浓度为25wt％的氢氧化钠溶液，在90℃条件下反应50min，继续加入70份浓度为98％的甲醇，降温至45℃，制得含氮量为20％的含氮酚醛树脂A；
(2)制备含氮酚醛树脂B：将100份苯酚、200份2,4-二氨基-6-苯基-1,3,5-三嗪和300份浓度为37wt％的甲醛水溶液投入反应釜，再加入10份浓度为10％的草酸水溶液，在90℃条件下反应30min，再加入300份环氧大豆油和2份氨水，氨水浓度为25wt％，在120℃条件下反应60min，减压脱水后，在155℃下测试胶化时间，控制胶化时间为110s，加入300份甲醇，制得含氮酚醛树脂B；
(3)制备漂白木浆纸第一次浸胶用树脂乳液：将30份步骤(1)制得的含氮酚醛树脂A、20份甲醇、20份软水和10份丙酮投入反应釜中，在45℃条件下搅拌均匀；
(4)制备漂白木浆纸第二次浸胶用树脂乳液：将5份酚醛环氧树脂、60份步骤(2)制得的含氮酚醛树脂B、5份氢氧化铝、8份氰尿酸三聚氰胺和10份甲醇投入反应釜中，在45℃℃条件下搅拌均匀；
(5)取漂白木浆纸浸渍在步骤(3)的树脂乳液中，控制其含胶量为15-30％，自然晾干后，再浸渍在步骤(4)的树脂乳液中，在160℃条件下烘干1min，控制含胶量为50±3％，流动度为10％，制得漂白木浆纸浸胶料片；
(6)取若干张步骤(5)制得的漂白木浆纸浸胶料片叠加在一起，在其双面各覆有一张铜箔，在40MPa、150℃条件下热压100min，冷却，制得覆铜板。
实施例2
一种无卤、无磷、环保阻燃型纸基覆铜板的制备方法，步骤如下：
(1)制备含氮酚醛树脂A：将50份尿素、260份三聚氰胺和500份浓度为37wt％的甲醛水溶液依次投入反应釜中，再加入3份浓度为25wt％的氢氧化钠溶液，在100℃条件下反应70min，继续加入100份浓度为98％的甲醇，降温至15℃，制得含氮量为35％的含氮酚醛树脂A；
(2)制备含氮酚醛树脂B：将150份苯酚、300份2,4-二氨基-6-苯基-1,3,5-三嗪和500份浓度为37wt％的甲醛水溶液投入反应釜，再加入10份浓度为15％的草酸水溶液，在100℃条件下反应50min，再加入600份环氧大豆油和2份三乙胺，在160℃条件下反应90min，减压脱水后，在165℃下测试胶化时间，控制胶化时间为160s，加入600份丙酮，制得含氮酚醛树脂B；
(3)制备漂白木浆纸第一次浸胶用树脂乳液：将50份步骤(1)制得的含氮酚醛树脂A、30份甲醇、40份软水和15份丙酮投入反应釜中，在10℃条件下搅拌均匀；
(4)制备漂白木浆纸第二次浸胶用树脂乳液：将10份酚醛环氧树脂、80份步骤(2)制得的含氮酚醛树脂B、10份氢氧化铝、15份氰尿酸三聚氰胺和20份甲醇投入反应釜中，在10℃条件下搅拌均匀；
(5)取漂白木浆纸浸渍在步骤(3)的树脂乳液中，控制其含胶量为15-30％，自然晾干后，再浸渍在步骤(4)的树脂乳液中，在160℃条件下烘干1min，控制含胶量为50±3％，流动度为16％，制得漂白木浆纸浸胶料片；
(6)取若干张步骤(5)制得的漂白木浆纸浸胶料片叠加在一起，在其单面覆有一张铜箔，在50MPa、160℃条件下热压130min，冷却，制得覆铜板。
对比例1
一种纸基覆铜板的制备方法，步骤如下：
(1)制备漂白木浆纸用树脂乳液：将10份含磷环氧树脂、20份含氮酚醛树脂、50份桐油改性酚醛树脂、10份磷酸三苯酯和10份丙酮加入反应釜混合，搅拌均匀；
(2)将步骤(1)的树脂乳液涂覆在漂白木浆纸上，在160℃条件下烘干1min，控制含胶量为48±1％，流动度为9±1％，制得漂白木浆纸浸胶料片；
(3)取5张步骤(2)制得的漂白木浆纸浸胶料片叠加在一起，然后在双面各覆有一张铜箔，在40MPa、150℃条件下热压100min，冷却，制得覆铜板。
对比例2
一种纸基覆铜板的制备方法，步骤如下：
(1)制备漂白木浆纸用树脂乳液：将10份无卤环氧树脂、80份含氮酚醛树脂、10份氢氧化铝、15份氰尿酸三聚氰胺和20份甲醇加入反应釜，搅拌均匀；
(2)将步骤(1)的树脂乳液涂覆在漂白木浆纸上，在160℃条件下烘干1min，控制含胶量为48±1％，流动度为9±1％，制得漂白木浆纸浸胶料片；
(3)取8张步骤(2)制得的漂白木浆纸浸胶料片叠加在一起，然后在单面覆有一张铜箔，在40MPa、150℃条件下热压100min，冷却，制得覆铜板。
表1为实施例1、实施例2和对比例1、对比例2所得样品的各项性能数据对照表。
表1
由表1可以看出，本发明制得的纸基覆铜板具备较好的剥离强度、耐浸焊、阻燃性和冲孔性能，卤素和磷含量极低，减少对环境的污染。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (7)

1.一种无卤、无磷、环保阻燃型纸基覆铜板的制备方法，其特征在于，步骤如下：
(1)制备含氮酚醛树脂A：将20-50份尿素、140-260份三聚氰胺和300-500份浓度为32-42wt％的甲醛水溶液依次投入反应釜中，再加入1-3份浓度为25wt％的氢氧化钠溶液，在90-100℃条件下反应50-70min，继续加入70-100份浓度为98％的甲醇，降温至15-45℃，制得含氮酚醛树脂A；
(2)制备含氮酚醛树脂B：将100-150份苯酚、200-300份2,4-二氨基-6-苯基-1,3,5-三嗪和300-500份浓度为32-42wt％的甲醛水溶液投入反应釜，再加入10份浓度为10-15％的草酸水溶液，在90-100℃条件下反应30-50min，再加入300-600份环氧大豆油和2份胺类催化剂，在120-160℃条件下反应60-90min，减压脱水后，在155-165℃下测试胶化时间，控制胶化时间为110-160s，加入300-600份溶剂，制得含氮酚醛树脂B；
(3)制备漂白木浆纸第一次浸胶用树脂乳液：将30-50份步骤(1)制得的含氮酚醛树脂A、20-30份甲醇、20-40份软水和10-15份丙酮投入反应釜中，在10-45℃条件下搅拌均匀；
(4)制备漂白木浆纸第二次浸胶用树脂乳液：将5-10份无卤环氧树脂、60-80份步骤(2)制得的含氮酚醛树脂B、5-10份氢氧化铝、8-15份氰尿酸三聚氰胺和10-20份甲醇投入反应釜中，在10-45℃条件下搅拌均匀；
(5)取漂白木浆纸浸渍在步骤(3)的树脂乳液中，控制其含胶量为15-30％，自然晾干后，再浸渍在步骤(4)的树脂乳液中，在160℃条件下烘干1min，控制含胶量为50±3％，流动度为10-16％，制得漂白木浆纸浸胶料片；
(6)取若干张步骤(5)制得的漂白木浆纸浸胶料片叠加在一起，在其双面各覆有一张铜箔或者在单面覆有一张铜箔，在40-50MPa、150-160℃条件下热压100-130min，冷却，制得覆铜板。
2.根据权利要求1所述的制备方法，其特征在于，步骤(1)制得的含氮酚醛树脂A的含氮量为20-35％。
3.根据权利要求1所述的制备方法，其特征在于，步骤(2)中所述的胺类催化剂为氨水、三乙胺、三乙醇胺或苄胺中的一种或两种以上混合。
4.根据权利要求1所述的制备方法，其特征在于，步骤(2)中所述的溶剂为甲醇、乙醇、丙酮、丁酮或水中的一种或两种以上混合。
5.根据权利要求1所述的制备方法，其特征在于，步骤(4)中所述的无卤环氧树脂的环氧当量为200-300g/eq。
6.根据权利要求1或5所述的制备方法，其特征在于，步骤(4)中所述的无卤环氧树脂为双官能、多官能酚醛型环氧树脂。
7.根据权利要求1所述的制备方法，其特征在于，步骤(5)中所述的含胶量是指浸胶用树脂乳液纯固体占浸胶料片重量的百分比；所述的流动度是指浸胶用树脂乳液在50±5kg/cm2的压力、155±2℃下流出的重量占浸胶用树脂乳液总重量的百分比。
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