CN103492449A - 环氧树脂及其制备方法及环氧树脂组合物 - Google Patents

环氧树脂及其制备方法及环氧树脂组合物 Download PDF

Info

Publication number
CN103492449A
CN103492449A CN201380000304.1A CN201380000304A CN103492449A CN 103492449 A CN103492449 A CN 103492449A CN 201380000304 A CN201380000304 A CN 201380000304A CN 103492449 A CN103492449 A CN 103492449A
Authority
CN
China
Prior art keywords
epoxy resin
resin
chemical formula
drops
phenol
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
Application number
CN201380000304.1A
Other languages
English (en)
Other versions
CN103492449B (zh
Inventor
李时畅
朴景浩
申泰圭
李镇洙
黄玄湊
禹弦律
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KOODTOH CHEMICALS CO Ltd
Kukdo Chemical Co Ltd
Original Assignee
KOODTOH CHEMICALS CO Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by KOODTOH CHEMICALS CO Ltd filed Critical KOODTOH CHEMICALS CO Ltd
Publication of CN103492449A publication Critical patent/CN103492449A/zh
Application granted granted Critical
Publication of CN103492449B publication Critical patent/CN103492449B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
    • C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
    • C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
    • C08G16/0225—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
    • C08G16/04—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/36—Chemically modified polycondensates by etherifying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

本发明提供化学式1的环氧树脂模塑料用自熄性环氧树脂。确认到，本发明的环氧树脂(组合物)即使不使用卤素类阻燃剂或磷类阻燃剂也呈现优秀的阻燃性，并且发现与现在最为商用化的日本化学药品公司的NC3000相比阻燃性为同等以上、收缩率也较低而尺寸稳定性优秀、具有更低的弯曲模数的同时玻璃化转变温度更高的环氧树脂模塑料组合物用环氧树脂是具有最理想的物性平衡性的高档级别的环氧树脂模塑料用自熄性环氧树脂。

Description

环氧树脂及其制备方法及环氧树脂组合物
技术领域
本发明涉及一种环氧树脂模塑料(EMC)用自熄性环氧树脂及其制备方法以及环氧树脂模塑料用环氧树脂组合物。更详细地，提供不使用溴类、磷类等的阻燃剂而在环氧树脂模塑料中具有自熄性的高档(High End)级别的环氧树脂模塑料用自熄性环氧树脂及其制备方法以及环氧树脂模塑料用环氧树脂组合物。
背景技术
环氧树脂模塑料(EMC，Epoxy Molding Compound)作为使用二氧化硅、环氧树脂、苯酚树脂、碳黑、阻燃剂等10种原料的复合材料，主要用途为，作为用于防止晶体管、二极管、微处理器、半导体存储器等受到热量、水分、冲击等的影响而进行密封的材料的半导体封装材料(密封材料)来使用。
环氧树脂模塑料虽然与半导体的价格相比，其比重小，但是由于是用于保护半导体元器件的结构材料，因此对半导体的功能起到非常重要的影响。尤其，环氧树脂模塑料的混合技术属于决定半导体的质量的核心技术。
可以将高档级别的环氧树脂模塑料的设计定义为平衡工程。由于环氧树脂模塑料要满足总是相克的许多要求特性，例如高玻璃化转变温度Vs低弯曲模量，因此需要高难度的技术。能够最有效地满足相克的要求特性的方法是使用物性平衡性优秀的高性能的环氧树脂。即，在开发高档级别的环氧树脂模塑料方面，高性能的环氧树脂是代表性的核心技术。
在本发明中提出的新颖的环氧树脂可以确保与作为现在商业上最常使用的半导体密封材料的联苯酚醛型环氧树脂的日本化学药品公司的NC3000相比，类似或更优秀的机械特性和可靠性。
另一方面，韩国专利第946206号(苯酚类聚合物及其制备方法以及用途)中提出一种作为用于半导体密封材料的固化剂的新颖结构的苯酚类聚合物，但是在实施例中将上述NC3000作为环氧树脂来使用。
发明内容
本发明起因于发现在对现有技术(韩国专利第946206号)中提出的苯酚类聚合物进行环氧化的情况下，能够提供优秀的物性的环氧树脂模塑料(EMC)用自熄性环氧树脂。
因此，本发明的目的在于，提供下述化学式1的环氧树脂模塑料用自熄性环氧树脂。
化学式1
Figure BDA00003272726200021
R1、R3、R4为H或CH3或烷基(Alkyl group)，
R2为
Figure BDA00003272726200022
(联苯基)或
Figure BDA00003272726200023
(苄基)
其中，n=1～100的自然数。
并且，本发明提供利用上述化学式1的树脂的环氧树脂模塑料用环氧树脂组合物。
确认到，本发明的环氧树脂(组合物)即使不使用卤素类阻燃剂或磷类阻燃剂也呈现优秀的阻燃性，并且，发现了阻燃性相比现在最商用化的日本化学药品公司的NC3000为同等以上、且因收缩率低而尺寸稳定性优秀、具有更低的弯曲模数的同时玻璃化转变温度则更高的环氧树脂模塑料组合物用环氧树脂是具有最理想的物性平衡性的高档级别的环氧树脂模塑料用自熄性环氧树脂。
为了解决上述问题，本发明者发现了如果将化学式1的环氧树脂作为环氧树脂模塑料组合物来利用，则为了环保而不使用卤素类阻燃剂和磷类阻燃剂，也可以在环氧树脂模塑料中获得具有自熄性且还具有优秀的物性平衡性(balance)的高档级别(高增值)的环氧树脂。
本发明的下述化学式1的树脂是分别对苯酚类和二甲基联苯类及苯甲醛或4-苯基苯甲醛进行反应来进行酚醛化之后，分别对此进行环氧化的高增值用自熄性环氧树脂。
化学式1
Figure BDA00003272726200031
R1、R3、R4为H或CH3或烷基，
R2为
Figure BDA00003272726200032
(联苯基)或
Figure BDA00003272726200033
(苄基)，
其中，n=1～100的自然数。
本发明的效果如下。
1.将本发明的环氧树脂使用于环氧树脂模塑料组合物的情况下，阻燃性呈现出V-O等级，由此可知即使不使用卤素类阻燃剂或磷类阻燃剂也呈现出优秀的阻燃性。并且确认到，与现在商用化的作为日本化学药品公司的NC3000相比也呈现同等以上的阻燃性，并且可以了解到其他物性平衡性也呈现出同等以上的性能。
2.可知，由于收缩率低，因而不仅具有优秀的尺寸稳定性，而且收缩率低于现有商用产品NC3000。
3.一般来说，如果玻璃化转变温度(Tg)高，则存在模数也一同提高的倾向性，但在本发明的物质的情况下(实施例2和实施例5)，相比现有商用产品NC3000(比较例1)，呈现出高玻璃化转变温度的同时模数相似或更低，由此可知，这对于环氧树脂模塑料的物性而言，具有非常理想的物性平衡性。
具体实施方式
本发明的环氧树脂可通过如下过程制备而得：将对苯酚类和二甲基联苯化合物、芳香醛进行反应而得的苯酚类聚合物制备成环氧树脂并将此制备成环氧组合物。
更仔细地，将苯酚和4,4’-二甲氧基甲基联苯(4，4’-(bismethoxymethyl biphenyl))及4-苯基苯甲醛或苯甲醛制备成酚醛树脂之后，使环氧氯丙烷与酚醛树脂的羟基进行反应来制备环氧树脂。
以下，更加具体地说明本发明的具体实施方式。
实施例1利用4-苯基苯甲醛的酚醛树脂的制备
在附有搅拌机、冷却机的烧瓶放入212g的4-苯基苯甲醛(4-phenylbenzaldehyde)、550g的苯酚、242g的4,4’-二甲氧基甲基联苯(BMMB，4，4’-Bis[methoxy-methylbiphenyl])、58g的纯化水(PPW，purified process water)并升温至90℃来进行溶解。作为催化剂投入1.41g的对甲苯磺酸一水合物(PTSA，para toluenesulfonicacid monohydrate)进行3小时反应之后，脱水至115℃之后，将苯酚回收至190℃×5torr。接着，滴下20g的纯化水来使残余苯酚含量最小化，从而合成了软化点为99℃、分子量为787、粘度为390cps(150℃)的化学式2的树脂。(第一步骤方法)
在附有搅拌机、冷却机的烧瓶投入212g的4-苯基苯甲醛、550g的苯酚、58g的纯化水并升温至90℃来进行溶解。作为催化剂投入1.41g的对甲苯磺酸一水合物进行1小时反应之后，投入242g的作为第二原料的4,4’-二甲氧基甲基联苯并进行3小时反应后，脱水至115℃后，将苯酚回收至190℃×5torr。接着，滴下20g的纯化水来使残余苯酚含量最小化，从而合成了软化点为99℃、分子量为787、粘度为390cps(150℃)的化学式2的树脂(第二步骤方法)。
化学式2
Figure BDA00003272726200051
其中，n=1～100的自然数。
实施例2酚醛环氧树脂的制备
在附有搅拌机、冷却机的烧瓶投入600g的化学式2的树脂和949.6g的环氧氯丙烷(Epichlorohydrin)并进行溶解之后，将150g的50%NaOH水溶液催化剂滴下4小时进行反应之后，回收剩余的环氧氯丙烷。在合成的树脂投入750g的甲基异丁基酮(Methylisobutyl ketone)、264g的纯化水来进行分液、水洗而除去生成的盐之后回收溶剂，从而合成了当量为270.1g/eq、氯浓度为280ppm、软化点为60.7度(B&R)的化学式3。
化学式3
Figure BDA00003272726200061
其中，n=1～100的自然数。
实施例3酚醛环氧树脂组合物的制备
混合作为环氧树脂的在实施例2中制备的化学式3的环氧树脂(100g)、作为固化剂的新酚(xylok)树脂(64.79g)、作为催化剂的三苯磷(1.5g)及作为填充剂(filler)的二氧化硅(1210g)来制备了环氧树脂组合物。
实施例4利用苯甲醛的酚醛树脂的制备
在附有搅拌机、冷却机的烧瓶投入182g的苯甲醛(benzaldehyde)、470g的苯酚、231g的4,4’-二甲氧基甲基联苯、47g的纯化水并升温至90℃来进行溶解。作为催化剂投入1.41g的对甲苯磺酸一水合物进行3小时反应后，脱水至115℃之后，将苯酚回收至190℃×5torr。接着，滴下20g的纯化水来使残余苯酚含量最小化，从而合成了软化点为92℃、分子量为859、粘度为67cps(150℃)的化学式4的树脂。(第一步骤方法)
在附有搅拌机、冷却机的烧瓶投入182g的苯甲醛、470g的苯酚、47g的纯化水并升温至90℃来进行溶解。作为催化剂投入1.41g的对甲苯磺酸一水合物来进行1小时反应后，投入231g的作为第二原料的4,4’-二甲氧基甲基联苯并进行3小时反应后，进行脱水至115℃之后，将苯酚回收至190℃×5torr。接着，滴下20g的纯化水来使残余苯酚含量最小化，从而合成了软化点为92℃、分子量为859、粘度为67cps(150℃)的化学式4的树脂。(第二步骤方法)
化学式4
Figure BDA00003272726200071
其中，n=1～100的自然数。
实施例5酚醛环氧树脂的制备
在附有搅拌机、冷却机的烧瓶投入208g的化学式4的树脂和412g的环氧氯丙烷来进行溶解之后，将80g的50%NaOH水溶液催化剂滴下4小时进行反应之后回收剩余的环氧氯丙烷。在合成的树脂投入528g的甲基异丁基酮、264g的纯化水并进行分液、水洗而除去生成的盐之后回收溶剂，从而合成当量为237.8g/eq、氯浓度为87ppm、软化点为60度(B&R)的化学式5。
化学式5
Figure BDA00003272726200072
其中，n=1～100的自然数。
实施例6酚醛环氧树脂组合物的制备
混合作为环氧树脂的在实施例5中制备的化学式5的环氧树脂(100g)、作为固化剂的新酚树脂(73.6g)、作为催化剂的三苯磷(1.5g)及作为填充剂(filler)的二氧化硅(1283g)来制备了环氧树脂组合物。
比较例1
除了作为自熄性环氧树脂使用作为最商用化的树脂的NC-3000(日本化学药品公司)以外，通过与实施例3相同的方法制备了环氧树脂组合物。
比较例2
除了作为环氧树脂使用作为普通类型的邻甲酚酚醛环氧树脂的YDCN-500-4P(韩国国都化学有限公司产品)来代替自熄性环氧树脂以外，通过与实施例3相同的方法制备了环氧树脂组合物。
在表1中表示了通过上述方法制备的环氧树脂(使用通过第二步骤方法制备的树脂)及在比较例中使用的环氧树脂的普通特性。
表1
通过实施例2和实施例5获得的环氧树脂的特性及在比较例1和比较例2中使用的环氧树脂的特性
Figure BDA00003272726200081
环氧树脂组合物的成分和含量见表2。
表2
Figure BDA00003272726200091
环氧树脂模塑料组合物的原料物质成分及含量
胶化时间(Gel Time)的测定
为了评价环氧树脂组合物的反应性而测定了胶化时间等。将脱离干燥状态的树脂并制备成粉末(powder)形态的1g的试样放在175℃的加热板(hot plate)上测定时间，即测定利用牙签搅拌并抬起时树脂像纱线一样延伸的时间。
阻燃性的测定
为了测定环氧树脂组合物的阻燃性，根据UL-94标准利用垂直燃烧法来评价了阻燃性。上述阻燃性的测定，用火焰烧焦试样10秒钟之后，除去火焰，并确认了在几秒钟内熄灭，如果在10秒钟内熄灭则呈现出UL V-0等级的阻燃性。
收缩率的测定
准备模具和试验片，并根据用卡尺测定的环氧树脂模塑料的收缩率测定方法来测定了模具和试验片的长度。
耐热性的测定
在90℃下维持2小时环氧树脂组合物之后，在150℃下维持4小时来进行固化后，通过差示扫描量热法(DSC，differentialscanning calorimetry)分析来测定了玻璃化转变温度(Tg)。
弯曲强度及弯曲模量
准备试验片，以微米测定了试验片的宽度和厚度，并通过利用U.T.M试验机的方法测定了弯曲强度及弯曲模量。
将以上的结果表示在表3
表3
Figure BDA00003272726200101
如表3所示，在使用本发明的环氧树脂的情况下，可以制备出即使不使用卤素类、磷类阻燃剂也具有优秀的阻燃性，尺寸稳定性优秀且物性平衡性也优秀的环氧树脂模塑料。

Claims (4)

1.一种环氧树脂，其特征在于，由下述化学式1表示：
化学式1
R1、R3、R4为H或CH3或烷基，
R2为(联苯基)或(苄基)，
其中，n=1～100的自然数。
2.一种制备环氧树脂的方法，其特征在于，包括如下步骤：
(1)在附有搅拌机、冷却机的烧瓶放入212g的4-苯基苯甲醛、550g的苯酚、242g的4,4’-二甲氧基甲基联苯、58g的纯化水并升温至90℃来进行溶解后，作为催化剂投入1.41g的对甲苯磺酸一水合物进行3小时反应后，进行脱水至115℃后，将苯酚回收至190℃×5torr之后，滴下20g的纯化水来使残余苯酚含量最小化，从而合成化学式2的树脂的步骤，或者
在附有搅拌机、冷却机的烧瓶放入212g的4-苯基苯甲醛、550g的苯酚58g的纯化水并升温至90℃来进行溶解之后，作为催化剂投入1.41g的对甲苯磺酸一水合物进行1小时反应后，投入242g的作为第二原料的4,4’-二甲氧基甲基联苯并进行3小时反应后进行脱水至115℃之后，将苯酚回收至190℃×5torr之后，滴下20g的纯化水来使残余苯酚含量最小化，从而合成化学式2的树脂的步骤，
化学式2
Figure FDA00003272726100022
其中，n=1～100的自然数；
(2)在附有搅拌机、冷却机的烧瓶投入600g的化学式2的树脂和949.6g的环氧氯丙烷进行溶解之后，将150g的50%NaOH水溶液催化剂滴下4小时进行反应后回收剩余的环氧氯丙烷之后，在合成的树脂投入750g的甲基异丁基酮、264g的纯化水来进行分液、水洗而除去生成的盐之后回收溶剂，从而制备化学式3的环氧树脂的步骤，
化学式3
其中，n=1～100的自然数。
3.一种合成环氧树脂的方法，其特征在于，包括如下步骤：
1)在附有搅拌机、冷却机的烧瓶投入182g的苯甲醛、420g(5mole)的苯酚、231g的4,4’-二甲氧基甲基联苯、47g纯化水并升温至90℃来进行溶解之后，作为催化剂投入1.41g的对甲苯磺酸一水合物来进行3小时反应后，进行脱水至115℃后，将苯酚回收至190℃×5torr之后，滴下20g的纯化水来使残余苯酚含量最小化，从而制备化学式4的树脂的步骤，或者
在附有冷却机的烧瓶投入182g的苯甲醛、470g的苯酚、47g的纯化水并升温至90℃来进行溶解之后，作为催化剂投入1.41g的对甲苯磺酸一水合物来进行1小时反应后，投入231g的作为第二原料的4,4’-二甲氧基甲基联苯并进行3小时后，进行脱水至115℃后，将苯酚回收至190℃×5torr之后，滴下20g的纯化水来使残余苯酚含量最小化，从而合成化学式4的树脂的步骤，
化学式4
其中，n=1～100的自然数；
2)在附有搅拌机、冷却机的烧瓶投入208g的化学式4的树脂和412g的环氧氯丙烷来进行溶解之后，将80g的50%NaOH水溶液催化剂滴下4小时进行反应之后回收剩余的环氧氯丙烷之后，在合成的树脂投入528g的甲基异丁基酮、264g的纯化水来进行分液、水洗而除去生成的盐之后回收溶剂，从而合成化学式5的树脂的步骤，
化学式5
Figure FDA00003272726100032
其中，n=1～100的自然数。
4.一种环氧树脂模塑料用环氧树脂组合物，其特征在于，上述环氧树脂模塑料用环氧树脂组合物在通过权利要求3或4所述的方法合成的环氧树脂中混合固化剂、催化剂及填充剂而形成。
CN201380000304.1A 2012-04-25 2013-04-22 环氧树脂及其制备方法及环氧树脂组合物 Active CN103492449B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR10-2012-0043297 2012-04-25
KR1020120043297A KR101385005B1 (ko) 2012-04-25 2012-04-25 에폭시몰딩컴파운드용 자기소화성 에폭시 수지 및 그 제법, 에폭시몰딩컴파운드용 에폭시 수지 조성물
PCT/KR2013/003403 WO2013162232A1 (ko) 2012-04-25 2013-04-22 에폭시몰딩컴파운드용 자기소화성 에폭시 수지 및 그 제법, 에폭시몰딩컴파운드용 에폭시 수지 조성물

Publications (2)

Publication Number Publication Date
CN103492449A true CN103492449A (zh) 2014-01-01
CN103492449B CN103492449B (zh) 2016-01-13

Family

ID=49483464

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380000304.1A Active CN103492449B (zh) 2012-04-25 2013-04-22 环氧树脂及其制备方法及环氧树脂组合物

Country Status (5)

Country Link
US (1) US20150232658A1 (zh)
JP (1) JP5754662B2 (zh)
KR (1) KR101385005B1 (zh)
CN (1) CN103492449B (zh)
WO (1) WO2013162232A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106928432A (zh) * 2017-04-24 2017-07-07 湖南嘉盛德材料科技有限公司 一种无卤本征阻燃环氧树脂及其合成方法
CN106995526A (zh) * 2017-04-24 2017-08-01 湖南嘉盛德材料科技有限公司 无卤本征阻燃环氧树脂固化剂及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101557538B1 (ko) * 2012-12-24 2015-10-06 제일모직주식회사 반도체 소자 밀봉용 에폭시 수지 조성물 및 이를 사용하여 밀봉된 반도체 소자
CN104371625A (zh) * 2014-12-04 2015-02-25 吴江固德电材系统股份有限公司 风电设备用高性能环氧胶粘剂
CN113698575B (zh) * 2021-09-02 2022-04-26 四川大学 一种基于硅氧烷席夫碱结构的高抗冲击可重塑阻燃环氧树脂及制备方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW350857B (en) * 1994-09-20 1999-01-21 Ube Industries Phenol novolak condensate and the uses thereof
JP3349963B2 (ja) 1998-10-21 2002-11-25 日本電気株式会社 難燃性エポキシ樹脂組成物及びそれを用いた半導体装置
JP2003213084A (ja) 2002-01-28 2003-07-30 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置
US20080200636A1 (en) 2005-02-25 2008-08-21 Masataka Nakanishi Epoxy Resin, Hardenable Resin Composition Containing the Same and Use Thereof
JP5170493B2 (ja) * 2005-10-14 2013-03-27 エア・ウォーター株式会社 フェノール系重合体、その製法及びその用途
CN1962713B (zh) * 2005-11-07 2010-05-05 中国科学院化学研究所 含氟酚醛树脂衍生物及其组合物与制备方法
JP5142180B2 (ja) * 2006-05-17 2013-02-13 日本化薬株式会社 エポキシ樹脂組成物、およびその硬化物
JP5573343B2 (ja) * 2009-09-16 2014-08-20 住友ベークライト株式会社 半導体封止用樹脂組成物、および半導体装置
JP5166610B2 (ja) * 2009-12-14 2013-03-21 新日鉄住金化学株式会社 エポキシ樹脂、その製造方法、それを用いたエポキシ樹脂組成物および硬化物
EP2537897B1 (en) * 2011-06-23 2017-06-28 Dow Global Technologies LLC Epoxy-based redispersible polymer powder

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106928432A (zh) * 2017-04-24 2017-07-07 湖南嘉盛德材料科技有限公司 一种无卤本征阻燃环氧树脂及其合成方法
CN106995526A (zh) * 2017-04-24 2017-08-01 湖南嘉盛德材料科技有限公司 无卤本征阻燃环氧树脂固化剂及其制备方法

Also Published As

Publication number Publication date
JP2014529348A (ja) 2014-11-06
KR101385005B1 (ko) 2014-04-16
JP5754662B2 (ja) 2015-07-29
CN103492449B (zh) 2016-01-13
KR20130120212A (ko) 2013-11-04
WO2013162232A1 (ko) 2013-10-31
US20150232658A1 (en) 2015-08-20

Similar Documents

Publication Publication Date Title
KR100946206B1 (ko) 페놀계 중합체, 그 제법 및 그 용도
CN103492449B (zh) 环氧树脂及其制备方法及环氧树脂组合物
CN103897143B (zh) 环氧树脂、环氧树脂的制造方法及其使用
CN102630233B (zh) 环氧树脂组合物
JPWO2014065152A1 (ja) エポキシ樹脂組成物、エポキシ樹脂硬化物の製造方法、及び半導体装置
CN103140523B (zh) 多羟基树脂、环氧树脂、它们的制造方法、环氧树脂组合物及其固化物
JP6139997B2 (ja) エポキシ樹脂、エポキシ樹脂組成物、及びその硬化物
JPWO2008050879A1 (ja) エポキシ樹脂組成物及び硬化物
CN106133017A (zh) 酚醛树脂、包含该酚醛树脂的环氧树脂组合物、该环氧树脂组合物的固化物、及具有该固化物的半导体装置
JP6620981B2 (ja) 熱硬化性成形材料、その製造方法および半導体封止材
JP5734603B2 (ja) フェノール性樹脂、エポキシ樹脂、それらの製造方法、エポキシ樹脂組成物及び硬化物
JP5841947B2 (ja) エポキシ樹脂組成物及び硬化物
EP1130041A1 (en) Epoxy resin composition and semiconductor device
JP5721519B2 (ja) フェノール系重合体、その製法およびその用途
JP4617531B2 (ja) エポキシ樹脂組成物及び半導体装置
JP2009242480A (ja) フェノール系重合体、その製法およびその用途
WO2003082976A1 (en) Thermosetting resin composition and epoxy resin molding material using the composition and semiconductor device
JP2001114863A (ja) エポキシ樹脂組成物及びその硬化物
JP2015160893A (ja) エポキシ樹脂組成物及びその硬化物
TWI491636B (zh) 環氧樹脂模塑膠用自熄性環氧樹脂及其製備方法以及環氧樹脂模塑膠用環氧樹脂組合物
JP2001316453A (ja) エポキシ樹脂組成物及び半導体装置
JPH10324733A (ja) エポキシ樹脂組成物、エポキシ樹脂の製造方法及び半導体封止材料
JP2007297539A (ja) エポキシ樹脂組成物及び硬化物
JP4622025B2 (ja) エポキシ樹脂組成物及び半導体装置
JP2012172122A (ja) フェノール系重合体、その製法およびその用途

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant