TW201035157A - Phosphorus-containing flame retardant epoxy resin composition, prepeg and laminate thereof - Google Patents

Phosphorus-containing flame retardant epoxy resin composition, prepeg and laminate thereof Download PDF

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Publication number
TW201035157A
TW201035157A TW098135940A TW98135940A TW201035157A TW 201035157 A TW201035157 A TW 201035157A TW 098135940 A TW098135940 A TW 098135940A TW 98135940 A TW98135940 A TW 98135940A TW 201035157 A TW201035157 A TW 201035157A
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TW
Taiwan
Prior art keywords
epoxy resin
resin composition
curable epoxy
coal
flame retardant
Prior art date
Application number
TW098135940A
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English (en)
Inventor
Sergei Levchik
Fabienne Samyn
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Icl Ip America Inc
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Publication date
Application filed by Icl Ip America Inc filed Critical Icl Ip America Inc
Publication of TW201035157A publication Critical patent/TW201035157A/zh

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    • 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
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    • 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
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    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • 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
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (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)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)

Description

.201035157 六、發明說明： 【發明所屬之技術領域】 本發明係關於阻燃性環氧樹脂組成物，特別是包含環 氧樹脂、聚烷基膦酸伸芳基酯硬化劑及四級鳞鹽或四級銨 鹽硬化觸煤之可硬化性阻燃性環氧樹脂組成物。可硬化性 阻燃性環氧樹脂組成物顯示用於預浸體的B-分段之可靠方 法的寛工作範圍（processing window)。 〇 【先前技術】 相關技術的詳細說明 阻燃性環氧樹脂由於極佳自熄性質、機械性質、抗水 蒸氣性及電性質而被使用於各種電絕緣材料中。在製備含 環氧樹脂之積層體中，習知將各種添加劑倂入環氧樹脂組 成物以改良所得積層體之阻燃性。已經建議許多類型的阻 燃性添加劑’然而，商業上最廣泛地使用之添加劑爲含鹵 Q 素之添加劑’例如四溴雙酚A，或用四溴雙酚A製備之環 氧樹脂。 雖然含鹵素之阻燃性添加劑例如四溴二苯基丙烷是有 效的’但從環境的觀點而言它們被被一些人認爲是不可取 的’且近幾年來已對無幽素環氧樹脂的調配物逐漸增加興 趣’其能夠符合阻燃性要求，該要求在標準“Underwriters
Lab oratory”測試方法UL 94中典型爲V-0。 有一些商業上可得之以磷爲主的阻燃性添加劑，其可 用以取代含鹵素之阻燃性添加劑。例如，藉由將添加型磷 -5- 201035157 系統阻燃劑例如磷酸三苯基酯（ΤΡΡ)、磷酸三甲苯基酯 (TCP)、磷酸甲苯酚基酯二苯基酯（CDP)、間苯二酧雙（磷 酸二苯基酯）（RDP)、雙酚A雙（磷酸二苯基酯）（BDP)等等（ 其爲磷酸酯系統化合物）倂入環氧樹脂組成物中，可維持 非燃性。該等調配物的例子係描述於例如美國專利第 5,919,844; 5,932,637; 6,348,523; 6,713，163 號及歐洲專 利申請案第1,3 59,1 74號。然而，因爲一般磷化合物例如 該等上文所描述者不與環氧樹脂反應，其他問題出現，例 如模製物件的吸濕後之焊料耐熱性及抗化學藥品性例如抗 鹼抵性等等被顯著地減少。因爲這些磷添加劑的顯著塑化 效果，所以經硬化之環氧樹脂的玻璃轉移溫度（Tg)也發現 顯著下降。 已建議使用反應性以磷爲主之阻燃劑取代環氧樹脂調 配物中的鹵化阻燃劑。現有技術對以磷爲主之阻燃性環氧 樹脂的槪述係由S. Levchik及E. Weil提供於“Review on thermal decomposition, combustion and fl am e - r e t ar d an c y of epoxy resins”，Polymer International，第 53 冊，2004 ’第1 9 0 1 - 1 9 2 9頁。在一些調配物中磷阻燃劑係與環氧樹 脂預反應而形成二-或多官能環氧樹脂，其然後用交聯劑 硬化。 先前技術描述使用某些含磷元素化合物作爲交聯或硬 化劑以與環氧樹脂一起使用作爲將磷元素引入環氧樹脂系 統的方法。例如，美國專利第4,973,63 1 ; 5,086，156 ; 6,403,220 ;6,740,732; 6,486,242; 6,733,698 及 6,887,950 號描述 -6- 201035157 使用二官能或三官能氧化膦交聯劑作爲有效硬化劑。上述 先前技術組成物不容易製備且需要外來的製備步驟。有利 的是提供一種可得自實際工業規模原料之化合物；且因此 ，會提供超越先前技術方法的經濟利益。 然而，環氧樹脂之最常利用的以磷爲主之阻燃性爲 9,10-二氫-9-氧雜-10-碟菲（？11〇3卩1161131^11“1^)10-氧化物 (DOPO)。通常知道二種將DOPO應用於環氧樹脂複合物的 方法》在第一方法中，如歐洲專利申請案第0,806,429及美 〇 國專利第6,645,63 1 ; 6,291,627及6,486,242號中所述，使 DOPO與環氧樹脂預反應。因爲DOPO爲單官能反應性化 合物，所以其終止環氧樹脂鏈且因此只有多官能（通常比 二官能環氧樹脂更貴）必須使用在這個步驟中。在第二個 方法中，如例如在歐洲專利申請案第1，1〇3,5 75及1，53 7，160 號及美國專利第 6,291，626 ; 6,441，067 ; 6,933,050 ; 6,534,601; 6,646,064; 6,762,251 及 6,984,716 號及在 Q PCT專利申請案第05/118604號中所述，使DOPO與苯醌 或酮型之化合物（具有這些功能性的部分，即二或多個的 氫氧基或胺基）預反應。此方法遭遇複雜性，其導致昂貴 的具有分子內低磷含量之化合物。 膦酸烷基及芳基酯類一般與環氧樹脂相容。特別是膦 酸低級烷基酯類是有價値的，因爲它們包含高比例的磷， 且因此能夠將良好的阻燃性質賦予膦酸低級烷基酯類倂入 其中之樹脂。膦酸酯使用在環氧樹脂中的例子顯示在例如 美國專利第5,710,305及6,353,080號中。然而，如果使 201035157 用膦酸酯作爲添加劑，他們遭遇到與上所述之未反應磷酸 酯類相似的問題。由於未反應膦酸酯的主要問題爲環氧化 合物之低玻璃轉移溫度及高吸濕性。當對於以鉛爲主的焊 料在約26(TC的溫度下或對於無鉛焊料在約288 °C下，引 進液體焊料浴時，一製造印刷電路板中的典型步驟，包含 高含量水分之積層體傾向於起泡及不合格。 羥基端基聚（甲基膦酸間-伸苯基酯）使用於環氧系統 係描述於PCT專利公開03/029258中。在此環氧樹脂在作 爲硬化觸煤之甲基咪唑存在下被聚（甲基膦酸間-伸苯基 醋）硬化。此外，如 T. Wu，A_M. Piotrowski，Q. Yao 及 S.V. Levchik 於 Journal of Applied Polymer Science，第 101 冊 ，第401 1 -4022頁中所述，此聚膦酸酯有效地硬化環氧樹 脂。因爲膦酸酯有效地倂入環氧樹脂網路中，最終硬化複 合物顯示高玻璃轉移溫度及低吸水性。PCT專利公開 04/06095 7描述一種使環氧樹脂與聚（甲基膦酸間-伸苯基 酯）預反應之方法，然而因爲此聚膦酸酯爲多官能化合物 ，所以其傾向於交聯環氧樹脂且因此預反應不能以商業規 模有效地控制。 因爲膦酸酯經由環氧基插入磷酸酯基P-O-C內而硬化 環氧樹脂’每單一反應在聚合物網路中造成分岐。此外， 一些常見環氧樹脂硬化觸煤，像咪唑類或三銨類，催化環 氧樹脂之自硬化連同環氧基插入P-〇_C。因此在較窄溫度 間隔中發生膠化。此限制預浸體之B-分段的工作範圍，因 爲在低溫度下或在短期內樹脂顯示過度流動，而在較高溫 -8 - 201035157 度下及/或經過在較長期間環氧樹脂可過度交聯而限制樹 脂流動。 在該技藝中眾所週知四級銨鹽類及錢鹽類，更明確地 四級鹵化銨及鹵化錢被使用於使環氧化物與包含酚系羥基 之化合物反應而產生高分子量環氧化合物。參見，例如： 美國專利第 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 ； p 3,948,8 55;及4,048,141號及歐洲專利第0,0 1 9,852號及 H. Lee 及 K. Neville 之環氧樹脂手冊，McGraw-Hill(1967) 及環氧樹脂之化學及技術，B. Ellis編輯，Blacie Academic 及Pro fessional(1993)。也描述在美國專利4,048,141中， 某些鳞觸煤促進鄰近環氧化物類及酚類、羧酸類或羧酸酐 類之間的反應。 在 S. Minegishi、S. Komatsu,、A. Kamey ama 及 T Nishikubo 之期刊出版（J. p〇lym. Sci·, Part A, Polym. ◎ Chem, 1999’第37冊’第959-965頁）中，描述使用四丁 基溴化銨、四丁基氯化銨、四丁基溴化辚及四丁基氯化鐵 作爲以使膦酸二芳基酯苯基酯與環氧化物反應之觸媒。反 應進行長時間（48小時）且產生線性聚磷酸酯。t. Wu、 A.M. Piotrowski、Q. Yao 及 S.V. Levchik(J· Applied polymer Science, 2006，第101冊，第4〇1i_4〇22頁）藉由示差掃描 卡計硏究環氧化物與聚（甲基膦酸間-伸苯基酯）之反應並 發現其減緩且不適合於商業環氧樹脂硬化循環。選擇2-甲 基咪唑作爲更有效率的觸煤。 -9 - 201035157 鑑於先前技術之限制，本發明之目的爲提供用於製備 環氧樹脂預浸體及環氧樹脂積層體及用製造印刷電路板及 多層印刷電路板之可硬化性阻燃性環氧樹脂組成物，其具 有寬工作範圍且因此其中預浸體可容易地B-分段。此外， 積層體必須顯示高熱穩定性及良好抗潮性。 【發明內容】 發明槪述 本發明提供一種可硬化性環氧樹脂組成物，其包含至 少一種可硬化性環氧樹脂、至少一種阻燃性硬化劑例如聚 烷基膦酸伸芳基酯硬化劑及至少一種硬化觸煤例如四級錢 或四級銨鹽硬化觸煤。 本發明係有關印刷電路板，例如，用於電子應用之印 刷電路板、電子元件之封裝材料、防護塗層、及結構及/ 或裝飾複合材料，其包含本文中所述之可硬化性阻燃性環 氧樹脂組成物。 較佳體系之說明 本發明之可硬化性阻燃性環氧樹脂組成物包含至少一 種可硬化性環氧樹脂作爲基本成分。此成分可爲含非鹵素 之環氧樹脂’例如，單官能環氧樹脂、脂族、環脂族及芳 族單官能環氧樹脂且包括該等化學如甲酚縮水甘油基醚、 苯甲基縮水甘油基醚。本發明之其他有效環氧樹脂包括（ 但不限制於）二官能、三官能、四官能及較高官能環氧樹 -10- 201035157 月旨。這些類型環氧樹脂的例子包括但不限制於雙酚A之二 縮水甘油醚類 '雙酚F之二縮水甘油醚類、雙酚S之二縮 水甘油醚' 二縮水甘油基—對一胺基酚、三縮水甘油基胺 基甲酚、三縮水甘油基一對—胺基酚、亞甲基二苯胺之四 縮水甘油醚類、酚系酚醛型環氧樹脂、甲酚系酚醛型環氧 樹脂、間苯二酚型環氧樹脂、具有萘骨架之環氧樹脂、聯 苯型環氧樹脂、二環戊二烯型環氧樹脂及二苯基莽型環氧 0 樹脂、等等。這些樹脂可個別地使用或以任何的適當組合 使用。即’可使用於本發明之其他有用環氧樹脂或此一般 類型的其他樹脂爲該等具有用於製造印刷電路板或其他電 子基板材料的效用者。同樣地，如果需要可使用任何這些 樹脂的相容混合物。 此成分（也就是，可硬化性環氧樹脂）之存在量範圍在 組成物的總重量之從約50至約9〇重量百分比。更佳地， M @ ft性環氧樹脂之存在量範圍在組成物的總重量之從約 Q 65至約90重量百分比。 Μ €基膦酸伸芳基酯硬化劑之存在量爲組成物的總重 量之從約5重量％至約4〇重量％，較佳地從約5重量％至 約25重量％。此阻燃性硬化劑，如更完全描述在Pct國 際專利公開號 WO 03/029258中，該專利之內容以其全文 引用方式合倂於本文中，爲包含重複單元_0P(0)(R)_0_伸 芳基-之寡聚膦酸酯，其中R可爲包含最多至約8個碳原 子·（較佳最多至約6個碳原子）之直鏈或支鏈烷基且其具有 大於約1 2重量％之磷含量。在組成物中之膦酸酯種類也包 -11 - 201035157 含該等包含-〇H端基者，可能地，該等不包含-〇H端基者 。較佳R基爲甲基，但可爲任何低級烷基。在一體系中， 該聚烷基膦酸伸芳基酯硬化劑爲聚（甲基膦酸間-伸苯基 醋）。 “伸芳基”表示任何二酚之基團。二酚較佳應中具有其 二個在非毗連位置的羥基。例子包括間苯二酚類；氫醌類 :及雙酚類，例如雙酚A、雙酚F及4,4’-雙酚、酚酞' 4,4'·硫二酚或4,4’-磺醯基二酚。伸芳基可爲l，3-伸苯基、 1,4-伸苯基、或雙酚二基單元，但較佳爲l，3-伸苯基。 在一體系中該硬化觸煤爲至少一種以下式描述者： Γ〒2 Ί
Ri—X-R3 Y'm L k」m 其中及R4各自獨立爲包含從1至約12 個碳原子的烴基或經惰性取代之烴基基團，X爲P或N， Y爲陰離子及m爲陰離子之價。在一體系中該烴基基團爲 包含最多至約12個碳原子之直鏈或支鏈烷基，其可經〇 、N或S惰性取代。這些化合物可替代性描述爲四烴基鐵 或四烴基銨鹽類。這些觸煤對於以適當反應速率選擇性地 催化環氧基插入P-0-C鍵之所要反應是令人驚訝地有效的 。在一體系中Y爲選自由溴離子、氯離子、碘離子、乙酸 根離子、乙酸根離子複合物、乙酸根離子/乙酸複合物、 憐酸根離子、磷酸根離子複合物及氫氧離子所組成群組之 -12- 201035157 陰離子。在一體系中m可爲1、2或3。 較佳觸煤爲（但不限制於）四級鐵及銨鹽類。四級鱗鹽 類包括（例如）四丁基氯化鱗、四丁基溴化銹、四丁基碘化 鱗、四丁基乙酸錢複合物、四苯基氯化錢、四苯基溴化鱗 '四苯基碘化鱗、乙基三苯基氯化鐵、乙基三苯基溴化鐵 、乙基三苯基碘化錢、乙基三苯基乙酸鱗複合物、乙基三 本基憐酸鱗複合物、丙基二苯基氯化鐵、丙基三苯基漠化 〇 鱗、丙基三苯基碘化錢、丁基三苯基氯化鱗、丁基三苯基 溴化鳞、丁基三苯基碘化鱗、乙基三-對一甲苯基乙酸鱗 /乙酸複合物、乙基二苯基乙酸錢/乙酸複合物或其組合等 等’如描述於美國專利第5,208,3 17、5,1 09,099及4,98 1,926 號中’各專利之內容以其全文引用方式合倂於本文中。最 佳觸煤包括四乙基溴化銨、四乙基氫氧化銨、乙基三甲苯 基乙酸鱗及乙基三苯基乙酸鱗。 四級銨鹽類包括（例如）四甲基氯化銨、四甲基溴化銨 Q 、四甲基碘化銨、三乙基苯甲基氯化銨、三乙基苯甲基溴 化銨、三乙基苯甲基換化銨、四乙基氯化錢、四乙基溴化 銨、四乙基碘化銨、四乙基氫氧化銨、四（正- 丁基）氯化 鞍、四（正一丁基）溴化錢、四（正_ 丁基）澳化錢、四（正一 丁基）氫氧化銨、四（正-辛基）氯化銨、四（正—辛基）溴化銨 、四（正一辛基）碘化銨、四（正一辛基）氫氧化銨、甲基參（正 —辛基）氯化錢、雙（四苯基正膦亞基（phosphoranylidene))氯 化銨、等等。 使用觸煤之量視觸煤的分子量、觸煤的活性及想要進 -13- 201035157 行之聚合的速度而定。一般，觸煤之使用量爲從每100份 的樹脂〇.〇1份（P.h.r.)至約1.0 p.h.r.，更佳地，從約0.〇! p.h.r.至約0.5 p.h.r.及最佳地，從約0.1 p.h.r.至約〇.5 p.h.r。在本文之一體系中，在此應了解樹脂的份數係有關 本文所述之可硬化性環氧樹脂的份數。 本發明之環氧樹脂組成物可包含任意添加劑，例如， 輔助阻燃性添加劑，以及下列類型之材料：纖維及/或布 加強添加劑；無機塡充劑，例如Al(OH)3、Mg(OH)2或砂 石；脫膜劑；著色劑；等等。 在本文之一體系中，環氧樹脂組成物可使用於其他應 用’例如電子應用’例如預浸體、印刷電路板、電子元件 之封裝材料、防護塗層、結構及/或裝飾複合材料，於如 S忍爲需要時視特別應用而定之量，但在一非限制較佳體系 中可使用於從約0.01 p.h.r·至約2.0 P.h.r·，更佳地從約 0 · 0 1 p · h · r _至約0.5 p · h · r ·及最佳地從約〇 · 1 p . h · r.至約〇 5 p . h · r ·之量。 【實施方式】 本發明以下列實例進一步說明： 實例 材料 環氧樹脂1 ’（PNE)酚系酚醛環氧樹脂，d.E.N. 43 8， 陶氏化學品牌 -14- 201035157 環氧樹脂2,（CNE)木焦油醇系酚醛環氧樹脂，EPON 164, H e X i ο η品牌 硬化劑，（ΡΜΡ)聚（甲基膦酸間-伸苯基酯），Fyrol ΡΜΡ, ICL-IP品牌 觸煤1:(ETPPA)乙基三苯基乙酸鱗（在甲醇中的70% 溶液），購自Alfa Aesar 觸煤2 : (ETPPB)乙基三苯基溴化辚，Dishman公司之 產品 0 觸煤3 : (2-MI)2 -甲基咪Π坐，Amicure AMI-2，空氣化 工產品公司（Air Products)品牌 觸煤 4 : (2-PI)2-苯基咪唑，Amicure PI-2，空氣化工 產品公司品牌 觸煤5: (DMAPM)雙（二甲胺基丙基）甲胺，Polycat 77 ，空氣化工產品公司品牌 觸煤 6 : (DMAMP)<90%參-2,4,6-(二甲胺基甲基）酚 Q +<10%雙（二甲胺基甲基）酚，Anc amide K54，空氣化工產 品公司品牌 溶劑：甲基乙基酮，（MEK)，購自Fluka 玻璃布：7628/50式樣，BGF工業之產品 銅箔：古爾德電子公司（Gould Electronics Inc_), (JTC，1·0 盎斯 /呎 2) 清漆之製備 將稱重之環氧樹脂及Fyrol ΡΜΡ在分開之廣口瓶中加 -15- 201035157 熱至100-120°的溫度。將樹脂及Fyrol PMP倒進安裝機械 攪拌器、溫度計及加熱包之3頸圓底燒瓶中。然後在連續 攪拌下加入25 p.h.r.之MEK直到獲得透明均勻的溶液。 以另外加入MEK將溶液的黏度調整到700- 1 000 cPa(@ 25°C )。將觸煤分開地溶解在MEK或丙酮中且加到清漆’最後 於 0.15-1.0 p.h.r 之量。 預浸體之製造 在室溫下在玻璃布（1 〇 . 5 X 1 0 · 5吋）之一側手工刷上清漆 。將玻璃布放置在175-185 °C之預熱空氣循環烘箱中且暴 露在熱下經某時段。用不同的暴露時間重複實驗。製造具 有約40%之樹脂含量的預浸體。 樹脂流動測量 根據IPC-TM-650測試2.3.16.2測試所得預浸體之樹 脂流動。樹脂流動根據暴露時間作圖，其正常地產生具有 負斜率的線性圖。計算之斜率表示工作範圍的特性。從-0.1 至-0.5之斜率表示寬工作範圍，而從-0.7至-1.5之斜率表 示窄工作範圍。 積層體之製造
將8個底部及上端具有銅箔之預浸體的積材放置在二 個不銹鋼板之間。將四張牛皮紙放置在板上面及下面。將 整個組合放置在液壓機中，其線性地加熱到1 85或20(TC • 16 - 201035157 。在170°C下施用200 psi之壓力。將積層體在等溫（185°c 或200°C)加熱90分鐘，接著在215°C或230°C下分別地後 硬化1 5分鐘而硬化。 壓力鍋測試 根據IPC-TM-650，測試2.3.7.1從積層體蝕刻銅。壓 力鍋測試（PCT)係根據IPC-TM 650，測試2.6.16使用下列 0 修正進行：（a)將樣品在高壓釜中暴露於蒸氣中經1，2及 4小時；（b)焊料浴的溫度固定在28 8 t，（c)將樣品浸在焊 料經5分鐘中。 玻璃轉移溫度（Tg) 玻璃轉移溫度係藉由示差掃描卡計（DSC)根據IPC-TM 650 ，測試2.4.2 5測量。 Q 熱穩定性 積層體之熱穩定性係藉由熱重分析（TGA)在氮的惰性 大氣中以1 0 °C /分鐘之加熱速率測量。5百分比重量損失 被記錄爲Td。 -17- 201035157
Mali晷忉鹦幽鹦岗Ma刮鬆N鹦螂鹋，鬆链1|忉殮赃一撇卜I嗽 比較 實例10 100 CN |觸煤6 1 q 1190__I -1.4 實例9 100 in cs |觸煤5 1 q r-H 180 1__-1.2 1 實例8 100 (S i觸煤4 CO d 180 C) o ΰ |實例7 | 100 (N i觸煤3 1 1 0.30 1 180 On 〇 實例6 100 V) (N 1觸煤3 1 1 0.15 1 g T-H o 185〇C > 90 215。。 ， 15 淡褐色 合格 不合格 1 m 365 本發明 實例5 37.5 37.5 : <N 觸煤2」 0.35 to 00 m o 200。。，90 230〇C > 15 黃色 1 合格 不合格 160 367 實例4 1—一37二5」 | 一 3—L5」 (N 觸煤1 0.35 g cn 〇 200〇C，90 230〇C ' 15 黃色 1 1 合格 On T—^ 367 實例3 〇〇 00 r〇 艺 1觸煤1 1 ! 0.35 180 m O 200°C，90 230〇C，15 黃色 1 合格 合格 § T—Η 367 實例2 JO (N 1觸煤1 1 I 0.35 1 180 L 0.5— .1 200°C，90 230〇C ' 15 黃色 合格 合格 不合格 » 1 ^ r-m |實例1 j JO <N [觸煤1」 I 0.35 I 180 o 185°C，90 215〇C ' 15 |黃色| I合格| 不合格 1 in 寸 378 環氧樹脂卜重量％ 環氧樹脂2，重量％ PH S I H pu, 觸煤 觸煤 ’ p.h.r. 預浸體 B-分段，°C 樹脂流動a 積層體 硬化週期， T°c/分鐘 顏色 PCT，1小時 PCT，2小時 PCT，4小時 Tg - (DSC) > °C Td，5重量％損失 -18- 201035157 從表1可知觸煤4、5及6產生用於預浸體的B -分段 之非常窄的工作範圍，因此它們不適用於積層體的製造。 觸煤3，雖然產生可接受的工作範圍，但於0.15 p.h.r.顯 示不良之積層體性質。觸煤3之濃度增加至〇 · 3 p · h · r ·造成 工作範圍的變窄。觸煤3、4、5、6也造成強烈地淡褐色 染色之積層體，其可能損害積層體的品質檢驗。 對於本發明之其他體系，熟習該項技術者從審議說明 書或本文所揭示的發明實務將會是顯而易知的。意欲說明 書及實例只被認爲是示範，且本發明的真實範圍及精神由 下列申請專利範圍定義。 "19-

Claims (1)

  1. 201035157 七、申請專利範圍： 1 · 一種可硬化性環氧樹脂組成物，其包含至少一種可 硬化性環氧樹脂、至少一種阻燃性硬化劑及至少一種硬化 觸煤。 2.如申請專利範圍第1項之可硬化性環氧樹脂組成物 ，其中該阻燃性硬化劑爲聚烷基膦酸伸芳基酯。 3 ·如申請專利範圍第1項之可硬化性環氧樹脂組成物 ，其中該阻燃性硬化劑爲聚（甲基膦酸間-伸苯基酯）。 〇 4.如申請專利範圍第1項之可硬化性環氧樹脂組成物 ，其中該可硬化性環氧樹脂係以範圍在該可硬化性環氧樹 脂組成物之總重量的從約50至約90重量百分比之量存在 〇 5 .如申請專利範圍第1項之可硬化性環氧樹脂組成物 ，其中該可硬化性環氧樹脂係以範圍在該可硬化性環氧樹 脂組成物之總重量的從約65至約90重量百分比之量存在 ❹ 6. 如申請專利範圍第2項之可硬化性環氧樹脂組成物 ，其中該聚烷基膦酸伸芳基酯係以範圍在該組成物之總重 量的從約5至約40重量百分比之量存在。 7. 如申請專利範圍第1項之可硬化性環氧樹脂組成物 ，其中該至少一種觸煤係以下式描述： Γ ί2 η Ri—X-R3 Y，m L t」m -20- 201035157 其中R1、R2 ' R3及R4各自獨立爲烴基或經惰性取代 之烴基基團’ X爲P或Ν，γ爲陰離子及m爲該陰離子之 價。 8 ·如申請專利範圍第1項之可硬化性環氧樹脂組成物 ，其中該觸煤爲銨四級鹽或鎸四級鹽。 9.如申請專利範圍第1項之可硬化性環氧樹脂組成物 其中該觸煤以每100份可硬化性環氧樹脂從約〇 〇1至 約1. 〇份的之量存在 10.—種預浸體， 其包含如申請專利範圍第 項之組 成物。 1·—種積層體 其包含如申請專利範圍第 項之組 成物。 1 2 · —種用於印刷電路板之封裝材 專利範圍第1項之組成物。 料’其包含如申請 1 3 .—種防護塗層，其包含如申§靑 組成物。 專利範圍第1項之 1 4 _ —種結構及/或裝飾複合材料 範圍第1項之組成物。 其包含如申請專利 201035157 四、指定代表圖： (一） 本案指定代表圖為：無 (二） 本代表圖之元件符號簡單說明：無 201035157 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無 -4-
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CN102203176A (zh) 2011-09-28
US20110201724A1 (en) 2011-08-18
JP2012507599A (ja) 2012-03-29
WO2010051182A1 (en) 2010-05-06

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