TW202325762A - 一種苯並噁嗪樹脂、其組成物及由其製成的銅箔基板 - Google Patents

一種苯並噁嗪樹脂、其組成物及由其製成的銅箔基板 Download PDF

Info

Publication number
TW202325762A
TW202325762A TW111119173A TW111119173A TW202325762A TW 202325762 A TW202325762 A TW 202325762A TW 111119173 A TW111119173 A TW 111119173A TW 111119173 A TW111119173 A TW 111119173A TW 202325762 A TW202325762 A TW 202325762A
Authority
TW
Taiwan
Prior art keywords
formula
resin
benzoxazine
benzoxazine resin
filler
Prior art date
Application number
TW111119173A
Other languages
English (en)
Other versions
TWI800386B (zh
Inventor
廖世灝
楊敏原
周雅燕
邱政鴻
陳正中
Original Assignee
元鴻應用材料股份有限公司
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 元鴻應用材料股份有限公司 filed Critical 元鴻應用材料股份有限公司
Application granted granted Critical
Publication of TWI800386B publication Critical patent/TWI800386B/zh
Publication of TW202325762A publication Critical patent/TW202325762A/zh

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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • B32B15/14—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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B5/22—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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • 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
    • B32B2262/10—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
    • 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
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • 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
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/06—Copolymers with styrene
    • 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
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

一種樹脂，包括如下式1-1的化合物： 其中，n介於1至5之間，R 1、R 2、R 3、R 4係如本文所定義。

Description

一種樹脂、其組成物及由其製成的銅箔基板
本發明關於一種樹脂，尤指一種適用於電子元件的苯並噁嗪樹脂。
苯並噁嗪是一種含氮且具有類似酚醛樹脂結構的熱固性樹脂，由 O 原子和 N 原子構成的六元雜環化合物體系，苯並噁嗪一般是由酚類化合物、一級胺和甲醛類化合物通過曼尼希反應(Mannich reaction)製得的化合物，在加熱或催化劑的作用下，開環聚合生成一種類似酚醛樹脂的網狀結構。
由於苯並噁嗪樹脂具有低體積收縮率(在聚合過程中無小分子副產物)；低吸濕率；優良的耐熱性、機械性、電氣性以及阻燃性等優點，因此，苯並噁嗪樹脂被廣泛應用於複合材料的基體樹脂、無溶劑浸漬漆、電子封裝材料、阻燃材料和電絕緣材料等領域，其中，苯並噁嗪樹脂乃為製造銅箔基板(Copper Clad Laminate，CCL)的重要材料。
習知的苯並噁嗪樹脂可參閱Jiangbing Chen等人在Applied Polymer Materials期刊於2019年所發表的「Design and Preparation of Benzoxazine Resin with High-Frequency Low Dielectric Constants and Ultralow Dielectric Losses」(Appl. Polym. Mater. 2019, 1, 625-630)，該文獻揭示的苯並噁嗪樹脂中的R 1是含甲基的DAM，因而使得苯並噁嗪樹脂的加工性差，脆性高，不利於後續製成為銅箔基板及電路板，且不易加工，故實用性不高。
隨現今對於電路板的要求日益升高，利用現有苯並噁嗪樹脂製成的銅箔基板的耐熱性、機械性及尺寸穩定性等性質仍有改善的空間。
本發明的主要目的在於解決現有苯並噁嗪樹脂製成的銅箔基板的耐熱性、機械性及尺寸穩定性等性質有待改善的問題。
為達上述目的，本發明提供一種樹脂，包括如下式1-1的化合物： (式1-1)
其中，n介於1至5之間，R 1選自以下所組成的群組： (式1-2) (式1-3) (式1-4) (式1-5) (式1-6) (式1-7) (式1-8) (式1-9) (式1-10) (式1-11)
其中，n2介於2至6之間； (式1-12)
其中，n3介於1至5之間； (式1-13) (式1-14) (式1-15)
其中，n4介於2至10之間； (式1-16)
其中，R 2為選自C1-C10碳鏈或以下所組成的群組： (式1-17) (式1-18) (式1-19) (式1-20) (式1-21) (式1-22) (式1-23)
其中，R 3為單鍵或選自以下所組成的群組： (式1-24) (式1-25) (式1-26) (式1-27) (式1-28) (式1-29) (式1-30) (式1-31) (式1-32) (式1-33) (式1-34) (式1-35)
其中，R 4為H、C1至C12烷基或烯丙基；
其中，R 5為苯環、H或C1至C12烷基。
為達上述目的，本發明還提供一種如下式的樹脂：
其中，n介於1至5之間。
為達上述目的，本發明更提供一種如下式的樹脂：
其中，n介於1至5之間。
本發明基於分子設計特性，提供一種長鏈型且含有可交聯官能基團的苯並噁嗪樹脂，具有高韌性與優異的機械性質(如抗拉強度與伸長率)，能大幅改善現有聚苯並噁嗪製成的銅箔基板之脆性、加工性不佳以及尺寸穩定性不佳的問題。根據選擇不同的R 1，長鏈(long chain)可改善機械性質(如抗拉強度與伸長率)，應用於銅箔基板之中可降低孔裂及白紋的產生；脂肪族(aliphatic)可改善苯並噁嗪樹脂的電氣性質，增加阻抗與降低Dk/Df，應用於銅箔基板之中可以增加絕緣阻抗且降低高頻損耗，且脂肪族(aliphatic)還可增加苯並噁嗪樹脂中對溶劑的溶解度，應用於銅箔基板之中可降低溶劑使用量，具有環保與低成本的優點；環鏈(cyclic chain)、長鏈(long chain)、環狀脂肪族(cyclic aliphatic)及Si皆可降低苯並噁嗪樹脂的吸濕性及降低Dk/Df；芳香族(aromatic)可增加苯並噁嗪樹脂的耐熱性以及機械性質。進一步地，利用本發明揭示的苯並噁嗪樹脂製備的印刷電路板，除阻燃性能達到UL94 V0級，也具有優異的耐熱性、高尺寸穩定性、高機械強度、高韌性、耐離子遷移性以及優異的加工性能。
本發明揭露一種具有如下式1-1的結構的苯並噁嗪樹脂： (式1-1)
其中，n介於1至5之間，可為整數或非整數，R 1選自以下所組成的群組： (式1-2) (式1-3) (式1-4) (式1-5) (式1-6) (式1-7) (式1-8) (式1-9) (式1-10) (式1-11)
其中，n2介於2至6之間； (式1-12)
其中，n3介於1至5之間； (式1-13) (式1-14) (式1-15)
其中，n4介於2至10之間。 (式1-16)
其中，R 2為選自C1-C10碳鏈或以下所組成的群組： (式1-17) (式1-18) (式1-19) (式1-20) (式1-21) (式1-22) (式1-23)
其中，R 3為單鍵或選自以下所組成的群組： (式1-24) (式1-25) (式1-26) (式1-27) (式1-28) (式1-29) (式1-30) (式1-31) (式1-32) (式1-33) (式1-34) (式1-35)
其中，R 4為H、C1至C12烷基或烯丙基。
其中，R 5為苯環、H或C1至C12烷基。
根據選擇不同的R 1，長鏈(long chain)可改善機械性質(如抗拉強度與伸長率)，應用於銅箔基板之中可降低孔裂及白紋的產生；脂肪族(aliphatic)可改善苯並噁嗪樹脂的電氣性質，增加阻抗與降低Dk/Df，應用於銅箔基板之中可以增加絕緣阻抗且降低高頻損耗，且脂肪族(aliphatic)還可增加苯並噁嗪樹脂中對溶劑的溶解度，應用於銅箔基板之中可降低溶劑使用量，具有環保與低成本的優點；環鏈(cyclic chain)、長鏈(long chain)、環狀脂肪族(cyclic aliphatic)及Si皆可降低苯並噁嗪樹脂的吸濕性及降低Dk/Df；芳香族(aromatic)可增加苯並噁嗪樹脂的耐熱性以及機械性質。
以本發明的苯並噁嗪樹脂的R 1的式1-3來說，由於採用了醚基化合物，與現有技術採用的DAM((4,4'-diaminodiphenyl)methane)相比，式1-3的加工性優異，大幅改善了苯並噁嗪樹脂的加工性(式1-3 、式1-4、式1-10、式1-11、式1-12、式1-15亦同)。另一方面，以本發明的苯並噁嗪樹脂的R 1為式1-2、式1-4、式1-5、式1-6、式1-7、式1-11、式1-12、式1-15來說，與上列的現有技術相比，側鍊的結構可以提高溶解度，亦提升可加工性，對於成品的外觀和物性，皆有正面的功效。
以本發明的苯並噁嗪樹脂的R 1為式1-8、式1-9、式1-16來說，環狀芳香族(cyclic aromatic chain)亦提供了低吸濕性及低Dk/Df，且改善耐熱性及機械性質。以本發明的苯並噁嗪樹脂的R 1為式1-13、式1-14來說，脂肪族長鏈(aliphatic long chain)提供優異的機械性質。
根據本發明一實施例，提供一種如下式結構的樹脂(後稱BZ-1)。即，在式1-1之中，R 1為 ，R 2為H，R 3為 ，R 4為H。
根據本發明一實施例，提供一種如下式結構的樹脂(後稱BZ-7)。即，在式1-1之中，R 1為 ，R 2為H，R 3為 ，R 4為H。
BZ-1以及BZ-7在玻璃轉化溫度(glass transition temperature，T g)、Z軸熱膨脹係數(Z-CTE)以及抗撕強度具備平衡的優異表現，因此特別適合用於實務上的量產。
在一實施例中，用於合成式1-1的苯並噁嗪樹脂的材料主要包括二元胺、二元酚、一元酚以及甲醛，製備上，先將二元胺、二元酚以及一元酚加入一四口可分離式反應瓶中而得到一溶液，該反應瓶配置有加熱裝置、溫度計、攪拌機、冷卻管、滴入裝置及減壓回收裝置，以甲苯作為溶劑，再滴入甲醛。反應的通式如下：
其中，n介於1至5之間，可為整數或非整數。舉例來說，Z1選自單價烴基、單價烴氧基及鹵基。Z2及/或Z3可為以下化合物： (式1-36) (式1-37) (式1-38) (式1-39) (式1-40) (式1-41) (式1-42)
以下為說明上述揭示的樹脂的合成方法。
[合成例1-1]
將846 g的二(3-甲基-4-氨基-6-乙基)苯甲烷(4,4'-Methylenebis(2-ethyl-6-methylaniline)，MMEA)、228 g的雙酚A(Bisphenol A，BPA)、376 g的酚(Phenol)以及600 g的甲苯加入一3公升的四口可分離式反應瓶中而得到一溶液，對該溶液升溫至約40℃並攪拌均勻，攪拌時在20分鐘內逐滴加入819 g的甲苯溶液(含有44 wt.%的甲醛)至該溶液中，並繼續加熱該溶液直到約90℃，維持該溶液於約90℃的溫度並反應3小時。
待反應3小時，停止加熱及攪拌並靜置20分鐘，待該溶液分成二層後，移除上層的水相及微量的乳化物，再加熱至約90℃並利用減壓(低於約90毫米汞柱)的方式回收溶劑，待溫度至約130℃且回收全部溶劑後，即獲得重量約1730 g之氮氧雜環化合物(即苯並噁嗪樹脂)。
[合成例1-2]
將600 g的4,4'二胺基二苯醚(4,4'-Oxydianiline，ODA)、456 g的雙酚A(Bisphenol A，BPA)、188 g的酚(Phenol)以及600 g的甲苯加入一四口可分離式反應瓶中而得到一溶液，對該溶液升溫至約40℃並攪拌均勻，攪拌時在20分鐘內逐滴加入819 g的甲苯溶液(含有44 wt.%的甲醛)至該溶液中，並繼續加熱該溶液直到約90℃，維持該溶液於約90℃的溫度並反應3小時，反應式如下。
待反應3小時，停止加熱及攪拌並靜置20分鐘，待該溶液分成二層後，移除上層的水相及微量的乳化物，再加熱至約90℃並利用減壓(低於約90毫米汞柱)的方式回收溶劑，待溫度至約130℃且回收全部溶劑後，即獲得重量約1385 g之氮氧雜環化合物(即苯並噁嗪樹脂)。
[合成例1-3至合成例1-8]
合成方法如以上所述，而所選用的材料及配比則和以上合成例1-1、1-2列如下表1。合成例1-1至合成例1-8分別對應表1中的BZ-1至BZ-8，而表1的數字為各合成例的單體莫爾比。
在應用上，式1-1的樹脂可以和其他材料混合來做使用，在一例子中，式1-1的樹脂可以和填料、熱固性樹脂、補強材料以及增韌劑在一溶劑中混合、溶解或分散而製成漆狀的形式，該溶劑可為任何可溶解或分散上述各成分、但不與該等成分反應的惰性溶劑，包含但不限於甲苯、γ-丁內酯、甲乙酮、環己酮、丁酮、丙酮、二甲苯、甲基異丁基酮、N,N-二甲基甲醯胺(N,N-dimethyl formamide，DMF)、N,N-二甲基乙醯胺(N,N-dimethyl acetamide，DMAc)、N-甲基吡咯烷酮(N-methyl-pyrolidone，NMP)或以上的組合。
另一方面，本發明還揭示一種樹脂組成物以及由該樹脂組成物製成的銅箔基板。該樹脂組成物包括重量百分比介於30至50之間的苯并噁嗪樹脂(如式1-1)、一重量百分比介於35至55之間的填料、一重量百分比介於6至15之間的熱固性樹脂以及一重量百分比介於8至20之間的增韌劑。
為具體說明本發明技術，以下以根據本發明式1-1的苯並噁嗪製作印刷電路板用的金屬箔積層板(Metal clad laminate plate)來說明，並與其他的比較例進行比較，比較例所採用的苯並噁嗪樹脂的化學式如下式2-1所列。表2顯示了不同實施例的配方，單位為重量比例。 (式2-1)
當式2-1的苯並噁嗪樹脂為ODA-BZ時，R如下式2-2所列： (式2-2)
當式2-1的苯並噁嗪樹脂為MDA-BZ時，R如下式2-3所列： (式2-3)
先將式1-1的苯並噁嗪和一填料、一熱固性樹脂以及一增韌劑在一溶劑中混合，該填料為粒徑為10 μm的二氧化矽(SiO 2)，該熱固性樹脂採用購自於大和化學型號為KI-70的雙馬來醯亞胺樹脂(BMI)，該增韌劑採用型號為Ricon® 100的丁二烯-苯乙烯共聚物，該溶劑為使用甲苯、甲乙酮、及γ-丁內酯之混合物作為溶劑，得到一漆，接著利用輥式塗佈機將一基材(或稱補強材料) 浸漬於該漆，之後在175°下乾燥，從而獲得半固化態的預浸漬片。本實施例中，該基材採用型號2116的玻璃纖維布，厚度為0.08毫米，而該預浸漬片之漆含量為54 wt.%。
將四片該預浸漬片堆疊後，在最上方及最下方各設置一張0.5盎司的銅箔。隨後置於一熱壓機中進行高溫熱壓固化，以3.0°C/分鐘的升溫速度升溫至200°C至220°C之間，並在該溫度下，以15公斤/平方公分的壓力熱壓180分鐘，接著冷卻至室溫，即製成一雙面覆銅積層板。
對上述製程得到的雙面覆銅積層板，進行玻璃轉化溫度(glass transition temperature，T g)、Z軸的熱膨脹係數(Z-CTE)、抗撕強度以及耐熱測試的量測，結果顯示在表3。
T g是利用動態熱機械分析儀(dynamic thermomechanical analyzer, DMA)依IPC-TM-650 2.4.24.4規範的方法進行測量。Z-CTE是利用熱機械分析儀(thermal mechanical analyzer，TMA)依IPC-TM-650 2.4.24.5規範的方法進行測量，在低於T g的溫度(50℃至260℃之間)量測在Z軸方向上的熱膨脹係數改變率。抗撕強度是測量需要多少力才能將1/8英寸寬度的銅箔自板面上垂直撕起。耐熱測試是將經乾燥的雙面覆銅積層板在300℃的錫焊浴中浸泡100秒，重複3次後觀察外觀，若外觀有鼓泡凸起則為不佳，若外觀無鼓泡凸起則表示耐熱性優良，紀錄為「○」。
表1
    BZ-1 BZ-2 BZ-3 BZ-4 BZ-5 BZ-6 BZ-7 BZ-8
Diamine MMEA 3 3 3 3 3 3 -- --
ODA -- -- -- -- -- -- 3 --
BAPP -- -- -- -- -- -- -- 3
Bisphenol BPA 1 2 -- -- -- 1 1 1
BPF -- -- 1 -- -- -- -- --
DOD -- -- -- 1 -- -- -- --
DCDP-Diol -- -- -- -- 1 -- -- --
Phenol Phenol 4 2 4 4 4 -- 4 4
2-Naphthol -- -- -- -- -- 4 -- --
Aldehyde Formaldehyde 12 12 12 12 12 12 12 12
表2
  例1 例2 例3 例4 例5 例6 例7 例8 例9 例10 例11 例12 比較例1 比較例2 比較例3
BZ-1 33 -- -- -- -- -- -- -- 45 39 -- -- -- -- --
BZ-2 -- 33 -- -- -- -- -- -- -- -- 32 28 -- -- --
BZ-3 -- -- 33   -- -- -- -- -- -- -- -- -- -- --
BZ-4 -- -- -- 33 -- -- -- -- -- -- -- -- -- -- --
BZ-5 -- -- -- -- 33 -- -- -- -- -- -- -- -- -- --
BZ-6 -- -- -- -- -- 33 -- -- -- -- -- -- -- -- --
BZ-7 -- -- -- -- -- -- 33 -- -- -- -- -- -- -- --
BZ-8 -- -- -- -- -- -- -- 33 -- -- -- -- -- -- --
ODA-BZ -- -- -- -- -- -- -- -- -- -- -- -- 33 -- 31
MDA-BZ -- -- -- -- -- -- -- -- -- -- -- -- -- 33 --
填料 43 43 43 43 43 43 43 43 35 39 43 48 43 43 41
熱固性樹脂 13 13 13 13 13 13 13 13 11 12 9 14 13 13 12
增韌劑 11 11 11 11 11 11 11 11 9 10 16 10 11 11 16
表3
  例1 例2 例3 例4 例5 例6 例7 例8 例9 例10 例11 例12 比較例1 比較例2 比較例3
T g(℃) 203 201 198 202 187 209 183 182 212 207 198 215 176 172 167
Z-CTE (%) 4.2 4.4 4.3 4.2 4.6 4.1 4.6 4.8 3.6 4.1 4.1 3.6 5.3 5.5 5.8
抗撕強度(lb/ft) 6.6 6.8 6.9 6.8 6.5 6.3 6.2 7.2 6.5 6.4 6.6 6.6 5.6 5.4 6.1
耐熱測試 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

Claims (9)

  1. 一種樹脂，包括如下式1-1的化合物： (式1-1) 其中，n介於1至5之間，R 1選自以下所組成的群組： (式1-2) (式1-3) (式1-4) (式1-5) (式1-6) (式1-7) (式1-8) (式1-9) (式1-10) (式1-11) 其中，n2介於2至6之間； (式1-12) 其中，n3介於1至5之間； (式1-13) (式1-14) (式1-15) 其中，n4介於2至10之間； (式1-16) 其中，R 2為選自C1-C10碳鏈或以下所組成的群組： (式1-17) (式1-18) (式1-19) (式1-20) (式1-21) (式1-22) (式1-23) 其中，R 3為單鍵或選自以下所組成的群組： (式1-24) (式1-25) (式1-26) (式1-27) (式1-28) (式1-29) (式1-30) (式1-31) (式1-32) (式1-33) (式1-34) (式1-35) 其中，R 4為H、C1至C12烷基或烯丙基。 其中，R 5為苯環、H或C1至C12烷基。
  2. 一種樹脂組成物，包括一如請求項1且重量百分比介於30至50之間的苯并噁嗪樹脂、一重量百分比介於35至55之間的填料、一重量百分比介於6至15之間的熱固性樹脂以及一重量百分比介於8至20之間的增韌劑。
  3. 一種銅箔基板，係由請求項2的樹脂組成物製成。
  4. 一種如下式的樹脂： 其中，n介於1至5之間。
  5. 一種樹脂組成物，包括一如請求項4且重量百分比介於30至50之間的苯并噁嗪樹脂、一重量百分比介於35至55之間的填料、一重量百分比介於6至15之間的熱固性樹脂以及一重量百分比介於8至20之間的增韌劑。
  6. 一種銅箔基板，係由請求項5的樹脂組成物製成。
  7. 一種如下式的樹脂： 其中，n介於1至5之間。
  8. 一種樹脂組成物，包括一如請求項7且重量百分比介於30至50之間的苯并噁嗪樹脂、一重量百分比介於35至55之間的填料、一重量百分比介於6至15之間的熱固性樹脂以及一重量百分比介於8至20之間的增韌劑。
  9. 一種銅箔基板，係由請求項8的樹脂組成物製成。
TW111119173A 2021-12-16 2022-05-23 一種苯並噁嗪樹脂、其組成物及由其製成的銅箔基板 TWI800386B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TW110147223 2021-12-16
TW110147223 2021-12-16

Publications (2)

Publication Number Publication Date
TWI800386B TWI800386B (zh) 2023-04-21
TW202325762A true TW202325762A (zh) 2023-07-01

Family

ID=86744165

Family Applications (1)

Application Number Title Priority Date Filing Date
TW111119173A TWI800386B (zh) 2021-12-16 2022-05-23 一種苯並噁嗪樹脂、其組成物及由其製成的銅箔基板

Country Status (3)

Country Link
US (1) US20230193027A1 (zh)
CN (1) CN116265445A (zh)
TW (1) TWI800386B (zh)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1803887A (zh) * 2005-12-31 2006-07-19 四川东材企业集团有限公司 一种含芳烷基结构的苯并噁嗪树脂及其制备方法和用途
CN102634019B (zh) * 2012-04-25 2013-10-30 哈尔滨工程大学 混合双酚型共聚芴基苯并噁嗪预聚体及其制备方法
CN103834168B (zh) * 2014-02-25 2016-09-07 广东生益科技股份有限公司 一种无卤阻燃型树脂组合物

Also Published As

Publication number Publication date
CN116265445A (zh) 2023-06-20
TWI800386B (zh) 2023-04-21
US20230193027A1 (en) 2023-06-22

Similar Documents

Publication Publication Date Title
CA1056541A (en) Heat-resistant resin composition comprising polyaminobismaleimide, polyepoxy compound and aromatic vinyl copolymer and method for using the same
WO2012083727A1 (zh) 无卤高tg树脂组合物及用其制成的预浸料与层压板
KR20080000633A (ko) 벤족사진 및 에폭시 수지를 포함하는 조성물
TWI671355B (zh) 樹脂組合物，以及使用該組合物所製得之預浸漬片、金屬箔積層板、與印刷電路板
TWI620763B (zh) 樹脂組成物、及使用該樹脂組成物所製得之預浸漬片、金屬箔積層板及印刷電路板
JP2010043253A (ja) 熱硬化性絶縁樹脂組成物、並びにこれを用いたプリプレグ、樹脂付フィルム、積層板、及び多層プリント配線板
TW201339243A (zh) 樹脂組合物及其應用
TWI781304B (zh) 樹脂組成物、清漆、積層板以及印刷配線基板
US20120097437A1 (en) Resin Composition, and Prepreg and Printed Circuit Board Prepared Using the Same
JP5010357B2 (ja) 新規ポリアミド酸、ポリイミド並びにその用途
TWI804796B (zh) 一種改性馬來醯亞胺化合物及其製備方法和應用
US9006377B2 (en) Resin composition and uses of the same
TW202325762A (zh) 一種苯並噁嗪樹脂、其組成物及由其製成的銅箔基板
CN114605779B (zh) 一种热固性树脂组合物及包含其的预浸料、电路基板和印刷电路板
TWI798102B (zh) 一種苯並噁嗪樹脂、其組成物及由其製成的銅箔基板
JPH03185066A (ja) 熱硬化性樹脂組成物
CN113185751A (zh) 一种无卤硅系阻燃型乙烯基树脂及其制备方法和在覆铜板中的应用
US8846790B2 (en) Resin composition, and prepreg and printed circuit board prepared using the same
TWI763282B (zh) 一種無鹵阻燃型樹脂組成物及其應用
TWI812412B (zh) 樹脂組成物、及使用該樹脂組成物所製得之半固化片、金屬箔積層板及印刷電路板
JP2007169392A (ja) ポリアミド酸ワニス組成物および金属ポリイミド複合体
KR0179655B1 (ko) 이미드계 프레폴리머 및 그 경화물
WO2023276379A1 (ja) 樹脂組成物、ワニス、積層板、プリント配線基板および成形品
TW201302836A (zh) 樹脂組合物及由其製成之半固化片與積層板
JPH07119300B2 (ja) 耐熱性積層板用プリプレグの製造方法