CN102203176A - 含磷阻燃环氧树脂组合物、其预浸料和层压板 - Google Patents

含磷阻燃环氧树脂组合物、其预浸料和层压板 Download PDF

Info

Publication number
CN102203176A
CN102203176A CN2009801435794A CN200980143579A CN102203176A CN 102203176 A CN102203176 A CN 102203176A CN 2009801435794 A CN2009801435794 A CN 2009801435794A CN 200980143579 A CN200980143579 A CN 200980143579A CN 102203176 A CN102203176 A CN 102203176A
Authority
CN
China
Prior art keywords
epoxy resin
resin composition
curable epoxy
epoxy
composition according
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
CN2009801435794A
Other languages
English (en)
Inventor
谢尔盖·V·列夫奇克
法比内·萨姆彦
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.)
ICL IP America Inc
Original Assignee
ICL IP America Inc
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 ICL IP America Inc filed Critical ICL IP America Inc
Publication of CN102203176A publication Critical patent/CN102203176A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/12—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • B32B2260/04—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
    • B32B2262/10—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
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat 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
    • 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
    • B32B2451/00—Decorative or ornamental articles
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01014—Silicon [Si]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/14—Integrated circuits
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Epoxy Resins (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

本申请提供一种了可固化环氧树脂组合物，其包括至少一种可固化环氧树脂，至少一种阻燃固化剂和至少一种固化催化剂。

Description

含磷阻燃环氧树脂组合物、其预浸料和层压板
技术领域
本发明涉及阻燃环氧树脂组合物，特别是可固化阻燃环氧树脂组合物，其包括环氧树脂、聚亚芳基烷基膦酸酯固化剂和一种季鏻盐或季铵盐固化催化剂。该可固化阻燃环氧树脂组合物表现出对预浸料的B-阶段固化进行可靠处理的宽的加工窗口。
相关申请的详细描述
阻燃环氧树脂由于其卓越的自熄性能、机械性能、耐水蒸汽和电性能而用于各种电绝缘材料。常规的是在制备含环氧树脂的层压板中将各种添加剂加入到环氧树脂组合物中以提高得到的层压板的阻燃性。已经提出了很多类型的阻燃添加剂，然而，商业上最广泛使用的添加剂是含卤素添加剂，例如四溴双酚A，或用四溴双酚A制备的环氧树脂。
虽然含卤素阻燃添加剂例如四溴二苯酚基丙烷很有效，但出于环境立场上的考虑一些人认为它们是不符合要求的，并且近年来人们已经对无卤素环氧树脂制剂越来越有兴趣，其可以达到在标准“Underwriters Laboratory”测试方法UL 94下典型地V-0的阻燃要求。
存在一些商业上可利用的磷基阻燃添加剂，其可以用来代替含卤素阻燃添加剂。例如，通过将添加型磷系阻燃剂如磷酸三苯酯(TPP)、磷酸三甲苯酯(TCP)、磷酸甲苯二苯酯(CDP)、间苯二酚双(磷酸二苯酯)(RDP)、双酚A双(磷酸二苯酯)(BDP)等磷酸酯系化合物加入到环氧树脂组合物中，可保持不易燃性。此类制剂的实例在例如美国专利5,919,844；5,932,637；6,348,523；6,713,163和欧洲专利申请1,359,174中被描述。然而，由于如上述的一般的含磷化合物不能与环氧树脂反应，因此出现了其它问题，例如模制品吸湿后的焊接耐热性和耐化学物质性例如耐碱性等显著降低。由于这些含磷添加剂显著的塑化作用，也发现固化环氧树脂的玻璃化转变温度(Tg)显著降低。
已经建议在环氧树脂制剂中使用反应性磷基阻燃剂代替卤化阻燃剂。“环氧树脂的热分解，燃烧和阻燃的综述(Review on thermal decomposition，combustion and flame-retardancy of epoxy resins)”的作者S.Levchik和E.Weil，Polymer International，Vol.53，2004，pp.1901-1929中给出了现有技术中关于磷基阻燃环氧树脂发展水平的综述。在一些制剂中，含磷阻燃剂与环氧树脂预反应以形成双或多官能环氧树脂，然后用交联剂使其固化。
现有技术描述了使用某些含磷元素的化合物作为环氧树脂的交联或固化剂，与环氧树脂一起使用，作为将磷元素引入环氧树脂体系的一种方式。例如，美国专利4,973,631；5,086,156；6,403,220；6,740,732；6,486,242；6,733,698和6,887,950描述了使用双官能或三官能氧化膦交联剂作为有效的固化剂。上述现有技术的组合物不容易制备，且需要特殊制备工艺。提供一种可以由实际的、工业规模的原材料获得的化合物将是有益的；从而将比现有技术的工艺更具经济优势。
然而，用于环氧树脂的最常使用的磷基阻燃剂是9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)。通常存在两种已知的方法将DOPO应用到环氧复合物中。第一种方法中，DOPO与环氧树脂预反应，如在欧洲专利申请0,806,429和美国专利6,645,631；6,291,627和6,486,242中描述的那样。因为DOPO是单官能反应化合物，其封端环氧链，所以必须在此工艺中使用只有多官能的比双官能环氧树脂更昂贵的环氧树脂。第二种方法中，DOPO与醌或酮类化合物预反应，这些化合物除了具有这些官能团还具有两个或更多羟基或胺基，例如欧洲专利申请1,103,575和1,537,160，美国专利6,291,626；6,441,067；6,933,050；6,534,601；6,646,064；6,762,251和6,984,716和PCT专利公开05/118604中描述的。此方法的问题在于其复杂性，该复杂性导致昂贵的化合物并且分子中磷含量低。
烷基和芳基膦酸酯通常与环氧树脂相容。特别是低级烷基膦酸酯是有价值的，因为其包含了高比例的磷，因此当其引入树脂中时能够赋予树脂良好的阻燃性能。在环氧树脂中使用膦酸酯的例子显示在例如美国专利5,710,305和6,353,080中。然而，如果膦酸酯作为添加剂使用，其会遇到与上述非反应性的磷酸酯相似的问题。非反应性的膦酸酯的主要问题是低玻璃化转变温度和环氧化合物的高吸湿性。当含有高水分的层压板在使用铅系焊料的情况下在260℃左右引入液体焊料槽中或在使用无铅焊料的情况下在288℃左右引入液体焊料槽中时，该含有高水分的层压板易于起泡和破裂，所述在使用铅系焊料的情况下在260℃左右引入液体焊料槽中或在使用无铅焊料的情况下在288℃左右引入液体焊料槽中是制备印刷电路板的典型步骤。
PCT专利公开03/029258描述了在环氧体系中使用羟基封端的聚(间-亚苯基甲基膦酸酯)。这里环氧树脂在甲基咪唑作为固化催化剂存在下被聚(间-亚苯基甲基膦酸酯)固化。此外，如T.Wu，A.M.Piotrowski，Q.Yao和S.V.Levchik在Journal of Applied Polymer Science，Vol.101，pp.4011-4022中描述的那样该聚膦酸酯有效地固化了环氧树脂。因为该膦酸酯被有效地引入环氧树脂网络中，最终固化复合物表现出高玻璃化转变温度和低吸水性。PCT专利公开04/060957描述了环氧树脂与聚(间-亚苯基甲基膦酸酯)预反应的过程，然而因为该聚膦酸酯是多官能化合物，其倾向于交联环氧树脂，因此预反应不能在商业规模上被有效地控制。
因为膦酸酯固化环氧树脂是通过将环氧基团插入磷酸酯基团P-O-C中，每单个反应都导致在聚合物网中支化。另外，一些常规的例如咪唑或叔胺的环氧固化催化剂，随着环氧插入P-O-C中催化环氧树脂自固化。因此凝胶化发生在相对窄的温度间隔内。这限制了预浸料B-阶段固化的加工窗口，因为在低温或短时间内，该树脂显示出过度的流动，反之在更高温度和/或经过更长时间，该环氧树脂可能过度交联限制树脂流动。
本领域公知使用季铵盐、季膦盐，更具体地说季铵卤化物和季鏻卤化物用于环氧化物与含有酚类羟基的化合物反应以制备高分子量环氧化合物。参见例如美国专利2,216,099；2,633,458；2,658,855；3,377,406；3,477,990；3,547,881；3,547,885；3,694,407；3,738,862；3,948,855；和4,048,141和欧洲专利0,019,852，以及H.Lee和K.Neville，McGraw-Hill(1967)的“Handbook of Epoxy Resins”，和由B.Ellis编辑的Chemistry and Technology of Epoxy Resins，Blacie Academic and Professional(1993)。在美国专利4,048,141中也描述了某些鏻催化剂促进邻位环氧化物与酚、羧酸或羧酸酐之间的反应。
在S.Minegishi，S.Komatsu，A.Kameyama and T.Nishikubo(J.Polym.Sci.，Part A，Polym.Chem，1999，Vol.37，pp.959-965)的期刊出版物中描述了使用四丁基铵溴化物、四丁基铵氯化物、四丁基鏻溴化物和四丁基鏻氯化物作为二芳基苯基膦酸酯与环氧化物反应的催化剂。反应进行很长时间(48小时)并制备得到直链聚膦酸酯。T.Wu，A.M.Piotrowski，Q.Yao和S.V.Levchik(J.Applied polymer Science，2006，Vol.101，pp.4011-4022)通过差示扫描量热法研究了环氧化物与聚(间-亚苯基甲基膦酸酯)的反应，发现其很慢并且不适合于商业化环氧固化周期。选择2-甲基咪唑作为更有效的催化剂。
根据现有技术的缺陷，本发明的目的是提供可固化阻燃环氧树脂组合物用于制备环氧预浸料和环氧层压板，和生产印刷电路板和多层印刷电路板，可固化阻燃环氧树脂组合物具有宽的加工窗口，因此预浸料可以容易地进行B-阶段固化。另外，层压板必须显示出高的热稳定性和良好的防潮性。
发明概述
本发明提供一种可固化环氧树脂组合物，其包括至少一种可固化环氧树脂，至少一种例如聚亚芳基烷基膦酸酯固化剂的阻燃固化剂，和至少一种例如季鏻或季铵盐固化催化剂的固化催化剂。
本申请涉及一种印刷电路板，例如包括本申请描述的可固化阻燃环氧树脂组合物的用于电子应用的印刷电路板，用于电子元件的密封剂，保护涂层，和结构和/或装饰复合材料。
优选实施例描述
本发明的可固化阻燃环氧树脂组合物包括至少一种可固化环氧树脂作为重要组分。该组分可以是不含卤素的环氧树脂，例如，单官能环氧化物、脂肪族、脂环族和芳族单官能环氧树脂和包括如甲酚缩水甘油醚、苄基缩水甘油醚这样的化合物。本发明其他有用的环氧树脂包括但不限于双官能、三官能、四官能和更高官能度的环氧树脂。这些类型的环氧树脂的例子包括，但不限于双酚A的二缩水甘油醚、双酚F的二缩水甘油醚、双酚S的二缩水甘油醚、二缩水甘油基-对-氨基苯酚、三缩水甘油基氨基甲酚、三缩水甘油基-对-氨基苯酚、二苯氨基甲烷的四缩水甘油醚、苯酚线型酚醛环氧树脂、甲酚线型酚醛环氧树脂、间苯二酚型环氧树脂、带有萘骨架的环氧树脂、联苯基型环氧树脂、双环戊二烯型环氧树脂和联苯芴型环氧树脂等。这些树脂可以单独或以任意合适的组合使用。此外，其它有用的环氧树脂或其它在本发明中有用的此类通用型树脂是那些对制造印刷电路板或其它电子基材有用的。照此，如有需要，这些树脂任何相容的混合物都可使用。
这个组分，即该可固化环氧树脂存在的量为按重量计组合物总重量的约50-约90％。更优选，该可固化环氧树脂存在的量为按重量计组合物总重量的约65-约90％。
聚亚芳基烷基膦酸酯固化剂，按重量计以组合物总重量的约5％-约40％的量存在，优选，按重量计为约5％-约25％。如在PCT国际专利公开物No.WO 03/029258中更充分的描述，所述WO 03/029258整体引入本文作为参考，该阻燃固化剂为包括重复单元-OP(O)(R)-O-亚芳基-的低聚膦酸酯，其中R可以是直链或支链包含至多约8个碳原子的烷基，优选至多约6个碳原子且其磷含量大于12wt％。该组合物中的膦酸酯物质包括那些包含-OH端基和可能那些不包含-OH端基的膦酸酯物质。优选的R基团是甲基，但其可以是任意的低级烷基。在一个实施方案中，聚亚芳基烷基膦酸酯固化剂是聚(间-亚苯基甲基膦酸酯)。
所谓“亚芳基”是指任何二元酚的基团。优选二元酚应该在非相邻的位置具有两个羟基。实例包括间苯二酚；氢醌；和双酚，例如双酚A、双酚F、4，4’-二苯酚、酚酞、4，4’-硫代联苯酚或4，4’-磺酰基二苯酚。该亚芳基可以是1，3-亚苯基，1，4-亚苯基或双酚双自由基单元，但是优选1，3-亚苯基。
在一个实施方案中，固化催化剂是该结构式描述的至少一种：
Figure BPA00001374729800061
其中R1、R2、R3和R4各自独立为烃基或含有1到约12个碳原子的惰性取代的烃基团，X为P或N，Y是阴离子，m是阴离子的化合价。在一个实施方案中，该烃基团是一个含有至多约12个碳原子的直链或支链烷基，其可以被O、N或S惰性地取代。这些化合物可以另外地描述为四烃基鏻或四烃基铵盐。这些催化剂在选择性地催化环氧基团以合适的反应速度插入P-O-C键的想要的反应是惊人的有效。在一个实施方案中，Y是选自溴化物、氯化物、碘化物、醋酸化物、醋酸化物复合物、醋酸化物/醋酸复合物、磷酸化物、磷酸化物复合物和氢氧化物的阴离子。在一个实施方案中，m可以是1、2或3。
优选的催化剂是季鏻盐和季铵盐，然而并不限于此。所述季鏻盐包括，例如四丁基鏻氯化物、四丁基鏻溴化物、四丁基鏻碘化物、四丁基鏻醋酸盐复合物、四苯基鏻氯化物、四苯基鏻溴化物、四苯基鏻碘化物、乙基三苯基鏻氯化物、乙基三苯基鏻溴化物、乙基三苯基鏻碘化物、乙基三苯基鏻醋酸盐复合物、乙基三苯基鏻磷酸盐复合物、丙基三苯基鏻氯化物、丙基三苯基鏻溴化物、丙基三苯基鏻碘化物、丁基三苯基鏻氯化物、丁基三苯基鏻溴化物、丁基三苯基鏻碘化物、乙基三-对-甲苯基鏻醋酸盐/醋酸复合物、乙基三苯基鏻醋酸盐/醋酸复合物或其组合等描述在美国专利5,208,317、5,109,099和4,981,926中，其内容整体以引入本文作为参考。最优选的催化剂包括四乙基铵溴化物、四乙基铵氢氧化物、乙基三甲苯基鏻醋酸盐和乙基三苯基鏻醋酸盐。
所述季铵盐包括，例如四甲基铵氯化物、四甲基铵溴化物、四甲基铵碘化物、三乙基苄基铵氯化物、三乙基苄基铵溴化物、三乙基苄基铵碘化物、四乙基铵氯化物、四乙基铵溴化物、四乙基铵碘化物、四乙基铵氢氧化物、四(正丁基)铵氯化物、四(正丁基)铵溴化物、四(正丁基)铵碘化物、四(正丁基)铵氢氧化物、四(正辛基)铵氯化物、四(正辛基)铵溴化物、四(正辛基)铵碘化物、四(正辛基)铵氢氧化物、甲基三(正辛基)铵氯化物、双(四苯基正膦亚基)铵氯化物等。
催化剂的使用量取决于催化剂的分子量、催化剂的活性和想要进行聚合的速度。一般说来，催化剂用量是从每100份树脂0.01份(p.h.r.))到约1.0p.h.r.，更优选，从约0.01p.h.r.到约0.5p.h.r，最优选，从约0.1p.h.r.到约0.5p.h.r.。在本文的一个实施方案中，此处的理解是树脂部分涉及本文描述的可固化环氧树脂部分。
本发明的该环氧树脂组合物可以含有任选的添加剂，例如，阻燃助剂，还有下列类型的材料：纤维和/或布增强添加剂；矿物填料例如Al(OH)3、Mg(OH)2或二氧化硅；脱模剂；着色剂等等。
在一个实施方案中，本文的环氧树脂组合物可被用于其它应用，例如电子应用，如预浸料、印刷电路板、用于电子元件的密封剂、防护涂层、结构和/或装饰性的复合材料，其用量取决于具体应用，但在一非限制性的优选实施方案中，可以使用量是从约0.01p.h.r.到约2.0p.h.r.，更优选从约0.01p.h.r.到约0.5p.h.r.，最优选从约0.1p.h.r.到约0.5p.h.r.。
本发明通过以下实施例进一步说明：
实施例
材料：
环氧树脂1，(PNE)苯酚线型酚醛环氧树脂，D.E.N.438，Dow Chemicals的品牌
环氧树脂2，(CNE)甲酚线型酚醛环氧树脂，EPON164，Hexion的品牌
固化剂，(PMP)聚(间-亚苯基甲基膦酸酯)，Fyrol PMP，ICL-IP的品牌
催化剂1：(ETPPA)乙基三苯基鏻醋酸盐(70％的甲醇溶液)，购自Alfa Aesar
催化剂2：(ETPPB)乙基三苯基鏻溴化物，Dishman Co.，的产品
催化剂3：(2-MI)2-甲基咪唑，Amicure AMI-2，Air Products的品牌
催化剂4：(2-PI)2-苯基咪唑，Amicure PI-2，Air Products的品牌
催化剂5：(DMAPM)双(二甲氨基丙基)甲胺，Polycat 77，Air Products的品牌
催化剂6：(DMAMP)＜90％三-2，4，6-(二甲基氨基甲基)苯酚+＜10％双(二甲基氨基甲基)苯酚，Ancamide K54，Air Products的品牌
溶剂：甲乙酮，(MEK)，购自Fluka
玻璃纤维布：7628/50型，BGF Industries的产品
铜箔：Gould Electronics Inc.，(JTC，1.0oz./Ω2)
清漆的制备
称重的环氧树脂和Fyrol PMP分别在不同的罐中预热至温度100-120℃。该树脂和Fyrol PMP倒入一个配有机械搅拌器、温度计和加热套的三颈圆底烧瓶中。然后在连续搅拌中加入25p.h.r的MEK直到得到一种澄清均匀的溶液。该溶液的粘度通过进一步添加MEK调整至700-1000cPa(@25℃)。该催化剂分别溶解在MEK或丙酮中并以0.15-1.0p.h.r的量添加到最后的清漆中。
预浸料的制造
将清漆在室温下手工刷在玻璃纤维布(10.5×10.5英寸)的两面上。该玻璃纤维布放在一空气循环烤箱中在175-185℃下预热，并暴露在该热度一段时间。使用不同的暴露时间重复实验。制造出树脂含量约40％的预浸料。
树脂流动测量
制备得到的预浸料的树脂流动根据IPC-TM-650试验2.3.16.2进行测试。该树脂流动绘制为暴露时间的函数，其通常产生负斜率的线性图形。该计算斜率代表了加工窗口的特性。斜率从-0.1至-0.5代表宽的加工窗口，而斜率从-0.7至-1.5代表窄的加工窗口。
层压板的制造
将底部和顶部有铜箔的8个预浸料的堆放置在两个不锈钢板中间。四张牛皮纸放置在板的下面和上面。整个组件处于液压机中，其线性加热至185℃或200℃。在170℃应用压力200psi。层压板等温(185℃或200℃)加热90分钟进行固化，随后在215℃或230℃分别后固化(postcuring)15分钟。
压力蒸煮器测试
根据IPC-TM-650试验2.3.7.1从层压板上刻蚀铜。压力蒸煮器测试(PCT)根据IPC-TM 650试验2.6.16用下列修改进行：(a)样本暴露在高压釜的蒸汽中1、2和4小时；(b)焊料槽保持温度在288℃，(c)样本浸入焊料中5分钟。
玻璃化转变温度(Tg)
玻璃化转变温度通过差示扫描量热计(DSC)根据IPC-TM 650，试验2.4.25测量。
热稳定性
层压板的热稳定性通过热重分析(TGA)在加热速度为10℃/分钟的氮气惰性气氛中测量。损失5重量百分数时记录为Td。
表1
下表1预浸料的清漆物理性质和层压板的物理性质的组合
Figure BPA00001374729800111
从表1可见催化剂4、5和6给出了非常窄的预浸料B-阶段固化的加工窗口，所以它们不能用于层压板的制造。催化剂3，虽然在0.15p.h.r.给出了可接受的加工窗口，但显示了性能差的层压板。催化剂3的浓度增加至0.3p.h.r.导致加工窗口变窄。催化剂3、4、5、6也导致强烈的褐色层压板，其可能损害层压板的质量检查。
本发明其它实施方案出于说明书和本发明公开的实施的考虑对本领域技术人员来说将是显而易见的。说明书和实施例被认为仅仅是示范性的，本发明的真实范围和精神由随附的权利要求限定。

Claims (14)

1.一种可固化环氧树脂组合物，其包括至少一种可固化环氧树脂，至少一种阻燃固化剂和至少一种固化催化剂。
2.根据权利要求1所述的可固化环氧树脂组合物，其中阻燃固化剂是聚亚芳基烷基膦酸酯。
3.根据权利要求1所述的可固化环氧树脂组合物，其中阻燃固化剂是聚(间-亚苯基甲基膦酸酯)。
4.根据权利要求1所述的可固化环氧树脂组合物，其中可固化环氧树脂的存在量按重量计是可固化环氧树脂组合物总重量的从约50％到约90％。
5.根据权利要求1所述的可固化环氧树脂组合物，其中可固化环氧树脂的存在量按重量计是可固化环氧树脂组合物总重量的从约65％到约90％。
6.根据权利要求2所述的可固化环氧树脂组合物，其中聚亚芳基烷基膦酸酯的存在量按重量计是可固化环氧树脂组合物总重量的从5％到约40％。
7.根据权利要求1所述的可固化环氧树脂组合物，其中至少一种催化剂如下式所示：
Figure FPA00001374729700011
其中R1、R2、R3和R4各自独立为烃基或惰性取代的烃基，X为P或N，Y是阴离子，m是阴离子的化合价。
8.根据权利要求1所述的可固化环氧树脂组合物，其中催化剂是季铵盐或季鏻盐。
9.根据权利要求1所述的可固化环氧树脂组合物，其中催化剂的存在量是每100份可固化环氧树脂从约0.01份到约1.0份。
10.一种包括权利要求1所述的组合物的预浸料。
11.一种包括权利要求1所述的组合物的层压板。
12.一种包括权利要求1所述的组合物的用于印刷电路板的密封剂。
13.一种包括权利要求1所述的组合物的防护涂层。
14.一种包括权利要求1所述的组合物的结构和/或装饰性复合材料。
CN2009801435794A 2008-10-29 2009-10-20 含磷阻燃环氧树脂组合物、其预浸料和层压板 Pending CN102203176A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US19761508P 2008-10-29 2008-10-29
US61/197,615 2008-10-29
PCT/US2009/061276 WO2010051182A1 (en) 2008-10-29 2009-10-20 Phosphorus-containing flame retardant epoxy resin composition, prepeg and laminate thereof

Publications (1)

Publication Number Publication Date
CN102203176A true CN102203176A (zh) 2011-09-28

Family

ID=41343405

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009801435794A Pending CN102203176A (zh) 2008-10-29 2009-10-20 含磷阻燃环氧树脂组合物、其预浸料和层压板

Country Status (6)

Country Link
US (1) US20110201724A1 (zh)
EP (1) EP2346939A1 (zh)
JP (1) JP2012507599A (zh)
CN (1) CN102203176A (zh)
TW (1) TW201035157A (zh)
WO (1) WO2010051182A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104379627A (zh) * 2012-06-15 2015-02-25 陶氏环球技术有限责任公司 潜伏型催化固化剂
CN110337484A (zh) * 2016-12-14 2019-10-15 溴化合物有限公司 不含锑阻燃性环氧树脂组合物
CN111094422A (zh) * 2017-09-13 2020-05-01 瀚森公司 环氧树脂体系
CN112574643A (zh) * 2020-12-16 2021-03-30 苏州太湖电工新材料股份有限公司 一种阻燃型水性绝缘漆及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8058363B2 (en) * 2009-04-09 2011-11-15 Iteq Corporation Varnish and prepreg, and substrates thereof
WO2014006855A1 (ja) * 2012-07-02 2014-01-09 サンアプロ株式会社 エポキシ樹脂硬化促進剤
TWI721024B (zh) * 2015-11-13 2021-03-11 美商Ｉｃｌ Ｉｐ美國股份有限公司 用於熱固性樹脂之活性酯類固化劑化合物、包含彼之阻燃劑組成物、及由其所製成之物件
KR101922288B1 (ko) * 2015-11-26 2018-11-27 삼성에스디아이 주식회사 반도체 소자 밀봉용 에폭시 수지 조성물 및 이를 이용하여 밀봉된 반도체 소자

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1639174A (zh) * 2001-10-04 2005-07-13 阿克佐诺贝尔股份有限公司 羟基封端的低聚膦酸酯
CN1795223A (zh) * 2003-05-22 2006-06-28 苏普雷斯塔有限责任公司 用于环氧树脂的聚膦酸酯阻燃固化剂

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL173809B (nl) * 1951-11-17 Rca Corp Beeldopneeminrichting met kleurcodeerstrookfilterstelsel.
US3377406A (en) * 1963-12-16 1968-04-09 Shell Oil Co Process of esterification of polyepoxides with ethylenically unsaturated monocarboxylic acids in the presence of onium salts of inorganic acids
US3547885A (en) * 1968-03-08 1970-12-15 Sun Oil Co Process for curing polyepoxides with anhydrides and phosphonium halide catalysts therefor
US3694407A (en) * 1970-08-11 1972-09-26 Shell Oil Co Epoxy-containing condensates,their preparation and use
US3948855A (en) * 1971-09-16 1976-04-06 The Dow Chemical Company Process for reacting a phenol with a vicinal epoxy compound in the presence of phosphorus or carbon containing acid, ester or acid ester
US3738862A (en) * 1971-11-08 1973-06-12 Shell Oil Co Process for preparing reinforced laminates in situ with epoxy-polyhydric phenol condensates
US4048141A (en) * 1975-11-06 1977-09-13 The Dow Chemical Company Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids
US4973631A (en) * 1989-10-06 1990-11-27 Virginia Tech Intellectual Properties Inc. Novel phosphorus containing epoxy networks
US5086156A (en) * 1989-10-06 1992-02-04 Virginia Tech Intellectual Properties, Inc. Novel phosphorus containing epoxy networks based on trihydrocarbyl phosphine oxides having active substituents
US5208317A (en) * 1990-02-06 1993-05-04 The Dow Chemical Company Composition comprising epoxy resin and cationic amine phosphonium catalyst
US4981926A (en) * 1990-02-06 1991-01-01 The Dow Chemical Company Composition of epoxy resin, amino group-containing phosphonium catalyst and curing agent
GB9516794D0 (en) * 1995-08-16 1995-10-18 Albright & Wilson Flame retardant product and process
US5919844A (en) * 1995-12-28 1999-07-06 Toray Industries, Inc. Epoxy resin composition
JPH1095898A (ja) * 1996-09-25 1998-04-14 Sumitomo Bakelite Co Ltd 難燃性樹脂組成物およびこれを用いた積層板
US6353080B1 (en) * 1997-06-26 2002-03-05 The Dow Chemical Company Flame retardant epoxy resin composition
JPH1180178A (ja) * 1997-09-12 1999-03-26 Hitachi Chem Co Ltd リン含有フェノール末端オリゴマー及びその製造法
TW528769B (en) * 1998-06-19 2003-04-21 Nat Science Council Flame retardant advanced epoxy resins and cured epoxy resins, and preparation thereof
JP3388538B2 (ja) * 1998-06-29 2003-03-24 信越化学工業株式会社 半導体封止用エポキシ樹脂組成物及び半導体装置
DE19836932B4 (de) * 1998-08-14 2004-03-04 KLÖCKNER, Lothar Papierspender
JP4124295B2 (ja) * 1998-08-20 2008-07-23 株式会社Ａｄｅｋａ 硬化性組成物
US6291627B1 (en) * 1999-03-03 2001-09-18 National Science Council Epoxy resin rendered flame retardant by reaction with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
US6486242B1 (en) * 1999-04-20 2002-11-26 Sumitomo Bakelite Company Limited Flame-retardant resin composition and prepreg and laminate using the same
AU2089701A (en) * 1999-12-13 2001-06-18 Dow Chemical Company, The Phosphorus element-containing crosslinking agents and flame retardant phosphoruselement-containing epoxy resin compositions prepared therewith
JP5485487B2 (ja) * 1999-12-13 2014-05-07 ダウ グローバル テクノロジーズ エルエルシー 難燃性リン元素含有エポキシ樹脂組成物
JP4588834B2 (ja) * 2000-04-06 2010-12-01 パナソニック電工株式会社 リン含有エポキシ樹脂組成物及び、該リン含有エポキシ樹脂を用いる難燃性の樹脂シート、樹脂付き金属箔、プリプレグ及び積層板、多層板
JP2002188442A (ja) * 2000-10-11 2002-07-05 Denso Corp 蓄熱タンク
KR100701455B1 (ko) * 2001-02-15 2007-03-29 그레이트 레이크스 케미칼 코포레이션 하이드록시아릴 포스핀 옥사이드의 혼합물 및 이의 제조방법, 및 이로부터 유도된 에폭시 올리고머 생성물, 난연성 에폭시 조성물, 수지-함침된 복합물 및 적층물
US6887950B2 (en) * 2001-02-15 2005-05-03 Pabu Services, Inc. Phosphine oxide hydroxyaryl mixtures with novolac resins for co-curing epoxy resins
US6441067B1 (en) * 2001-08-23 2002-08-27 Chung-Shan Institute Of Science & Technology Phosphorus-containing compounds and their use in flame retardance
KR100425376B1 (ko) * 2001-10-29 2004-03-30 국도화학 주식회사 인 및 실리콘 변성 난연성 에폭시수지
JP3888254B2 (ja) * 2002-07-29 2007-02-28 富士電機ホールディングス株式会社 多層プリント配線板
US6762251B2 (en) * 2002-09-04 2004-07-13 Tohto Kasei Co., Ltd. Thermoplastic polyhydroxypolyether resin and an insulation film produced therefrom
TWI296001B (zh) * 2002-10-22 2008-04-21 Chang Chun Plastics Co Ltd
WO2005118604A1 (en) * 2004-05-28 2005-12-15 Dow Global Technologies Inc. Phosphorus-containing compounds useful for making halogen-free, ignition-resistant polymers
CN103254465A (zh) * 2007-06-14 2013-08-21 巴斯夫欧洲公司 阻燃组合物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1639174A (zh) * 2001-10-04 2005-07-13 阿克佐诺贝尔股份有限公司 羟基封端的低聚膦酸酯
CN1795223A (zh) * 2003-05-22 2006-06-28 苏普雷斯塔有限责任公司 用于环氧树脂的聚膦酸酯阻燃固化剂

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TAO WU ET AL.: "Curing of Epoxy Resin with Poly(m-phenylenemethylphosphonate)", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104379627A (zh) * 2012-06-15 2015-02-25 陶氏环球技术有限责任公司 潜伏型催化固化剂
CN110337484A (zh) * 2016-12-14 2019-10-15 溴化合物有限公司 不含锑阻燃性环氧树脂组合物
US11560448B2 (en) 2016-12-14 2023-01-24 Bromine Compounds Ltd. Antimony free flame-retarded epoxy compositions
CN111094422A (zh) * 2017-09-13 2020-05-01 瀚森公司 环氧树脂体系
CN115260453A (zh) * 2017-09-13 2022-11-01 瀚森公司 环氧树脂体系
CN115260453B (zh) * 2017-09-13 2023-10-03 瀚森公司 环氧树脂体系
CN112574643A (zh) * 2020-12-16 2021-03-30 苏州太湖电工新材料股份有限公司 一种阻燃型水性绝缘漆及其制备方法和应用

Also Published As

Publication number Publication date
US20110201724A1 (en) 2011-08-18
EP2346939A1 (en) 2011-07-27
TW201035157A (en) 2010-10-01
WO2010051182A1 (en) 2010-05-06
JP2012507599A (ja) 2012-03-29

Similar Documents

Publication Publication Date Title
CN102203176A (zh) 含磷阻燃环氧树脂组合物、其预浸料和层压板
US20020032279A1 (en) Flame retardant resin and flame retardant composition containing the same
US6733698B2 (en) Mixture of mono-, bis- and tris-(hydroxyaryl) phosphine oxides useful to make polyglycidyl ethers or in epoxy compositions
US20080097014A1 (en) Non-Halogen Flame Retardant and Highly Heat Resistant Phosphorous-Modified Epoxy Resin Compositions
JP2013166959A (ja) 混合触媒系を含む硬化性エポキシ樹脂組成物およびそれから作られた積層体
JP2000080251A (ja) リン変性難燃性エポキシ樹脂組成物およびその製造方法およびそのリン変性難燃性エポキシ樹脂組成物を用いた成形品および積層体
US8404161B2 (en) Hydroxyphenyl phosphine oxide mixtures and their use as flame retardant's for epoxy resins
JP2004143424A (ja) 非ハロゲン系樹脂組成物
JP5793086B2 (ja) エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
EP2368930A1 (en) Novel low dielectric resin varnish composition for laminates and the preparation thereof
JP4253092B2 (ja) ラジカル重合性樹脂組成物の製造方法
JP5686512B2 (ja) リン含有エポキシ樹脂、樹脂組成物、およびその難燃性硬化物
US20130025916A1 (en) Flame retardant epoxy laminate containing metal phosphonate
KR101954455B1 (ko) 인 함유 페놀 수지와 그 제조 방법, 그 수지 조성물, 경화물
KR20100021409A (ko) 신규 난연성 에폭시 수지와 그 에폭시 수지를 필수성분으로 하는 에폭시 수지조성물 및 그 경화물
US8772424B2 (en) Curable phosphorus-containing flame retardant epoxy resin
JP5653374B2 (ja) リン含有エポキシ樹脂、該樹脂を含有するエポキシ樹脂組成物、該樹脂を含有する硬化性エポキシ樹脂組成物、及びそれらから得られる硬化物
US20030069356A1 (en) Phosphorous-containing epoxy resin, flame-retardant highly heat-resistant epoxy resin composition containing the resin, and laminate
JP5214658B2 (ja) エポキシ樹脂、エポキシ樹脂組成物および硬化物
JPH0853533A (ja) 積層板用臭素化エポキシ樹脂組成物
US9388340B2 (en) Preparation of hydroxyphenyl phosphine oxide mixtures
TWI487781B (zh) 磷氮型無鹵耐燃樹脂組成物、預浸材及膠片、銅箔積層板及其印刷電路板
US20140221582A1 (en) Hydroxyphenyl Phosphine Oxide Mixtures and Their Use as Flame Retardants for Epoxy Resins

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20110928