CN106751499A - Dopo衍生物与环氧树脂组合物于高频基板上应用 - Google Patents

Dopo衍生物与环氧树脂组合物于高频基板上应用 Download PDF

Info

Publication number
CN106751499A
CN106751499A CN201611103953.6A CN201611103953A CN106751499A CN 106751499 A CN106751499 A CN 106751499A CN 201611103953 A CN201611103953 A CN 201611103953A CN 106751499 A CN106751499 A CN 106751499A
Authority
CN
China
Prior art keywords
epoxy resin
compound
curing agent
resin composition
composite resin
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
Application number
CN201611103953.6A
Other languages
English (en)
Inventor
谢东颖
沈琦
吕荣哲
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.)
Jiangsu Yoke Technology Co Ltd
Original Assignee
Jiangsu Yoke Technology 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 Jiangsu Yoke Technology Co Ltd filed Critical Jiangsu Yoke Technology Co Ltd
Priority to CN201611103953.6A priority Critical patent/CN106751499A/zh
Publication of CN106751499A publication Critical patent/CN106751499A/zh
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/08—Animal fibres, e.g. hair, wool, silk
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/08—Epoxidised polymerised polyenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation

Abstract

一种复合材料、用其制作的高频电路基板及其制作方法。该复合材料包括固体组分如下：DOPO(9,10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物)衍生化合物10‑70重量份，固化剂10‑50重量份，一种或多种环氧树脂10‑90重量份以及无机填充材10‑40重量份。本发明的无卤低介电树脂组合物，采用了高纯度的DOPO(9,10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物)衍生物以细微小颗粒分散于组成物中，不仅不会降低组合物的交联程度，反而增加耐热性与耐燃性。用该树脂组合物所制成的印刷电路板用预浸料和覆铜箔层压板，具有优良的介电性能，高玻璃化转变温度，可以满足印刷电路覆铜板行业电子信号传输的高频化和信息处理的高速化需求。

Description

DOPO衍生物与环氧树脂组合物于高频基板上应用
本申请是申请日为2014年11月10日、申请号为201410629878.1、发明名称为“DOPO衍生物与环氧树脂组合物于高频基板上应用”的发明专利申请的分案申请。
技术领域
本发明涉及化学材料领域的阻燃剂，以DOPO的衍生化合物，用固化剂与环氧树脂的环氧基进行反应，获得对环境友好、低介电特性、耐热性能优异的无卤阻燃环氧树脂固化组合物。
背景技术
环氧树脂本身的化学结构决定了其在反应性、强韧性、柔软性等方面均有优异的性能，且具有良好的机械性能、电气性能和尺寸稳定性；对于不同的基材而言，其粘结性也相当优越，固化后的环氧树脂不仅能保持基材原来的特性，而且对于水、气及化学物质更具阻隔性，且具有质轻、成本低等优点，所以环氧树脂被广泛应用于电子和航天工业，特别是半导体封装材与印刷电路板基材等领域。另一方面，随着科技日新月异，许多电脑资讯产业、通讯业及消费性电子产品，其变化非常的快。综观整个电子产业，其发展特色具有：
1.使用的频率越来越高
2.制造技术层次越来越高。
以印刷电路板而言，将朝低介电、低热膨胀化、多层化、高耐热化等方向发展，同时为符合环境友好之要求，电子、通讯产品亦趋向轻、薄、短小、高可靠度、多功能化与环保之需求。随着无线网路、通讯器材使用的高频化，高频基板必成为未来发展趋势。高频通讯基板所使用的材料要求不外乎能够快速传送资料，并且在传送的过程不会造成资料的损失或被干扰，因此在选取制作高频通讯器材时必须具有以下几个基本特性：
(1)介电常数小而且稳定；
(2)介电消耗因子必须小；
(3)低吸水率；
(4)抗化性佳；
(5)耐热性良好；
(6)无卤阻燃性需求。
相对来说，有机磷系阻燃剂因发烟量低，不易形成有毒气体和腐蚀性气体，具有环境友好性，被公认为可替代卤系阻燃剂的重要品种。在环氧树脂和板材领域，反应型的有机磷系阻燃剂，如DOPO衍生物，应用较为常见，它们通过共价键的方式连接到环氧树脂上面，对材料的性能本身影响较小。而作为添加型的有机磷系阻燃剂，在环氧树脂领域的应用则相对较少，因为它对阻燃剂的熔点和稳定性要求较高，一般的阻燃剂难以达到要求。
作为添加型的阻燃剂，以醚键连接的DOPO衍生物虽然有少量专利报导(参见日本专利申请特开平11[1999]-106619和日本专利申请特开P2001-270993A)。但对其合成方法研究得较少，且该制备方法产率低成本高。将其作为环氧树脂组合物的阻燃剂应用在高频载板上，也从未见报导。
发明内容
本发明针对现有技术的不足，不仅提供了一种简单、高效的DOPO衍生物制备方法，衍生物变得易于提纯，且收率高、成本低。再将其透过与环氧树脂组合物的搭配，可生产出具有低介电常数，高耐热、耐燃性佳的电子材料可应用于印刷电路板使用。
DOPO衍生物的制备，其特征在于化合物(B)与化合物(C)在催化剂、夹带剂、溶剂的存在下，在一个大气压、150-220℃下脱水反应4-30小时制得化合物(A)。
化合物(A)的分子式为：
其中，R1，R2为氢、烷基、芳基或者杂环取代基(取代基上均不能与醇羟基反应的位点)；X为氧原子或无取代基，m和n分别为1-8；
化合物(B)的分子式为：
其中，R1和R2的定义与上述相同；
化合物(C)的分子式为；
其中，m、n和X的定义与上述相同。
反应式为：
化合物(C)和化合物(B)的投料莫耳比优选为0.4到3.0。比例太低，则化合物(B)转换率难以提高；比例过高时，则单取代物增多，且面临着化合物(C)的回收问题。
反应式中，催化剂为适用于脱水反应或着Arbuzov反应的催化剂，包括烷基卤化物、碱金属卤化物、碱土金属卤化物、过度金属卤化物或者酸催化剂。具体的包括碘化钠、溴化钠、碘化钾、溴化钾、氯化锂、溴化锂、碘化锂、C1-C6的烷基碘化物，C1-C6的烷基溴化物，氯化铁、溴化铁、氯化亚铁、溴化亚铁、氯化镁、氯化镍、溴化镍、氯化铝、氯化钛、氯化锡、氯化锌、铜粉、氯化铜、氯化钴、溴化锶、硫酸、盐酸、氯酸、高氯酸、磷酸、氢溴酸、氢氟酸，硝酸、草酸、烷基磺酸、聚合物磺酸的一种或组合。催化剂的用量为化合物(B)摩尔量的0.1-7.0％。
反应所需之溶剂为高沸点溶剂，也就是在常压下沸点大于150℃；熔点大于-100℃。具体包括二苯甲烷、二苯乙烷、二苯丙烷、联苯、二苯醚、环乙基苯、乙二醇二甲醚、乙二醇二乙醚，或者上述化合物的混合物。
反应所需之夹带剂为低沸点溶剂，即常压下其沸点小于150℃，具体包括苯、甲苯、二甲苯、二氯乙烷、氯仿、四氯化碳、戊烷、己烷、庚烷、辛烷、环己烷，或者它们的混合物。
化合物(A)的合成是通过化合物(B)的P-H键与化合物(C)的-OH两个活性位点之间进行反应，而化合物(B)的取代基R1与R2不参与反应，同时化合物(C)中的烷氧基链也不参与反应，因此R1、R2以及m、n的变化对反应条件都没有太大影响。
在另一个实施方案中，反应后之DOPO衍生物可为化合物(A-1)，结构式如下：
在另一个实施方案中，反应后之DOPO衍生物可为化合物(A-2)，结构式如下：
在另一个实施方案中，反应后之DOPO衍生物可为化合物(A-3)，结构式如下：
本发明复合材料树脂组合物中，其所用之固化剂包括酚类固化剂、胺类固化剂、酸类或酸酐固化剂，酯类固化剂，含磷固化剂中的一种或多种。
本发明复合材料树脂组合物中，其所用之环氧树脂包括以下化合物中的至少一种：
(1)双官能环氧树脂，其包括双酚A型环氧树脂，双酚F型环氧树脂，联苯型环氧树脂，萘环型环氧树脂，双环戊二烯型环氧树脂，氰酸酯型环氧树脂。
(2)酚醛环氧树脂，其包括本酚酚醛环氧树脂，双酚A酚醛环氧树脂，邻甲基酚醛环氧树脂。
(3)含磷环氧树脂，其包括二氢氧杂磷菲氧化物(DOPO)改性环氧树脂，10-(2,5-二羟基萘基)二氢氧杂磷菲氧化物。
(4)萘环环氧树脂。
(5)联苯环氧树脂。
上述环氧树脂可根据用途单独使用或混合使用，如使用联苯型环氧树脂、萘环型或邻甲基酚醛型环氧树脂则固化物具有较高的玻璃化转变温度与较好的耐热性能。
本发明复合材料树脂组合物中，其所用之无机填充材包括氢氧化铝、沸石、硅灰石、二氧化硅、氧化镁、硅酸钙、碳酸钙、粘土、滑石及云母中的一种或多种。
使用该上述的复合材料树脂组合物磷含量控制在1-5％，以该组合物制得预浸料，包括基料与通过含浸泡干燥后附着其上的复合材料树脂组合物，其使用织物或无纺织物为基料，例如天然纤维，有机合成纤维以及无机纤维均可采用。本发明组合物为常规的制备方法，先行将固形物放入，然后加溶剂，所用溶剂可以是丙酮、丁酮、环己酮、乙二醇甲醚、丙二醇甲醚、丙二醇甲醚醋酸酯等中的一种或多种，搅拌直到完全溶解后，再加入液态树脂，继续搅拌均匀平衡即可。将上述的组合物加到一个容器中，将促进剂、固化剂先溶解在一定的丁酮溶剂中，用丁酮溶剂适当调整溶液的固体含量65％至75％而制成胶液，使用玻璃纤维布等之物或有机物韩进该胶液，将浸好的玻璃纤维布在170℃的烘箱中烘3-5分钟，即制成预浸料。
上述复合材料组合物制作的覆铜箔层压板，包括多个迭合的预浸料，每一个预浸料包括基料及通过含浸泡干燥之后附着在基料上面的复合材料树脂组合物。
本发明的印刷电路板用覆铜箔层压板，试通过加热和加压，使用两片或两片以上的预浸料粘合在一起而制成的层压板，在层压板的一面或两面覆合上铜箔制成。所述的覆铜层压板须满足以下要求：1.层压的升温速率通常在料温80-170℃时的升温速率应控制在1-3℃/min；2.层压的压力设置，外层料温在80-100℃时施加满压，满压压力为250psi左右；3.固化时，控制料温在180℃，并持温120min；所覆盖的金属箔除铜箔外，还可以是铝箔等，其材质不限。
具体实施制成的印刷电路用覆铜箔层压板(8片黏结片)测其界电损耗因子，耐热性、吸水性、玻璃化转变温度、阻燃性等性能，如下述实施例进一步给予详加说明与描述。
具体实施方式
兹将本实施例详细说明如下，但本发明并非局限在实施例范围。
实施例与比较例中所用的各成分详述如下：
环氧化聚丁二烯：
(A)环氧化聚丁二烯
苯并恶螓：
(B)烯丙基苯并恶螓
环氧树脂：
(C-1)邻甲基酚醛环氧树脂
(C-2)双环戊二烯环氧树脂
硬化剂
(D-1)苯乙烯-马来酸酐低聚物SMA-FE40
(D-2)含磷固化剂DHP-60H
添加型阻燃剂
(E-1)苯氧基磷晴SPB-100
(E-2)化合物(A-2)
(E-3)化合物(A-3)
(E-4)化合物(A-4)
(E-5)磷酸酯阻燃剂OP-935
固化促进剂
(F)2-甲基-4乙基咪侳
无机填充材
(G)球型硅微粉
胶水组合物配方：
物性评估表：
以上物性的测试方法如下：
(1)玻璃化转移温度：
使用升温速率＝20℃/min微差扫瞄热分析仪(DSC)测试。
(2)剥离强度：
将试片裁为长方形，放入测试设备中，以一定速度与拉力测试金属覆盖层的剥离强度。
(3)耐燃性：
试片裁成0.5in×4.7in长方形，以焰高2cm之蓝色火焰燃烧10秒后移开，共烧两次后，纪录火焰移开后之自熄时间。
(4)热安定性：
将试片裁切磨平后，放入热重分析仪(TMA)测试。
(5)吸水性：
试样在120℃及2atm高压锅中加热30分钟。
(6)电气特性：
将已蚀刻后基板裁成5cm2正方形试片，于105℃烘箱内烘2hr后，取出以板厚测定仪量测试片三处的板厚。再将试片夹入介电测量仪中，测三点的数据后取平均值。
(7)T288爆板：
试样在120℃及2atm高压锅中加热120分钟后，浸在288的焊锡槽中20秒，以肉眼观察有无分层。
综合上述结果可知，依照本发明可达到低介电，耐燃佳，吸水率低的特性。本发明同时也充分利用环氧化聚丁二烯、苯并恶螓、环氧树脂、硬化剂之协同效应，而且应用无卤素板材，也能符合环保要求。以上所述，仅为本发明的较佳实施例，对于本领域的普通技术人员来说，可根据本发明的技术方案与构思做出其他各种相应的变化，而这些变化都属于本发明权利要求的保护范围。

Claims (7)

1.一种复合材料树脂组合物，按固形物重量份计，其包括：
DOPO衍生化合物10-70重量份，其DOPO衍生化合物具有以下结构：
其中，R1，R2为氢、烷基、芳基或者杂环取代基(取代基上均不能与醇羟基反应的位点)；X为氧原子或无取代基，m和n分别为1；
其中，所述DOPO衍生化合物是由化合物(B)与化合物(C)在催化剂、夹带剂、溶剂的存在下，在1-6个大气压、150-220℃下脱水反应制备；
其中，化合物(B)具有以下结构：
其中，R1和R2的定义与上述相同；
其中，化合物(C)的具有以下结构：
其中，m、n和X的定义与上述相同，所述的催化剂为适用于脱水反应或者Arbuzov反应的催化剂；
固化剂10-50重量份；
一种或多种环氧树脂10-90重量份；和
无机填充材10-40重量份。
2.如权利要求1所述所述复合材料树脂组合物，其固化剂为酚类固化剂、胺类固化剂、酸类或酸酐固化剂，酯类固化剂，含磷固化剂中的一种或多种。
3.如权利要求1所述所述复合材料树脂组合物，其环氧树脂包含以下化合物中的至少一种：
双官能环氧树脂、酚醛环氧树脂、含磷环氧树脂、萘环环氧树脂和联苯环氧树脂。
4.如权利要求1所述所述复合材料树脂组合物，其中无机填充材为氢氧化铝、沸石、硅灰石、二氧化硅、氧化镁、硅酸钙、碳酸钙、粘土、滑石及云母中的一种或多种。
5.一种利用如权利要求1所述的复合材料树脂组合物制作的预浸料，包括基料及通过含浸泡干燥后附着其上的复合材料树脂组合物。
6.如权利要求5所述的预浸料，其中该基料为织物或无纺织物。
7.一种利用如权利要求1所述的复合材料树脂组合物制备的覆铜层压板，包括多个迭合的预浸料，及压覆在迭合的预浸料的一面或两面上的铜箔，每一预浸料包括基料及通过含浸泡干燥之后附着在基料上的复合材料树脂组合物。
CN201611103953.6A 2014-11-10 2014-11-10 Dopo衍生物与环氧树脂组合物于高频基板上应用 Pending CN106751499A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611103953.6A CN106751499A (zh) 2014-11-10 2014-11-10 Dopo衍生物与环氧树脂组合物于高频基板上应用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410629878.1A CN105566851A (zh) 2014-11-10 2014-11-10 Dopo衍生物与环氧树脂组合物于高频基板上应用
CN201611103953.6A CN106751499A (zh) 2014-11-10 2014-11-10 Dopo衍生物与环氧树脂组合物于高频基板上应用

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201410629878.1A Division CN105566851A (zh) 2014-11-10 2014-11-10 Dopo衍生物与环氧树脂组合物于高频基板上应用

Publications (1)

Publication Number Publication Date
CN106751499A true CN106751499A (zh) 2017-05-31

Family

ID=55877524

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201611103953.6A Pending CN106751499A (zh) 2014-11-10 2014-11-10 Dopo衍生物与环氧树脂组合物于高频基板上应用
CN201410629878.1A Pending CN105566851A (zh) 2014-11-10 2014-11-10 Dopo衍生物与环氧树脂组合物于高频基板上应用

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201410629878.1A Pending CN105566851A (zh) 2014-11-10 2014-11-10 Dopo衍生物与环氧树脂组合物于高频基板上应用

Country Status (4)

Country Link
US (1) US9956742B2 (zh)
JP (2) JP2016089179A (zh)
CN (2) CN106751499A (zh)
TW (1) TWI651361B (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI667276B (zh) * 2014-05-29 2019-08-01 美商羅傑斯公司 具改良耐燃劑系統之電路物質及由其形成之物件
US10233365B2 (en) 2015-11-25 2019-03-19 Rogers Corporation Bond ply materials and circuit assemblies formed therefrom
CN106700424B (zh) * 2016-12-30 2019-09-24 浙江华正新材料股份有限公司 一种低损耗树脂组合物、半固化片和层压板
CN107383340A (zh) * 2017-07-20 2017-11-24 沈阳化工大学 一种dopo改性酸酐环氧树脂阻燃固化剂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102428091A (zh) * 2009-05-19 2012-04-25 雅宝公司 Dopo衍生的阻燃剂及环氧树脂组合物
CN103408595A (zh) * 2013-07-05 2013-11-27 江苏雅克科技股份有限公司 一类dopo衍生物的制备方法
CN103408594A (zh) * 2013-07-05 2013-11-27 江苏雅克科技股份有限公司 一种高纯度dopo衍生物的制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3897138B2 (ja) 1997-10-03 2007-03-22 有限会社斉藤化成品研究所 難燃性ポリエステル樹脂組成物およびその製造方法
JP2001172555A (ja) 1999-12-16 2001-06-26 Sumitomo Durez Co Ltd 難燃性エポキシ樹脂粉体塗料
JP2001270993A (ja) 2000-01-21 2001-10-02 Daicel Chem Ind Ltd 難燃性樹脂組成物
JP4156180B2 (ja) 2000-07-10 2008-09-24 住友ベークライト株式会社 エポキシ樹脂組成物、プリプレグ及びそれを用いた銅張積層板
EP1366053B1 (en) 2001-01-22 2005-01-05 Huntsman Advanced Materials (Switzerland) GmbH Flame-proofing agents
JP2004197032A (ja) 2002-12-20 2004-07-15 Hitachi Chem Co Ltd 難燃性樹脂組成物およびこの組成物を用いるプリプレグ，積層板，プリント配線板
JP5034181B2 (ja) 2005-07-22 2012-09-26 住友ベークライト株式会社 プリプレグおよび積層板
KR20090035532A (ko) 2006-07-20 2009-04-09 쇼와 하이폴리머 컴패니 리미티드 인 함유 벤조옥사진 화합물, 그 제조 방법, 경화성 수지 조성물, 경화물 및 적층판
TWI598357B (zh) 2009-05-19 2017-09-11 亞比馬利股份有限公司 Ｄｏｐｏ衍生物阻燃劑
ES2693528T3 (es) 2010-03-31 2018-12-12 Albemarle Corporation Procedimiento para la preparación de compuestos derivados de DOPO y composiciones de los mismos
WO2012064703A1 (en) 2010-11-12 2012-05-18 Albemarle Corporation Dopo-derived flame retardant and synthetic hydrogarnets for epoxy resin compositions
CN102504532B (zh) * 2011-10-18 2013-09-18 广东生益科技股份有限公司 无卤低介电树脂组合物及使用其制作的预浸料与覆铜箔层压板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102428091A (zh) * 2009-05-19 2012-04-25 雅宝公司 Dopo衍生的阻燃剂及环氧树脂组合物
CN103408595A (zh) * 2013-07-05 2013-11-27 江苏雅克科技股份有限公司 一类dopo衍生物的制备方法
CN103408594A (zh) * 2013-07-05 2013-11-27 江苏雅克科技股份有限公司 一种高纯度dopo衍生物的制备方法

Also Published As

Publication number Publication date
TWI651361B (zh) 2019-02-21
JP2017110014A (ja) 2017-06-22
CN105566851A (zh) 2016-05-11
JP2016089179A (ja) 2016-05-23
US9956742B2 (en) 2018-05-01
TW201617401A (zh) 2016-05-16
US20160129666A1 (en) 2016-05-12

Similar Documents

Publication Publication Date Title
CN106366128B (zh) 膦菲类化合物及其制备方法和应用
CN103013110B (zh) 无卤素树脂组成物及应用其的铜箔基板及印刷电路板
CN103131131B (zh) 无卤素树脂组合物及其应用的铜箔基板及印刷电路板
CN103540101B (zh) 无卤素树脂组合物及应用其的铜箔基板及印刷电路板
CN103881299B (zh) 无卤素树脂组合物及其应用
CN104177809B (zh) 低介电的无卤素树脂组合物及其应用
US9867287B2 (en) Low dielectric resin composition with phosphorus-containing flame retardant and preparation method and application thereof
US10189988B2 (en) High-CTI and halogen-free epoxy resin composition for copper-clad plates and use thereof
EP3219758B1 (en) Thermosetting resin composition and prepreg and laminated board prepared therefrom
TWI646142B (zh) Resin composition and copper foil substrate and printed circuit board using same
CN105936745A (zh) 一种树脂组合物
CN103131130B (zh) 环氧树脂组成物及应用其的低介电常数绝缘材料
CN103421273A (zh) 无卤素树脂组成物
CN105566621A (zh) 低介电含磷聚酯化合物组成及其制法
CN105348742B (zh) 含三聚氰胺型苯并噁嗪树脂的热固性树脂组合物、半固化片及层压板
CN103382242A (zh) 含磷阻燃酚醛树脂及以其为原料制备的阻燃环氧树脂固化物
CN103980708A (zh) 用于集成电路的无卤阻燃热固性树脂组合物、半固化片及层压板
CN103992622A (zh) 一种无卤树脂组合物以及使用它的预浸料和印制电路用层压板
KR101915919B1 (ko) 열경화성 수지 조성물 및 이로 제조한 프리프레그와 적층판
CN106751499A (zh) Dopo衍生物与环氧树脂组合物于高频基板上应用
CN103980667A (zh) 集成电路用热固性树脂组合物、半固化片及层压板
CN105131597A (zh) 一种无卤树脂组合物以及使用它的预浸料和印制电路用层压板
CN104194262A (zh) 一种热固性树脂组合物及使用其制作的半固化片和层压板
CN104194261A (zh) 热固性树脂组合物及使用其制作的半固化片和层压板
CN103304809A (zh) 一种无卤阻燃预聚物及使用其制作的半固化片及层压板

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20170531

RJ01 Rejection of invention patent application after publication