TW202225321A - Low expansion coefficient, low df, high rigidity, halogen-free resin composition, laminates and printed circuit boards - Google Patents

Abstract

A low expansion coefficient, low Df, hight rigidity, halogen-free resin composition, laminate and printed circuit board are provided. The composition includes (a) 1 to 10 parts by weight of cresol novolac epoxy resin, (b) 50 to 70 parts by weight of bismaleimide resin, (c) 30 to 45 parts by weight of polyhydroxy modified styrene resin, (d) 60 to 90 parts by weight of cyanate ester hardener and (e) 1 to 20 parts by weight of non-DOPO phosphorus-containing flame retardant. By the halogen-free epoxy resin composition with a specific composition and ratio, the halogen-free epoxy resin composition has a low dielectric loss, also improves the toughness and heat resistance of the board.

Description

低膨脹係數低介電損耗高剛性無鹵樹脂組成物、積層板以及印刷電路板Low expansion coefficient, low dielectric loss, high rigidity, halogen-free resin composition, laminates, and printed circuit boards

本發明涉及一種樹脂組成物以及使用環氧樹脂組成物積層板與印刷電路板，特別是涉及一種低膨脹係數、低介電損耗、高剛性的無鹵樹脂組成物、積層板以及印刷電路板。The invention relates to a resin composition, a laminate and a printed circuit board using the epoxy resin composition, in particular to a halogen-free resin composition, laminate and printed circuit board with low expansion coefficient, low dielectric loss and high rigidity.

在通訊電子市場持續發燒下，高頻高速傳輸已成必要選項，而扮演著承載元件、電源供應以及訊號傳輸的電路板，即成為本領域發展上的關鍵，而現有技術環氧樹脂及酚醛樹脂材料的印刷電路板，已無法滿足高頻的進階應用。Under the continuous fever of the communication electronics market, high-frequency and high-speed transmission has become a necessary option, and the circuit board, which plays the role of carrying components, power supply and signal transmission, has become the key to the development of this field. The existing epoxy resin and phenolic resin The printed circuit board of the material can no longer meet the advanced application of high frequency.

印刷電路板技術中，主要是包括環氧樹脂與硬化劑的熱固性樹脂組成物，並與補強材料(例如玻璃纖維布)加熱結合形成半固化膠片(prepreg)，再於高溫高壓將其與上、下兩片銅箔壓合而成銅箔積層板(或稱銅箔基板)。一般熱固性樹脂組成物使用具有羥基(-OH)的酚醛(phenol novolac)樹脂硬化劑，其與環氧樹脂結合後會使環氧基開環形成羥基，而羥基則會提高介電常數及介電損耗值，且易與H ₂O鍵結，造成吸濕性增加。 In the printed circuit board technology, it is mainly a thermosetting resin composition including epoxy resin and hardener, which is heated and combined with a reinforcing material (such as glass fiber cloth) to form a prepreg, which is then combined with the upper, The next two pieces of copper foil are pressed together to form a copper foil laminate (or copper foil substrate). Generally, phenol novolac resin hardener with hydroxyl group (-OH) is used for thermosetting resin composition. After combining with epoxy resin, the epoxy group will open the ring to form hydroxyl group, and the hydroxyl group will increase the dielectric constant and dielectric Loss value, and easy to bond with H ₂ O, resulting in increased hygroscopicity.

現有技術的環氧樹脂組成物使用含鹵素成份的阻燃劑(特別是溴系阻燃劑)，如四溴環己烷、六溴環癸烷以及2,4,6-三(三溴苯氧基)-1,3,5-三氮雜苯等，含鹵素成份的阻燃劑具有阻燃性好且添加少的優點，然而，鹵素產品在產品製造、使用，更甚至在回收或丟棄時易對環境造成污染，除此之外，含鹵素的電子設備廢棄物在燃燒時會產生腐蝕性、毒性氣體及煙霧，且在燃燒後產物會檢測出二噁英、二苯並呋喃等致癌物質。因此，無鹵阻燃印刷電路板已成為本領域的開發重點。The epoxy resin composition of the prior art uses halogen-containing flame retardants (especially brominated flame retardants), such as tetrabromocyclohexane, hexabromocyclodecane and 2,4,6-tris(tribromobenzene) oxy)-1,3,5-triazabenzene, etc., halogen-containing flame retardants have the advantages of good flame retardancy and less addition. However, halogen products are used in product manufacturing, use, and even recycling or discarding. In addition, the halogen-containing electronic equipment waste will produce corrosive, toxic gas and smoke when burned, and the products after burning will detect carcinogens such as dioxin and dibenzofuran. substance. Therefore, halogen-free flame retardant printed circuit boards have become the focus of development in this field.

除了發展無鹵阻燃印刷電路板之外，銅箔基板的耐熱性、難燃性、低介電損耗、低吸濕性、高交聯密度、高玻璃轉化溫度、高接合性、適當之熱膨脹性等特性更是印刷電路板的開發及製造的重要課題，是以，環氧樹脂、硬化劑及補強材的材料選擇成了主要影響因素。In addition to the development of halogen-free flame retardant printed circuit boards, copper foil substrates have heat resistance, flame retardancy, low dielectric loss, low moisture absorption, high crosslink density, high glass transition temperature, high bonding, and appropriate thermal expansion. Properties such as properties are more important issues in the development and manufacture of printed circuit boards. Therefore, the material selection of epoxy resin, hardener and reinforcing material has become the main influencing factor.

本發明所要解決的技術問題在於，針對現有技術的不足提供一種低膨脹係數、低介電損耗、高剛性的無鹵樹脂組成物、積層板以及印刷電路板。The technical problem to be solved by the present invention is to provide a halogen-free resin composition, a laminate and a printed circuit board with low expansion coefficient, low dielectric loss and high rigidity in view of the deficiencies of the prior art.

為了解決上述的技術問題，本發明所採用的其中一技術方案是提供一種低膨脹係數低介電損耗高剛性的無鹵樹脂組成物，其包括： (a)   1至10重量份的鄰甲酚醛環氧樹脂； (b)  50至70重量份的雙馬來醯亞胺樹脂； (c)   30至45重量份的多元羥基改質苯乙烯樹脂； (d)  60至90重量份的氰酸酯硬化劑 ；以及 (e)   1至20重量份的非DOPO含磷阻燃劑。 In order to solve the above-mentioned technical problems, one of the technical solutions adopted in the present invention is to provide a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, which comprises: (a) 1 to 10 parts by weight of o-cresol epoxy resin; (b) 50 to 70 parts by weight of bismaleimide resin; (c) 30 to 45 parts by weight of polyhydroxy modified styrene resin; (d) 60 to 90 parts by weight of a cyanate ester hardener; and (e) 1 to 20 parts by weight of a non-DOPO phosphorus-containing flame retardant.

為了解決上述的技術問題，本發明所採用的另外一技術方案是提供一種積層板，其包括：一樹脂基板，其包括多個半固化膠片，且每一所述半固化膠片由一玻璃纖維布經由塗覆本發明的低膨脹係數低介電損耗高剛性的無鹵樹脂組成物所製成；以及一金屬箔層，其設置於所述樹脂基板的至少一表面上。In order to solve the above-mentioned technical problem, another technical solution adopted by the present invention is to provide a laminated board, which includes: a resin substrate, which includes a plurality of prepreg films, and each of the prepreg films is made of a glass fiber cloth It is made by coating the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity of the present invention; and a metal foil layer, which is arranged on at least one surface of the resin substrate.

為了解決上述的技術問題，本發明所採用的另外再一技術方案是，提供一種印刷電路板，其包括如本發明的積層板。In order to solve the above technical problem, another technical solution adopted by the present invention is to provide a printed circuit board, which includes the laminate of the present invention.

本發明的其中一有益效果在於，本發明所提供的低膨脹係數低介電損耗高剛性無鹵樹脂組成物、積層板以及印刷電路板，其能通過特定的組成份及比例，可提供，同時提升板材韌性及耐熱性，並降低成本。再者，此組成物可製作成半固化膠片或樹脂膜，進而達到可應用於銅箔基板及印刷電路板之目的，就產業上的可利用性而言，利用本發明所衍生的產品，當可充分滿足目前市場的需求。One of the beneficial effects of the present invention is that the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, laminated board and printed circuit board provided by the present invention can be provided by specific components and proportions, and at the same time Improve sheet toughness and heat resistance, and reduce costs. Furthermore, the composition can be made into a prepreg or resin film, which can then be applied to copper foil substrates and printed circuit boards. It can fully meet the needs of the current market.

為使能更進一步瞭解本發明的特徵及技術內容，請參閱以下有關本發明的詳細說明與圖式，然而所提供的圖式僅用於提供參考與說明，並非用來對本發明加以限制。For a further understanding of the features and technical content of the present invention, please refer to the following detailed descriptions and drawings of the present invention. However, the drawings provided are only for reference and description, and are not intended to limit the present invention.

以下是通過特定的具體實施例來說明本發明所公開有關“低膨脹係數低介電損耗高剛性無鹵樹脂組成物、積層板以及印刷電路板”的實施方式，本領域技術人員可由本說明書所公開的內容瞭解本發明的優點與效果。本發明可通過其他不同的具體實施例加以施行或應用，本說明書中的各項細節也可基於不同觀點與應用，在不背離本發明的構思下進行各種修改與變更。以下的實施方式將進一步詳細說明本發明的相關技術內容，但所公開的內容並非用以限制本發明的保護範圍。另外，本文中所使用的術語“或”，應視實際情況可能包括相關聯的列出項目中的任一個或者多個的組合。The following are specific specific examples to illustrate the embodiments of the “low expansion coefficient, low dielectric loss, high rigidity halogen-free resin composition, laminate and printed circuit board” disclosed in the present invention. Those skilled in the art can learn from this specification. The disclosure provides an understanding of the advantages and effects of the present invention. The present invention can be implemented or applied through other different specific embodiments, and various details in this specification can also be modified and changed based on different viewpoints and applications without departing from the concept of the present invention. The following embodiments will further describe the related technical contents of the present invention in detail, but the disclosed contents are not intended to limit the protection scope of the present invention. In addition, the term "or", as used herein, should include any one or a combination of more of the associated listed items, as the case may be.

本發明所要解決的技術問題在於，針對現有技術的不足提供一種低膨脹係數、低介電損耗、高剛性的無鹵樹脂組成物、積層板以及印刷電路板。The technical problem to be solved by the present invention is to provide a halogen-free resin composition, a laminate and a printed circuit board with low expansion coefficient, low dielectric loss and high rigidity in view of the deficiencies of the prior art.

為了解決上述的技術問題，本發明所採用的其中一技術方案是提供一種低膨脹係數低介電損耗高剛性的無鹵樹脂組成物，其包括： (a)   1至10重量份的鄰甲酚醛環氧樹脂； (b)  50至70重量份的雙馬來醯亞胺樹脂； (c)   30至45重量份的多元羥基改質苯乙烯樹脂； (d)  60至90重量份的氰酸酯硬化劑 ；以及 (e)   1至20重量份的非DOPO含磷阻燃劑。 In order to solve the above-mentioned technical problems, one of the technical solutions adopted in the present invention is to provide a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, which comprises: (a) 1 to 10 parts by weight of o-cresol epoxy resin; (b) 50 to 70 parts by weight of bismaleimide resin; (c) 30 to 45 parts by weight of polyhydroxy modified styrene resin; (d) 60 to 90 parts by weight of a cyanate ester hardener; and (e) 1 to 20 parts by weight of a non-DOPO phosphorus-containing flame retardant.

本發明的鄰甲酚醛環氧樹脂的分子結構是在每一個苯環上連接有一個環氧基團，相較於現有技術的雙酚A型環氧樹脂，鄰甲酚醛環氧樹脂的環氧值高達0.5 eq/100g以上，樹脂固化時能夠提供2.5倍的交聯點，極易形成高交聯密度的三維結構，具有較佳的熱穩定性、機械強度、電氣絕緣性能、耐水性、耐化學藥品性、較高的玻璃化溫度（Tg），應用於電子元器件中，在高溫、潮濕的環境下仍可維持良好的電氣絕緣性能。較佳地，鄰甲酚醛環氧樹脂可以是可商業購得的南亞塑膠工業股份有限公司製造的NPCN-701、NPCN-702、NPCN-703、NPCN-704（均為商品名）；長春人造樹脂廠製造的CNE202；大日本油墨化學工業株式會社製造的N-665、N-670、N-673、N-680、N-690、N-695；日本東都化成株式會社製造的YDCN-701、YDCN-702、YDCN-703、YDCN-704、YDCN-701P、YDCN-702P、YDCN-703P、YDCN-704P、YDCN-701S、YDCN-702S、YDCN-703S；山東聖泉化工製造的SQCN700-1、SQCN700-2、SQCN700-3、SQCN700-4、SQCN700-4.5、SQCN702、SQCN703、SQCN700-1、SQCN704L、SQCN704ML、SQCN707、SQCN704H。The molecular structure of the o-cresol epoxy resin of the present invention is that each benzene ring is connected with an epoxy group. Compared with the bisphenol A type epoxy resin in the prior art, the epoxy resin of the o-cresol epoxy resin has The value is as high as 0.5 eq/100g or more. When the resin is cured, it can provide 2.5 times more cross-linking points, and it is easy to form a three-dimensional structure with high cross-linking density. It has better thermal stability, mechanical strength, electrical insulation performance, water resistance, resistance Chemical properties, high glass transition temperature (Tg), used in electronic components, and can maintain good electrical insulation performance in high temperature and humid environments. Preferably, the o-cresol epoxy resin can be commercially available NPCN-701, NPCN-702, NPCN-703, NPCN-704 (all trade names) manufactured by Nanya Plastics Industry Co., Ltd.; Changchun Artificial Resin CNE202 manufactured by the factory; N-665, N-670, N-673, N-680, N-690, N-695 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; YDCN-701, YDCN manufactured by Toto Chemical Co., Ltd., Japan -702, YDCN-703, YDCN-704, YDCN-701P, YDCN-702P, YDCN-703P, YDCN-704P, YDCN-701S, YDCN-702S, YDCN-703S; SQCN700-1, SQCN700 manufactured by Shandong Shengquan Chemical Co., Ltd. -2, SQCN700-3, SQCN700-4, SQCN700-4.5, SQCN702, SQCN703, SQCN700-1, SQCN704L, SQCN704ML, SQCN707, SQCN704H.

本發明的雙馬來醯亞胺樹脂並未特別的限制，主要是分子中含有兩個馬來醯亞胺基團的化合物，也可以使用雙馬來醯亞胺化合物的預聚物，或雙馬來醯亞胺化合物與胺化合物的預聚物。較佳地，雙馬來醯亞胺是選自雙(4-馬來醯亞胺基苯基)甲烷、2, 2-雙(4-(4-馬來醯亞胺基苯氧基)-苯基)丙烷、雙(3, 5-二甲基-4-馬來醯亞胺基苯基)甲烷、雙(3-乙基-5-甲基-4-馬來醯亞胺基苯基)甲烷和雙(3, 5-二乙基-4-馬來醯亞胺基苯基)甲烷所組成的群組。The bismaleimide resin of the present invention is not particularly limited, and is mainly a compound containing two maleimide groups in the molecule. Prepolymers of bismaleimide compounds, or bismaleimide compounds can also be used. Prepolymers of maleimide compounds and amine compounds. Preferably, bismaleimide is selected from bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)- Phenyl)propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl) ) methane and bis(3,5-diethyl-4-maleimidophenyl)methane.

本發明的多元羥基改質苯乙烯樹脂由多元羥基化合物與苯乙烯類樹脂加成而得。本發明的多元羥基改質苯乙烯樹脂可有效降低電性，並提供較佳的硬化性及可燃性，進一步來說，本發明的多元羥基改質苯乙烯樹脂可選自以下化學式(I)以及(II)所組成的群組：

(I)、

(II)； The polyvalent hydroxyl modified styrene resin of the present invention is obtained by addition of a polyvalent hydroxyl compound and a styrene resin. The polyhydroxyl modified styrene resin of the present invention can effectively reduce electrical properties and provide better hardenability and flammability. Further, the polyhydroxyl modified styrene resin of the present invention can be selected from the following chemical formula (I) and (II) Groups consisting of:

(I),

(II);

其中，R ₁為氫或碳數1至6之烴基，R ₂為

所表示之取代基，n為0至20之數，p為0.1至2.5之數，X為氫或碳數1至6之烴基。 wherein, R ₁ is hydrogen or a hydrocarbon group with 1 to 6 carbon atoms, and R ₂ is

In the represented substituent, n is a number from 0 to 20, p is a number from 0.1 to 2.5, and X is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.

本發明的氰酸酯硬化劑包括：30至45重量份的酚醛型(PN型)氰酸酯硬化劑以及30至45重量份的雙酚A型 (BPA型)氰酸酯硬化劑。本發明特定的氰酸酯樹脂可增加樹脂結構中的反應官能團，提高玻璃轉化溫度，更降低電性。酚醛型氰酸酯硬化劑具有酚醛樹脂的耐熱性、阻燃性，又具有氰酸酯的介電性能。較佳地，酚醛型氰酸酯硬化劑包括可商業購得的揚州天啟型號CE-05CS，雙酚A型氰酸酯硬化劑包括可商業購得的Lonza型號ULL-950S。The cyanate hardener of the present invention includes: 30 to 45 parts by weight of a novolac type (PN type) cyanate hardener and 30 to 45 parts by weight of a bisphenol A type (BPA type) cyanate hardener. The specific cyanate resin of the present invention can increase the reactive functional groups in the resin structure, increase the glass transition temperature, and further reduce the electrical properties. Phenolic cyanate hardener has the heat resistance and flame retardancy of phenolic resin and the dielectric properties of cyanate. Preferably, the novolac type cyanate hardener includes commercially available Yangzhou Tianqi model CE-05CS, and the bisphenol A type cyanate hardener includes commercially available Lonza model ULL-950S.

更詳細來說，氰酸酯硬化劑具有以下結構：

， In more detail, the cyanate ester hardener has the following structure:

,

其中Ar ₁及Ar ₂各自獨立地為伸苯基、伸聯苯基、伸萘基及伸蒽基；X ₁及X ₂各自獨立地為C1-C8伸烷基、C1-C8鹵烯基、C3-C16伸環烷基、-S-、羰基或羧基；且各R1獨立地為氫或C1-C8烷基，且n為0至10之整數。 Wherein Ar ₁ and Ar ₂ are each independently phenylene, biphenylene, naphthylene and anthracenyl; X ₁ and X ₂ are each independently C1-C8 alkylene, C1-C8 haloalkenyl, and each R1 is independently hydrogen or C1-C8 alkyl, and n is an integer from 0 to 10.

其中，酚醛型(PN型)氰酸酯硬化劑具有以下結構：

， Among them, the novolac type (PN type) cyanate hardener has the following structure:

,

其中，R ₁、R ₂分別獨立地表示為氫原子或C1-C5的脂肪族烴基、苯基。 Here, R ₁ and R ₂ each independently represent a hydrogen atom, a C1-C5 aliphatic hydrocarbon group, or a phenyl group.

其中，雙酚A型 (BPA型)氰酸酯硬化劑具有以下結構：

， Wherein, the bisphenol A type (BPA type) cyanate hardener has the following structure:

,

其中，R ₁、R ₂分別獨立地表示為氫原子或C1-C5的脂肪族烴基、苯基。 Here, R ₁ and R ₂ each independently represent a hydrogen atom, a C1-C5 aliphatic hydrocarbon group, or a phenyl group.

本發明所定義的非DOPO含磷阻燃劑，意即不含9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)衍生物。詳細而言，DOPO結構內的P-O-C鍵結容易水解為P-OH，會使材料介電常數及介電損耗上升，故選用非DOPO阻燃劑可避免提升材料之Dk以及DF，其中，Dk即為介電常數(Dielectric Constant，εr)，DF為介電損耗。較佳地，非DOPO含磷阻燃劑是選自次磷酸金屬鹽（phosphinate）、聚磷酸鹽（polyphosphate）、鏻鹽（phosphonium salt）、磷酸酯（phosphate ester）、磷腈（phosphazene）以及亞磷酸酯（phosphite ester）所組成的群組。A non-DOPO phosphorus-containing flame retardant as defined in the present invention means that it does not contain 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives. In detail, the P-O-C bond in the DOPO structure is easily hydrolyzed to P-OH, which will increase the dielectric constant and dielectric loss of the material. Therefore, the use of non-DOPO flame retardants can avoid increasing the Dk and DF of the material, where Dk is is the dielectric constant (Dielectric Constant, εr), and DF is the dielectric loss. Preferably, the non-DOPO phosphorus-containing flame retardant is selected from the group consisting of phosphinate, polyphosphate, phosphonium salt, phosphate ester, phosphazene, and phosphazene. A group consisting of phosphite esters.

次磷酸金屬鹽可選自二烷基次磷酸鋁、三（二乙基次磷酸）鋁、三（甲基乙基次磷酸）鋁、三（二苯基次磷酸）鋁、雙（二乙基次磷酸）鋅、雙（甲基乙基次磷酸）鋅、雙（二苯基次磷酸）鋅、雙（二乙基次磷酸）氧鈦、雙（甲基乙基次磷酸）氧鈦以及雙（二苯基次磷酸）氧鈦所組成的群組。更詳細來說，如商業上可購得的科萊恩（CLARIANT）型號為OP-935。The metal hypophosphite can be selected from the group consisting of dialkylaluminum hypophosphite, tris(diethylhypophosphite)aluminum, tris(methylethylhypophosphite)aluminum, tris(diphenylhypophosphite)aluminum, bis(diethylhypophosphite)aluminum Hypophosphite) zinc, bis(methyl ethyl hypophosphite) zinc, bis(diphenyl hypophosphite) zinc, bis(diethyl hypophosphite) titanyl, bis(methyl ethyl hypophosphite) titanyl, and bis(methyl ethyl hypophosphite) (Diphenyl hypophosphite) titanium oxide group. In more detail, for example, the commercially available CLARIANT model is OP-935.

聚磷酸鹽的實例包括但不限於聚磷酸三聚氰胺（melamine polyphosphate）、聚磷酸蜜白胺（melam polyphosphate）、及聚磷酸蜜勒胺（melem polyphosphate）。商業上可購得之聚磷酸鹽包括可購自巴斯夫（BASF）之型號為Melapur 200的產品。鏻鹽可選自四苯基鏻四苯基硼酸鹽（tetraphenylphosphonium tetraphenylborate）。磷酸酯可選自縮合磷酸酯化合物以及環狀磷酸酯化合物。Examples of polyphosphates include, but are not limited to, melamine polyphosphate, melam polyphosphate, and melem polyphosphate. Commercially available polyphosphates include the product available from BASF as Melapur 200. The phosphonium salt may be selected from tetraphenylphosphonium tetraphenylborate. The phosphoric acid ester may be selected from condensed phosphoric acid ester compounds and cyclic phosphoric acid ester compounds.

縮合磷酸酯化合物可選自磷酸三苯酯（triphenyl phosphate）、磷酸三甲苯酯（tricresyl phosphate）、磷酸二甲苯二苯酯（xylenyl-diphenyl phosphate）、磷酸甲苯二苯酯（cresyl-diphenyl phosphate）、間苯二酚雙-二甲苯基磷酸酯 （resorcinol dixylenylphosphate，RDXP）、間苯二酚雙-二苯基磷酸酯（resorcinol bis-diphenylphosphate，RDP）。商業上可購得之磷酸酯包括可購自大八化學之型號為PX-200及PX-202的產品。The condensed phosphate compound can be selected from triphenyl phosphate, tricresyl phosphate, xylenyl-diphenyl phosphate, cresyl-diphenyl phosphate, Resorcinol bis-xylenylphosphate (resorcinol dixylenylphosphate, RDXP), resorcinol bis-diphenylphosphate (resorcinol bis-diphenylphosphate, RDP). Commercially available phosphate esters include those available from Daeba Chemicals under the model numbers PX-200 and PX-202.

磷腈化合物包括環狀磷腈化合物及直鏈狀磷腈化合物。商業上可購得之磷腈包括可購自大塚化學之型號為BP-PZ、SPB-100及SPH-100的產品。亞磷酸酯可選自亞磷酸三甲酯（trimethylphosphite）及亞磷酸三乙酯（triethylphosphite）。The phosphazene compound includes a cyclic phosphazene compound and a linear phosphazene compound. Commercially available phosphazenes include those available from Otsuka Chemical under the model numbers BP-PZ, SPB-100 and SPH-100. The phosphite may be selected from trimethylphosphite and triethylphosphite.

較佳地，本發明的非DOPO含磷阻燃劑是1至10重量份的間苯二酚雙二甲苯基磷酸鹽(如PX-200)搭配1至10重量份的磷腈化合物（如SPB-100），其可提供優異的無鹵阻燃效果。Preferably, the non-DOPO phosphorus-containing flame retardant of the present invention is 1 to 10 parts by weight of resorcinol bis-xylyl phosphate (such as PX-200) and 1 to 10 parts by weight of a phosphazene compound (such as SPB). -100), which can provide excellent halogen-free flame retardant effect.

除此之外，本發明的樹脂組成物進一步包括：硬化促進劑，其可使氰酸酯開環反應，是選自磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、胍系硬化促進劑、金屬系硬化促進劑、過氧化物系硬化促進劑。較佳是金屬系硬化促進劑與過氧化物系硬化促進劑混合。更佳地，可以是基於環氧樹脂100重量份1重量份的金屬系硬化促進劑與3重量份過氧化物系硬化促進劑。In addition, the resin composition of the present invention further comprises: a hardening accelerator, which can make the cyanate ester ring-opening reaction, selected from the group consisting of phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and guanidine-based hardening accelerators. Hardening accelerator, metal hardening accelerator, peroxide hardening accelerator. Preferably, a metal-based hardening accelerator and a peroxide-based hardening accelerator are mixed. More preferably, based on 100 parts by weight of the epoxy resin, 1 part by weight of a metal-based hardening accelerator and 3 parts by weight of a peroxide-based hardening accelerator can be used.

更具體來說，金屬系硬化促進劑，可舉出例如鈷、銅、鋅、鐵、鎳、錳、錫等的金屬之有機金屬錯合物或有機金屬鹽。作為有機金屬錯合物的具體例，可舉出乙醯基丙酮酸鈷(II)、乙醯基丙酮酸鈷(III)等的有機鈷錯合物、乙醯基丙酮酸銅(II)等的有機銅錯合物、乙醯基丙酮酸鋅(II)等的有機鋅錯合物、乙醯基丙酮酸鐵(III)等的有機鐵錯合物、乙醯基丙酮酸鎳(II)等的有機鎳錯合物、乙醯基丙酮酸錳(II)等的有機錳錯合物。作為有機金屬鹽，可舉出例如辛酸鋅、辛酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅。較佳地，金屬系硬化促進劑是乙醯基丙酮酸鈷(III)(Co(acac) ₃)。 More specifically, metal-based hardening accelerators include metal organometallic complexes or organometallic salts such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, and copper(II) acetylacetonate. organo-copper complexes, organozinc complexes such as zinc (II) acetylacetonate, organo-iron complexes such as iron (III) acetylacetonate, nickel (II) acetylacetonate etc. organo-nickel complexes, manganese (II) acetylacetonate and other organo-manganese complexes. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. Preferably, the metal-based hardening accelerator is cobalt(III) acetylacetonate (Co(acac) ₃ ).

過氧化物系硬化促進劑，可舉出例如環己酮過氧化物、過氧化苯甲酸叔丁基酯、甲基乙基酮過氧化物、過氧化二異丙苯、叔丁基過氧化異丙苯、二叔丁基過氧化物、過氧化氫二異丙苯、氫過氧化異丙苯、叔丁基過氧化氫。較佳地，過氧化物系硬化促進劑是自Arkema商業購得的過氧化二異丙苯(DCP)。Peroxide-based curing accelerators include, for example, cyclohexanone peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, and t-butyl isopropyl peroxide. Propylbenzene, di-tert-butyl peroxide, dicumyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide. Preferably, the peroxide-based hardening accelerator is dicumyl peroxide (DCP) commercially available from Arkema.

除此之外，本發明的樹脂組成物進一步包括：無機填料，其可增加無鹵低介電環氧樹脂組成物的熱傳導性，改良其熱膨脹性以及機械強度，較佳地，無機填料是均勻分佈於無鹵低介電環氧樹脂組成物中。較佳地，無機填料可經由矽烷偶合劑預先進行表面處理。較佳地，無機填料可為球型、片狀、粒狀、柱狀、板狀、針狀或不規則狀的無機填料。較佳地，無機填料選自二氧化矽(如熔融態、非熔融態、多孔質或中空型的二氧化矽)、氧化鋁、氫氧化鋁、氧化鎂、氫氧化鎂、碳酸鈣、氮化鋁、氮化硼、碳化鋁矽、碳化矽、二氧化鈦、氧化鋅、氧化鋯、硫酸鋇、碳酸鎂、碳酸鋇、雲母、滑石、石墨烯所組成的群組。較佳地，無機填料的添加量可以是以100重量份的環氧樹脂為基準的150至200重量份。較佳地，可使用Nomoray公司製的NQ-1035I，可有效提升熱傳導性、機械強度及降低熱膨脹性。In addition, the resin composition of the present invention further comprises: inorganic filler, which can increase the thermal conductivity of the halogen-free low-dielectric epoxy resin composition, improve its thermal expansion and mechanical strength, preferably, the inorganic filler is uniform Distributed in halogen-free low-dielectric epoxy resin composition. Preferably, the inorganic filler can be pre-treated with a silane coupling agent. Preferably, the inorganic filler can be spherical, flake, granular, columnar, plate, needle or irregular. Preferably, the inorganic filler is selected from silica (such as molten, non-molten, porous or hollow silica), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, nitride A group consisting of aluminum, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene. Preferably, the addition amount of the inorganic filler may be 150 to 200 parts by weight based on 100 parts by weight of the epoxy resin. Preferably, NQ-1035I manufactured by Nomoray Company can be used, which can effectively improve thermal conductivity, mechanical strength and reduce thermal expansion.

此外，本發明的無鹵低介電環氧樹脂組成物更進一步包括適量的溶劑，舉例而言，酮類、酯類、醚類、醇類等，更具體而言，本發明的溶劑是選自丙酮、丁酮、丙二醇甲醚、丙二醇甲醚醋酸酯、二甲基乙醯胺以及環己酮所組成的群組。舉例來說，溶劑可以選自50至60重量份的丁酮(MEK)以及40至50重量份的環己酮(Cyclohexanone)的組合或其他溶劑等的組合。In addition, the halogen-free low-dielectric epoxy resin composition of the present invention further includes an appropriate amount of solvent, for example, ketones, esters, ethers, alcohols, etc. More specifically, the solvent of the present invention is selected from From the group consisting of acetone, methyl ethyl ketone, propylene glycol methyl ether, propylene glycol methyl ether acetate, dimethylacetamide, and cyclohexanone. For example, the solvent may be selected from a combination of 50 to 60 parts by weight of butanone (MEK) and 40 to 50 parts by weight of cyclohexanone or a combination of other solvents and the like.

為了解決上述的技術問題，本發明所採用的另外一技術方案是提供一種積層板，其包括：一樹脂基板，其包括多個半固化膠片，且每一所述半固化膠片由一玻璃纖維布經由塗覆本發明的低膨脹係數低介電損耗高剛性的無鹵樹脂組成物所製成；以及一金屬箔層，其設置於所述樹脂基板的至少一表面上。In order to solve the above-mentioned technical problem, another technical solution adopted by the present invention is to provide a laminated board, which includes: a resin substrate, which includes a plurality of prepreg films, and each of the prepreg films is made of a glass fiber cloth It is made by coating the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity of the present invention; and a metal foil layer, which is arranged on at least one surface of the resin substrate.

本發明還提供另外一技術方案是一種積層板，其包括：(a)樹脂基板，其包括多個半固化膠片，且每一所述半固化膠片由一玻璃纖維布經由塗覆如本發明的無鹵低介電環氧樹脂組成物所製成；以及(b)金屬箔層，其設置於樹脂基板的至少一表面上，或可視需求使得樹脂基板上下設置金屬箔層。The present invention also provides another technical solution, which is a laminate, which includes: (a) a resin substrate, which includes a plurality of prepreg films, and each of the prepreg films is coated with a glass fiber cloth according to the present invention. and (b) a metal foil layer, which is disposed on at least one surface of the resin substrate, or the resin substrate can be provided with metal foil layers up and down as required.

除此之外，本發明更提供另外再一技術方案是一種印刷電路板，其包括本發明的積層板。Besides, the present invention further provides another technical solution, which is a printed circuit board including the laminate of the present invention.

以下將針對本發明的無鹵環氧樹脂組成物以及進行多組實施例以及比較例的，以說明藉由本發明特定的之組成比例調配而達成最佳的積層板特性。The following will focus on the halogen-free epoxy resin composition of the present invention, as well as several groups of examples and comparative examples, to illustrate that the optimum laminate properties can be achieved by the specific composition ratio of the present invention.

[實施例][Example]

以下實施例E1~E4是使用本發明的無鹵低介電環氧樹脂組成物在一連續的過程中製造半固化膠片。通常是以玻璃纖維布作基材。卷狀的玻璃纖維布連續地穿過一系列滾輪進入上膠槽，槽裏裝有本發明的無鹵低介電環氧樹脂組成物。在上膠槽裏玻璃纖維布被樹脂充分浸潤，然後經過計量輥刮除多餘的樹脂，進入上膠爐烘烤一定的時間，使溶劑蒸發並使樹脂固化一定程度，冷卻，收卷，形成半固化膠片，然後將上述批製得的半固化膠片，取同一批之半固化膠片四張及兩張18 μm銅箔，依銅箔、四片半固化膠片、銅箔之順序進行疊合，再於真空條件下經由220℃壓合2小時形成銅箔基板，其中四片半固化膠片固化形成兩銅箔間之絕緣層。The following Examples E1 to E4 are the use of the halogen-free low-dielectric epoxy resin composition of the present invention to manufacture prepreg films in a continuous process. Usually glass fiber cloth is used as the base material. Rolled fiberglass cloth is continuously passed through a series of rollers into a gluing tank containing the halogen-free, low-dielectric epoxy resin composition of the present invention. In the gluing tank, the glass fiber cloth is fully infiltrated with the resin, and then the excess resin is scraped off by the metering roller, and then enters the gluing furnace to bake for a certain period of time, so that the solvent evaporates and the resin is solidified to a certain extent. Curing the film, then the prepreg film obtained in the above batch, take four prepreg films and two 18 μm copper foils from the same batch, and stack them in the order of copper foil, four prepreg films, and copper foil, and then Under vacuum conditions, the copper foil substrate was formed by pressing at 220° C. for 2 hours, in which four pieces of prepreg film were cured to form an insulating layer between the two copper foils.

表1 組成份 E1 E2 E3 E4 環氧樹脂 Cresol novolac epoxy * 10 10 0 0 一般樹脂 Bismaleimides* 50 50 70 70 Styrene modified resin 40 40 30 30 硬化劑 Cyanate ester* (PN type) 30 40 30 45 Cyanate ester* (BPA type) 40 30 40 30 阻燃劑 Resorcinol dixylenylphosphate 5 10 5 5 含磷阻燃劑 5 5 10 5 無機填料 球型二氧化矽 200 200 200 200 促進劑 Cobaltic acetylacetonate 1 1 1 1 Dicumyl peroxide 3 3 2 2 溶劑 MEK(丁酮) 50 50 50 50 Cyclohexanone (環己酮) 40 40 40 40 Table 1 composition E1 E2 E3 E4 epoxy resin Cresol novolac epoxy * 10 10 0 0 General resin Bismaleimides* 50 50 70 70 Styrene modified resin 40 40 30 30 hardener Cyanate ester* (PN type) 30 40 30 45 Cyanate ester* (BPA type) 40 30 40 30 flame retardant Resorcinol dixylenylphosphate 5 10 5 5 Phosphorus Flame Retardant 5 5 10 5 Inorganic filler spherical silica 200 200 200 200 accelerator Cobaltic acetylacetonate 1 1 1 1 Dicumyl peroxide 3 3 2 2 solvent MEK (Butanone) 50 50 50 50 Cyclohexanone (cyclohexanone) 40 40 40 40

*Cresol novolac epoxy ：長春人造樹脂 公司製CNE-202 甲酚醛環氧樹脂。*Cresol novolac epoxy: CNE-202 cresol novolac epoxy resin manufactured by Changchun Synthetic Resin Company.

*Bismaleimides：KI公司製KI-70。*Bismaleimides: KI-70 manufactured by KI Corporation.

*Cyanate ester(PN type)：揚州天啟公司製CE-05CS。*Cyanate ester(PN type): CE-05CS manufactured by Yangzhou Tianqi Company.

*Cyanate ester(BPA type)：Lonza公司製ULL-9505。*Cyanate ester (BPA type): ULL-9505 manufactured by Lonza Corporation.

[比較例][Comparative example]

依據下述表2的比較例C1至C7的組份及比例在一連續的過程中製造半固化膠片。通常是以玻璃纖維布作基材。卷狀的玻璃纖維布連續地穿過一系列滾輪進入上膠槽，槽裏裝有本發明的無鹵低介電環氧樹脂組成物。在上膠槽裏玻璃纖維布被樹脂充分浸潤，然後經過計量輥刮除多餘的樹脂，進入上膠爐烘烤一定的時間，使溶劑蒸發並使樹脂固化一定程度，冷卻，收卷，形成半固化膠片，然後將上述批製得的半固化膠片，取同一批之半固化膠片四張及兩張18 μm銅箔，依銅箔、四片半固化膠片、銅箔之順序進行疊合，再於真空條件下經由220℃壓合2小時形成銅箔基板，其中四片半固化膠片固化形成兩銅箔間之絕緣層。Prepreg films were produced in a continuous process according to the compositions and ratios of Comparative Examples C1 to C7 in Table 2 below. Usually glass fiber cloth is used as the base material. Rolled fiberglass cloth is continuously passed through a series of rollers into a gluing tank containing the halogen-free, low-dielectric epoxy resin composition of the present invention. In the gluing tank, the glass fiber cloth is fully infiltrated with the resin, and then the excess resin is scraped off by the metering roller, and then enters the gluing furnace to bake for a certain period of time, so that the solvent evaporates and the resin is solidified to a certain extent. Curing the film, then the prepreg film obtained in the above batch, take four prepreg films and two 18 μm copper foils from the same batch, and stack them in the order of copper foil, four prepreg films, and copper foil, and then Under vacuum conditions, the copper foil substrate was formed by pressing at 220° C. for 2 hours, in which four pieces of prepreg film were cured to form an insulating layer between the two copper foils.

表2 組成份 C1 C2 C3 C4 C5 環氧樹脂 HP-7200 40 40 40 40 40 NC-3000 60 60 60 60 60 馬來酸酐硬化劑 苯乙烯馬來酸酐(SMA) EF60 30 - -     式1之改質型馬來酸酐共聚物 - - 20 - - 式2之改質型馬來酸酐共聚物 - - 20 - - 式3之馬來酸酐改質聚醯亞胺樹脂 - - - 40 35 苯並噁嗪樹脂 LZ8280 - 60 - 50 20 阻燃劑 式I阻燃劑 36 - - - - 式II阻燃劑 - - 60 - - 式III阻燃劑 - 62 - - - SAYTEX 8010 - - - 30 - 阻燃性化合物 PX-200(間苯二酚雙二甲苯基磷酸鹽) - - - - - TCEP(磷酸三(2-氯乙基)酯) - - - - - TMP - - - - - 無機填料 熔融二氧化矽 28 57 47 41 30 硬化促進劑 2E4MI (2-乙基-4-甲基咪唑) 1 1 1 1 1 溶劑 MEK(丁酮) 42 80 114 97 56 PMA(丙二醇甲醚乙脂) 20 - - - - Table 2 composition C1 C2 C3 C4 C5 epoxy resin HP-7200 40 40 40 40 40 NC-3000 60 60 60 60 60 Maleic anhydride hardener Styrene Maleic Anhydride (SMA) EF60 30 - - Modified maleic anhydride copolymer of formula 1 - - 20 - - Modified maleic anhydride copolymer of formula 2 - - 20 - - Maleic anhydride modified polyimide resin of formula 3 - - - 40 35 benzoxazine resin LZ8280 - 60 - 50 20 flame retardant Formula I flame retardant 36 - - - - Formula II flame retardant - - 60 - - Formula III flame retardant - 62 - - - SAYTEX 8010 - - - 30 - flame retardant compound PX-200 (resorcinol bis-xylyl phosphate) - - - - - TCEP (tris(2-chloroethyl) phosphate) - - - - - TMP - - - - - Inorganic filler Fused silica 28 57 47 41 30 hardening accelerator 2E4MI (2-ethyl-4-methylimidazole) 1 1 1 1 1 solvent MEK (Butanone) 42 80 114 97 56 PMA (propylene glycol methyl ether ethyl ester) 20 - - - -

* HP-7200：DCPD(二環戊二烯型)型環氧樹脂。* HP-7200: DCPD (dicyclopentadiene type) epoxy resin.

* NC-3000：日本化藥公司聯苯型環氧樹脂。* NC-3000: Nippon Kayaku Co., Ltd. biphenyl type epoxy resin.

*式1~3之馬來酸酐改質聚醯亞胺樹脂以及式I~III阻燃劑：參酌第TWI632190專利號及第TW109106662申請號。* Maleic anhydride modified polyimide resins of formulas 1-3 and flame retardants of formulas I-III: refer to Patent No. TWI632190 and Application No. TW109106662.

[物性測試][physical property test]

分別將上述實施例E1至E4及比較例C1至C7的銅箔積層板進行物性測試，並紀錄測試結果於表3：The copper foil laminates of the above-mentioned Examples E1 to E4 and Comparative Examples C1 to C7 were respectively tested for physical properties, and the test results were recorded in Table 3:

玻璃轉化溫度(Tg)：根據差示掃描量熱法(DSC)，依據IPC-TM-650 2.4.25所規定的DSC方法進行測定。Glass transition temperature (Tg): Measured by differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-650 2.4.25.

銅箔積層板耐熱性(T288)：亦稱“漂錫結果”，耐熱實驗是依據產業標準IPC-TM-650 2.4.24.1，將銅箔積層板浸泡於288℃錫爐至爆板所需時間。Heat resistance of copper foil laminates (T288): also known as "tin bleaching results", the heat resistance test is based on the industry standard IPC-TM-650 2.4.24.1, the time required to soak the copper foil laminates in a tin furnace at 288°C until the board bursts .

含銅箔積層板吸濕後浸錫測試：使用含銅箔層的半固化膠片進行耐熱性(T288)測試，依據產業標準IPC-TM-650 2.4.24.1，將銅箔積層板浸泡於288℃錫爐至爆板所需時間。Immersion tin test for copper-clad laminates after moisture absorption: use the prepreg containing copper foil for heat resistance (T288) test, according to industry standard IPC-TM-650 2.4.24.1, soak the copper-clad laminates at 288°C The time it takes for the tin furnace to explode.

銅箔積層板耐熱性(S/D)測試：含銅基板浸錫測試(solder dip 288℃，10秒，測耐熱回數)。Copper foil laminate heat resistance (S/D) test: copper-containing substrate dip tin test (solder dip 288 ℃, 10 seconds, measure the number of heat resistance cycles).

銅箔積層板耐熱性(PCT)測試：不含銅基板PCT吸濕後浸錫測試(pressure cooking at 121℃，1小時後，測solder dip 288℃，20秒觀看有無爆板)。Copper foil laminated board heat resistance (PCT) test: PCT without copper substrate absorbs moisture and then dip tin test (pressure cooking at 121 ℃, after 1 hour, measure solder dip 288 ℃, 20 seconds to see whether there is a burst board).

銅箔與基板間拉力(peeling strength, half ounce copper foil, P/S)：依據IPC－TM－650 2.4.1檢測規範進行測定。Tensile strength between copper foil and substrate (peeling strength, half ounce copper foil, P/S): measured according to IPC-TM-650 2.4.1 testing specification.

介電常數(Dk)：依據IPC－TM－650 2.5.5檢測規範進行測定，介電常數代表所製膠片的電子絕緣特性，數值越低代表電子絕緣特性越好。Dielectric constant (Dk): Measured according to IPC-TM-650 2.5.5 testing specifications, the dielectric constant represents the electronic insulation properties of the film made, and the lower the value, the better the electronic insulation properties.

介電損耗(Df)：依據IPC－TM－650 2.5.5檢測規範進行測定，介電損耗表示物質在一定温度下吸收某一頻率之微波的能力，通常在通訊產品的規範裡，介電損耗數值需越低越好。Dielectric loss (Df): Measured according to IPC-TM-650 2.5.5 test specification, dielectric loss indicates the ability of a substance to absorb microwaves of a certain frequency at a certain temperature, usually in the specification of communication products, the dielectric loss The lower the value, the better.

耐燃性(flaming test，UL94)：依據UL94垂直燃燒法測定，其以塑膠材料標準試片經火焰燃燒後之自燃時間、自燃速度、掉落之顆粒狀態來訂定塑膠材料之耐燃等級。而依耐燃等級優劣，依次是HB、V-2、V-1、V-0、最高為5V等級。而UL 94測試方法是指塑膠材料以垂直方式在火燄上燃燒。以每十秒為一測試週期，其步驟如下：步驟一：將試片放進火焰中十秒再移開，測定移開之後該試片繼續燃燒時間(T1)；步驟二：當試片火焰熄滅後，再放進火焰中十秒再移開，再測定移開之後該試片繼續燃燒時間(T2)；步驟三：重複數次實驗並取其平均值；步驟四：計算T1+T2之總合。而UL 94 V-0等級的要求是為在試片單一燃燒時間T1之平均及T2之平均皆不得超過10秒，且其T1與T2的總合不得超過50秒方符合UL 94 V-0要求。Flame resistance (flaming test, UL94): measured according to the UL94 vertical combustion method, which determines the flame resistance level of plastic materials based on the self-ignition time, self-ignition speed, and dropped particle state of the standard test piece of plastic material after being burned by flame. According to the flame resistance grade, the order is HB, V-2, V-1, V-0, and the highest is 5V. The UL 94 test method refers to the burning of plastic materials on a flame in a vertical manner. Taking every ten seconds as a test cycle, the steps are as follows: Step 1: Put the test piece into the flame for ten seconds and then remove it, and measure the continuous burning time (T1) of the test piece after the removal; Step 2: When the test piece flame After being extinguished, put it into the flame for ten seconds and then remove it, and then measure the continuous burning time (T2) of the test piece after removal; Step 3: Repeat the experiment several times and take the average value; Step 4: Calculate the ratio of T1+T2 total. The requirement of UL 94 V-0 grade is that the average of T1 and T2 of the single burning time of the test piece shall not exceed 10 seconds, and the total of T1 and T2 shall not exceed 50 seconds to meet the requirements of UL 94 V-0 .

X/Y軸熱膨脹係數(CTE) ：依據IPC-TM-650-2.4.24檢測規範進行測定。X/Y-axis thermal expansion coefficient (CTE): Measured according to IPC-TM-650-2.4.24 test specification.

Z軸熱膨脹係數(CTE) (50-260℃) ：依據IPC-TM-650-2.4.24.1檢測規範進行測定。Z-axis coefficient of thermal expansion (CTE) (50-260°C): Measured according to IPC-TM-650-2.4.24.1 testing specification.

Modulus(X/Y) 依據“IPC-TM-650 2.4.24.4” 檢測規範進行測定。Modulus(X/Y) is determined according to the "IPC-TM-650 2.4.24.4" test specification.

表3  性質 測試 測試 方法 E1 E2 E3 E4 C1 C2 C3 C4 C5 Tg DSC 276 280 285 283 161 168 147 171 174 T288 TMA ＞60 ＞60 ＞60 ＞60 5 22 32 ＞70 ＞70 S/D dip cycles ＞60 ＞60 ＞60 ＞60 3 18 8 ＞20 ＞20 PCT 20s /288℃ 合格 合格 合格 合格 不合格 合格 不合格 合格 合格 P/S Hoz Cu foil 7.1 6.9 6.7 7.2 6.7 5.2 5.8 6.3 6.9 Dk 10GHz 4.07 4.13 4.22 4.11 3.93 4.14 4.25 4.21 4.04 Df 10GHz 0.006 0.006 0.007 0.006 0.015 0.009 0.012 0.013 0.011 可燃性 UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-2 X/Y CTE IPC-TM-650-2.4.24(ppm/℃) 8.3 8.5 8.8 8.1 14.6 15.0 15.7 15.3 14.8 Z CTE(50-260℃) TMA(IPC-TM-650-2.4.24.1)(%) 1.08 1.10 1.11 1.06 2.90 2.93 2.96 2.95 2.92 Modulus(X/Y) DMA (MPa (260℃)) 9988 10016 10100 9968 4316 4713 5120 5005 4588 其他 PP外觀 佳 佳 佳 佳 佳 差 差 佳 佳 table 3 property test testing method E1 E2 E3 E4 C1 C2 C3 C4 C5 Tg DSC 276 280 285 283 161 168 147 171 174 T288 TMA >60 >60 >60 >60 5 twenty two 32 >70 >70 S/D dip cycles >60 >60 >60 >60 3 18 8 >20 >20 PCT 20s /288℃ qualified qualified qualified qualified Failed qualified Failed qualified qualified P/S Hoz Cu foil 7.1 6.9 6.7 7.2 6.7 5.2 5.8 6.3 6.9 Dk 10GHz 4.07 4.13 4.22 4.11 3.93 4.14 4.25 4.21 4.04 Df 10GHz 0.006 0.006 0.007 0.006 0.015 0.009 0.012 0.013 0.011 Flammability UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-2 X/Y CTE IPC-TM-650-2.4.24(ppm/℃) 8.3 8.5 8.8 8.1 14.6 15.0 15.7 15.3 14.8 Z CTE(50-260℃) TMA(IPC-TM-650-2.4.24.1)(%) 1.08 1.10 1.11 1.06 2.90 2.93 2.96 2.95 2.92 Modulus(X/Y) DMA (MPa (260℃)) 9988 10016 10100 9968 4316 4713 5120 5005 4588 other PP appearance good good good good good Difference Difference good good

[實施例的有益效果][Advantageous effects of the embodiment]

本發明的其中一有益效果在於，本發明所提供的低膨脹係數低介電損耗高剛性無鹵樹脂組成物、積層板以及印刷電路板，其能通過特定的組成份及比例，可提供，同時提升板材韌性及耐熱性，並降低成本。再者，此組成物可製作成半固化膠片或樹脂膜，進而達到可應用於銅箔基板及印刷電路板之目的，就產業上的可利用性而言，利用本發明所衍生的產品，當可充分滿足目前市場的需求。One of the beneficial effects of the present invention is that the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, laminated board and printed circuit board provided by the present invention can be provided by specific components and proportions, and at the same time Improve sheet toughness and heat resistance, and reduce costs. Furthermore, the composition can be made into a prepreg or resin film, which can then be applied to copper foil substrates and printed circuit boards. It can fully meet the needs of the current market.

更進一步來說，本發明所提供的低膨脹係數、低介電損耗、高剛性無鹵樹脂組成物所製得的銅箔積層板具有自較低的膨脹係數，相較於現有技術X/Y軸的CTE低於10 ppm/℃、Z軸CTE(50-260℃)低於2%，在10GHz下低於0.007的介電損耗(Df)，提供更優異的玻璃轉化溫度(Tg)，板材韌性上也具有較佳剛性，且明顯相較於現有技術有較佳的耐熱效果。Furthermore, the low expansion coefficient, low dielectric loss, and high rigidity halogen-free resin composition provided by the present invention provides a copper foil laminate with a relatively low expansion coefficient, compared with the prior art X/Y Axis CTE below 10 ppm/°C, Z-axis CTE (50-260°C) below 2%, dielectric loss (Df) below 0.007 at 10GHz, providing better glass transition temperature (Tg), sheet It also has better rigidity in terms of toughness, and obviously has better heat resistance effect than the prior art.

以上所公開的內容僅為本發明的優選可行實施例，並非因此侷限本發明的申請專利範圍，所以凡是運用本發明說明書及圖式內容所做的等效技術變化，均包含於本發明的申請專利範圍內。The contents disclosed above are only preferred feasible embodiments of the present invention, and are not intended to limit the scope of the present invention. Therefore, any equivalent technical changes made by using the contents of the description and drawings of the present invention are included in the application of the present invention. within the scope of the patent.

Claims (10)

一種低膨脹係數低介電損耗高剛性無鹵樹脂組成物，其包括： (a)        1至10重量份的鄰甲酚醛環氧樹脂； (b)        50至70重量份的雙馬來醯亞胺樹脂； (c)        30至45重量份的多元羥基改質苯乙烯樹脂； (d)        60至90重量份的氰酸酯硬化劑；以及 (e)        1至20重量份的非DOPO含磷阻燃劑。 A halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, comprising: (a) 1 to 10 parts by weight of o-cresol epoxy resin; (b) 50 to 70 parts by weight of bismaleimide resin; (c) 30 to 45 parts by weight of polyvalent hydroxyl modified styrene resin; (d) 60 to 90 parts by weight of a cyanate ester hardener; and (e) 1 to 20 parts by weight of a non-DOPO phosphorus-containing flame retardant. 如請求項1所述的低膨脹係數低介電損耗高剛性無鹵樹脂組成物，其中，所述雙馬來醯亞胺是選自雙(4-馬來醯亞胺基苯基)甲烷、2, 2-雙(4-(4-馬來醯亞胺基苯氧基)-苯基)丙烷、雙(3, 5-二甲基-4-馬來醯亞胺基苯基)甲烷、雙(3-乙基-5-甲基-4-馬來醯亞胺基苯基)甲烷和雙(3, 5-二乙基-4-馬來醯亞胺基苯基)甲烷所組成的群組。The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, wherein the bismaleimide is selected from bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and bis(3,5-diethyl-4-maleimidophenyl)methane group. 如請求項1所述的低膨脹係數低介電損耗高剛性無鹵樹脂組成物，其中，所述多元羥基改質苯乙烯樹脂是選自以下化學式(I)以及(II)所組成的群組：

(I)、

(II)； 其中，R ₁為氫或碳數1至6之烴基，R ₂為

所表示之取代基，n為0至20之數，p為0.1至2.5之數，X為氫或碳數1至6之烴基。 The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, wherein the polyvalent hydroxyl modified styrene resin is selected from the group consisting of the following chemical formulae (I) and (II) :

(I),

(II); wherein, R ₁ is hydrogen or a hydrocarbon group with 1 to 6 carbon atoms, and R ₂ is

In the represented substituent, n is a number from 0 to 20, p is a number from 0.1 to 2.5, and X is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. 如請求項1所述的低膨脹係數低介電損耗高剛性無鹵樹脂組成物，其中，所述氰酸酯硬化劑包括：30至45重量份的PN型氰酸酯硬化劑；以及30至45重量份的BPA型氰酸酯硬化劑。The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, wherein the cyanate ester hardener comprises: 30 to 45 parts by weight of a PN type cyanate ester hardener; 45 parts by weight of BPA type cyanate hardener. 如請求項1所述的低膨脹係數低介電損耗高剛性無鹵樹脂組成物，其中，所述非DOPO含磷阻燃劑是選自次磷酸金屬鹽（phosphinate）、聚磷酸鹽（polyphosphate）、鏻鹽（phosphonium salt）、磷酸酯（phosphate ester）、磷腈（phosphazene）以及亞磷酸酯（phosphite ester）所組成的群組。The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, wherein the non-DOPO phosphorus-containing flame retardant is selected from the group consisting of phosphinate, polyphosphate , phosphonium salts, phosphate esters, phosphazenes, and phosphite esters. 如請求項1所述的低膨脹係數低介電損耗高剛性無鹵樹脂組成物，其中，所述非DOPO含磷阻燃劑是1至10重量份的間苯二酚雙二甲苯基磷酸鹽，以及1至10重量份的磷腈化合物。The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, wherein the non-DOPO phosphorus-containing flame retardant is 1 to 10 parts by weight of resorcinol bis-xylyl phosphate , and 1 to 10 parts by weight of a phosphazene compound. 如請求項1所述的低膨脹係數低介電損耗高剛性無鹵樹脂組成物，進一步包括：一硬化促進劑，所述硬化促進劑是選自磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、胍系硬化促進劑、金屬系硬化促進劑以及過氧化物系硬化促進劑所組成的群組。The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, further comprising: a hardening accelerator, the hardening accelerator is selected from phosphorus-based hardening accelerators, amine-based hardening accelerators, A group consisting of an imidazole-based hardening accelerator, a guanidine-based hardening accelerator, a metal-based hardening accelerator, and a peroxide-based hardening accelerator. 如請求項1所述的低膨脹係數低介電損耗高剛性無鹵樹脂組成物，進一步包括：一無機填料，所述無機填料是選自二氧化矽、氧化鋁、氫氧化鋁、氧化鎂、氫氧化鎂、碳酸鈣、氮化鋁、氮化硼、碳化鋁矽、碳化矽、二氧化鈦、氧化鋅、氧化鋯、硫酸鋇、碳酸鎂、碳酸鋇、雲母、滑石以及石墨烯所組成的群組。The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, further comprising: an inorganic filler selected from the group consisting of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, Group consisting of magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene . 一種積層板，其包括： 一樹脂基板，其包括多個半固化膠片，且每一所述半固化膠片由一玻璃纖維布經由塗覆如請求項1所述的低膨脹係數低介電損耗高剛性無鹵樹脂組成物所製成；以及 一金屬箔層，其設置於所述樹脂基板的至少一表面上。 A laminate comprising: A resin substrate comprising a plurality of prepreg films, and each of the prepreg films is made of a glass fiber cloth coated with the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity as described in claim 1 made; and A metal foil layer is disposed on at least one surface of the resin substrate. 一種印刷電路板，其包括如請求項9所述的積層板。A printed circuit board comprising the laminate as claimed in claim 9.