TW202134340A - Halogen-free low-dielectric composition, laminated substrate and printed circuit board therof - Google Patents

Halogen-free low-dielectric composition, laminated substrate and printed circuit board therof Download PDF

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TW202134340A
TW202134340A TW109106662A TW109106662A TW202134340A TW 202134340 A TW202134340 A TW 202134340A TW 109106662 A TW109106662 A TW 109106662A TW 109106662 A TW109106662 A TW 109106662A TW 202134340 A TW202134340 A TW 202134340A
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epoxy resin
halogen
resin
dielectric composition
free low
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TWI724806B (en
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于達元
陳凱楊
林鴻名
苑紹傑
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聯茂電子股份有限公司
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Abstract

The present invention provides a halogen-free low-dielectric composition, a laminated board and a printed circuit board, wherein the halogen-free low-dielectric composition (a) 100 parts by weight of epoxy resin; (b) 10 to 25 parts by weight of DOPO modification hardener; (c) 10 to 20 parts by weight of benzoxazine resin; (d) 100 to 120 parts by weight of active ester compound; (e) 10 to 20 parts by weight of maleic anhydride modification hardener And (f) 20 to 45 parts by weight of a non-DOPO flame retardant. The halogen-free low-dielectric composition of the present invention provides a halogen-free epoxy resin composition with a specific composition and proportion, and has high glass transition temperature, low dielectric constant, low dielectric loss, high Characteristics of heat resistance and high storage modulus.

Description

無鹵低介電組成物、積層板以及印刷電路板Halogen-free low-dielectric composition, laminate and printed circuit board

本發明涉及一種低介電組成物、積層板以及印刷電路板,特別是涉及一種無鹵低介電組成物、積層板以及印刷電路板。The invention relates to a low-dielectric composition, a laminated board and a printed circuit board, in particular to a halogen-free low-dielectric composition, a laminated board and a printed circuit board.

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H2 O鍵結,造成吸濕性增加。 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,在全球環保意識抬頭下,加上歐盟實施RoHS環保規章,使得無鉛製程的銅箔基板及無鹵素等環保基板,逐漸取代傳統FR-4基板。In the printed circuit board technology, the thermosetting resin composition mainly includes epoxy resin and hardener, which is heated and combined with the reinforcing material to form a prepreg, which is then pressed with the upper and lower copper foils at high temperature and high pressure Combined into a copper foil laminated board (or copper foil substrate). Generally, the thermosetting resin composition uses a phenol novolac resin hardener with a hydroxyl group (-OH). After it is combined with an epoxy resin, the epoxy group will open the ring to form a 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. The prior art epoxy resin composition 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, with the rise of global environmental awareness, the EU has implemented RoHS environmental regulations , Enabling lead-free copper foil substrates and halogen-free environmentally friendly substrates to gradually replace traditional FR-4 substrates.

因此,如何開發出具有優異介電性能以及符合印刷電路板其他特性需求,諸如高玻璃轉化溫度(Tg)、低熱膨脹係數、低吸水率之特性的材料,並將其應用於高頻印刷電路板之製造,乃是現階段印刷電路板材料供應商亟欲解決之問題。Therefore, how to develop materials with excellent dielectric properties and meet other characteristics of printed circuit boards, such as high glass transition temperature (Tg), low thermal expansion coefficient, and low water absorption, and apply them to high-frequency printed circuit boards The manufacturing of printed circuit board materials is a problem that the suppliers of printed circuit board materials urgently want to solve at this stage.

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無鹵低介電組成物、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 low-dielectric composition, a laminated board and a printed circuit board 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,提供一種無鹵低介電組成物,其包括: (a)     100重量份的環氧樹脂; (b)10至25重量份的DOPO改質硬化劑; (c)     10至20重量份的苯並噁嗪樹脂; (d)100至120重量份的活性酯合物; (e)     10至20重量份的馬來酸酐改質硬化劑;以及 (f)      20至45重量份的非DOPO阻燃劑。In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide a halogen-free low-dielectric composition, which includes: (a) 100 parts by weight of epoxy resin; (b) 10 to 25 parts by weight of DOPO modified hardener; (c) 10 to 20 parts by weight of benzoxazine resin; (d) 100 to 120 parts by weight of active ester compound; (e) 10 to 20 parts by weight of maleic anhydride modified hardener; and (f) 20 to 45 parts by weight of non-DOPO 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,且每一個所述半固化膠片由一玻璃纖維布經塗覆本發明的無鹵低介電組成物所製成;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 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 The cloth is made by coating the halogen-free low-dielectric composition of the present invention; and a metal foil layer disposed 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-mentioned technical problems, another technical solution adopted by the present invention is to provide a printed circuit board, which includes the laminated board according to the present invention.

本發明的其中一有益效果在於,本發明的無鹵低介電組成物藉著特定之組成份及比例,可提供不含鹵素的環氧樹脂組成物,且其具有高玻璃轉化溫度、低介電常數、低介電損耗、高耐熱性及高儲存模數的特性。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 low-dielectric composition of the present invention can provide a halogen-free epoxy resin composition with a specific composition and ratio, and it has a high glass transition temperature and a low dielectric. The characteristics of electric constant, low dielectric loss, high heat resistance and high storage modulus. It can be made into semi-cured film or resin film to achieve the purpose of being applicable to copper foil substrates and printed circuit boards; in terms of industrial applicability, the products derived from the present invention can fully satisfy the current market need.

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。In order to further understand the features and technical content of the present invention, please refer to the following detailed description and drawings about the present invention. However, the provided drawings are only for reference and description, and are not used 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“無鹵低介電組成物、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,在不悖離本發明的構思下進行各種修改與變更。另外,本發明的附圖僅為簡單示意說明,並非依實際尺寸的描繪,事先聲明。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。The following are specific examples to illustrate the implementation of the “halogen-free low-dielectric composition, laminate and printed circuit board” disclosed in the present invention. Those skilled in the art can understand the present invention from the content disclosed in this specification. Advantages and effects. The present invention can be implemented or applied through other different specific embodiments, and various details in this specification can also be based on different viewpoints and applications, and various modifications and changes can be made without departing from the concept of the present invention. In addition, the drawings of the present invention are merely schematic illustrations, and are not drawn according to actual dimensions, and are stated in advance. The following embodiments will further describe the related technical content of the present invention in detail, but the disclosed content is not intended to limit the protection scope of the present invention.

應當可以理解的是,雖然本文中可能會使用到“第一”、“第二”、“第三”等術語來描述各種元件或者信號,但這些元件或者信號不應受這些術語的限制。這些術語主要是用以區分一元件與另一元件,或者一信號與另一信號。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。It should be understood that although terms such as "first", "second", and "third" may be used herein to describe various elements or signals, these elements or signals should not be limited by these terms. These terms are mainly used to distinguish one element from another, or one signal from another signal. In addition, the term "or" used in this document may include any one or a combination of more of the associated listed items depending on the actual situation.

本發明第一實施例提供一種無鹵低介電組成物,其包括: (a)100重量份的環氧樹脂; (b)10至25重量份的DOPO改質硬化劑; (c)10至20重量份的苯並噁嗪樹脂; (d)100至120重量份的活性酯合物; (e)10至20重量份的馬來酸酐改質硬化劑;以及 (f)20至45重量份的非DOPO阻燃劑。The first embodiment of the present invention provides a halogen-free low-dielectric composition, which includes: (a) 100 parts by weight of epoxy resin; (b) 10 to 25 parts by weight of DOPO modified hardener; (c) 10 to 20 parts by weight of benzoxazine resin; (d) 100 to 120 parts by weight of active ester compound; (e) 10 to 20 parts by weight of maleic anhydride modified hardener; and (f) 20 to 45 parts by weight of non-DOPO flame retardant.

於本發明的一具體實施例中,本發明的環氧樹脂是選自由雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、雙酚A酚醛型環氧樹脂、雙酚F酚醛型環氧樹脂、二苯乙烯型環氧樹脂、含三嗪骨架之環氧樹脂、含芴骨架之環氧樹脂、三酚酚甲烷型環氧樹脂、聯苯型環氧樹脂、亞二甲苯基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂、脂環式環氧樹脂、多官能酚類及稠環芳香族類之二縮水甘油醚化合物、分子內具有3個或4個環氧基的三官能及四官能環氧樹脂以及含磷環氧樹脂所組成的群組之至少一者。In a specific embodiment of the present invention, the epoxy resin of the present invention is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, Cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, stilbene epoxy resin, epoxy resin containing triazine skeleton, epoxy resin containing fluorene skeleton , Triphenol phenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin Resins, alicyclic epoxy resins, polyfunctional phenols and condensed ring aromatic diglycidyl ether compounds, trifunctional and tetrafunctional epoxy resins with 3 or 4 epoxy groups in the molecule, and phosphorus-containing rings At least one of the group consisting of oxy resin.

更詳細來說,含磷環氧樹脂是將磷化合物導入前述環氧樹脂而成的含磷環氧樹脂;而多官能酚類及稠環芳香族類之二縮水甘油醚化合物可進一步包括:分子結構中含有海因環(五元二氮雜環)的縮水甘油胺型環氧樹脂(海因環氧樹脂),如下式:In more detail, the phosphorus-containing epoxy resin is a phosphorus-containing epoxy resin obtained by introducing phosphorus compounds into the aforementioned epoxy resin; and the diglycidyl ether compound of polyfunctional phenols and condensed ring aromatics may further include: Glycidylamine epoxy resin (hydantoin epoxy resin) containing a hydantoin ring (five-membered diaza heterocyclic ring) in the structure, as shown in the following formula:

Figure 02_image001
(式一);其中,R1 和R2 為甲基或乙基,n為介於0至10之間的正整數;
Figure 02_image001
(Formula 1); wherein, R 1 and R 2 are methyl or ethyl, and n is a positive integer between 0 and 10;

Figure 02_image003
(式二);其中,R為苯環或萘環。
Figure 02_image003
(Formula 2); Wherein, R is a benzene ring or a naphthalene ring.

Figure 02_image005
(式三)。
Figure 02_image005
(Equation three).

詳細來說,海因環氧樹脂(Hydantion Epoxy Resin) 是分子結構中含有海因環(五元二氮雜環)的縮水甘油胺型環氧樹脂,最常見的是二甲基海因環氧樹脂。具體而言,海因環可有效提升韌性、剛性、水溶性及提高玻璃轉化溫度Tg(至約175℃)。除此之外,低分子量的二甲基海因環氧樹脂還可進一步與活性增韌劑改性,以提高環氧樹脂的韌性(如式二所示);或可與丙烯酸反應,使縮水基開環引入雙鍵,改質為水溶性光固化樹脂(如式三所示)。In detail, Hydantion Epoxy Resin is a glycidylamine epoxy resin containing a hydantoin ring (five-membered diazacyclic ring) in the molecular structure, and the most common one is dimethyl hydantoin epoxy Resin. Specifically, the hydantoin ring can effectively improve toughness, rigidity, water solubility and increase the glass transition temperature Tg (to about 175°C). In addition, the low-molecular-weight dimethylhydantoin epoxy resin can be further modified with an active toughening agent to improve the toughness of the epoxy resin (as shown in formula 2); or it can react with acrylic acid to shrink The ring-opening of the base introduces a double bond, and it is modified into a water-soluble light-curable resin (as shown in formula 3).

較佳地,環氧樹脂可以是由前述類型的樹脂依照不同比例組成,舉例來說,本發明的環氧樹脂可以由20至40重量份的二環戊二烯型環氧樹脂、10至20重量份的多官能酚類及稠環芳香族類之二縮水甘油醚化合物以及40至60重量份的甲酚酚醛型環氧樹脂所組成。更詳細來說,二環戊二烯型(DCPD)環氧樹脂可以有效降低介電常數(Dk )數值,降低Dk 至4.0。多官能酚類及稠環芳香族類之二縮水甘油醚化合物可提高玻璃轉化溫度(Tg),更可提升產物的結構韌性。甲酚酚醛型環氧樹脂可提高玻璃轉化溫度(Tg),更降低電性。Preferably, the epoxy resin can be composed of the aforementioned types of resins in different proportions. For example, the epoxy resin of the present invention can be composed of 20 to 40 parts by weight of dicyclopentadiene epoxy resin, 10 to 20 parts by weight. Parts by weight of polyfunctional phenols and condensed ring aromatic diglycidyl ether compounds and 40 to 60 parts by weight of cresol novolac epoxy resin. In more detail, the dicyclopentadiene (DCPD) epoxy resin can effectively reduce the dielectric constant (D k ) value, reducing D k to 4.0. Multifunctional phenols and fused-ring aromatic diglycidyl ether compounds can increase the glass transition temperature (Tg) and improve the structural toughness of the product. Cresol-type epoxy resin can increase the glass transition temperature (Tg) and reduce the electrical properties.

9,10-二氫-9-氧雜-10-磷菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO)改質硬化劑於本發明主要是做為與環氧樹脂結合的硬化劑使用,改質硬化劑除了可提供良好的熱穩定性和低介電性外,更可提升阻燃的功效,本發明的無鹵低介電組成物中DOPO改質硬化劑是選自DOPO-對苯二酚樹脂、DOPO-萘二醇樹脂、DOPO-酚醛清漆樹脂以及DOPO-雙酚酚醛樹脂所組成的群組。更進一步而言,DOPO-雙酚酚醛樹脂是選自DOPO-雙酚A線型酚醛樹脂(DOPO-BPAN)、DOPO-雙酚F線型酚醛樹脂(DOPO-BPSN)以及DOPO-雙酚S線型酚醛樹脂(DOPO-BPSN)所組成的群組。9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO) modification hardener is mainly used in the present invention It is used as a hardener combined with epoxy resin. In addition to providing good thermal stability and low dielectric properties, the modified hardener can also improve the flame retardant effect. The halogen-free low-dielectric composition of the present invention The DOPO modified hardener is selected from the group consisting of DOPO-hydroquinone resin, DOPO-naphthalene glycol resin, DOPO-novolac resin and DOPO-bisphenol phenolic resin. Furthermore, DOPO-bisphenol phenolic resin is selected from DOPO-bisphenol A novolac resin (DOPO-BPAN), DOPO-bisphenol F novolac resin (DOPO-BPSN) and DOPO-bisphenol S novolac resin (DOPO-BPSN).

於本發明的一具體實施例中,苯並噁嗪樹脂是選自下列群組之至少一者: BPA型苯並噁嗪、BPF型苯並噁嗪、BPS型苯並噁嗪、DDM型苯並噁嗪、ODA型苯並噁嗪以及聚醯亞胺化苯並噁嗪(polybenzoxazine with polyimide)。苯並噁嗪樹脂可降低介電常數Dk (1-10GHz,平均大約4.1)、介電耗損因數Df (1-10GHz,平均大約0.008)及提升耐熱性。In a specific embodiment of the present invention, the benzoxazine resin is selected from at least one of the following groups: BPA type benzoxazine, BPF type benzoxazine, BPS type benzoxazine, DDM type benzene And oxazine, ODA type benzoxazine and polybenzoxazine with polyimide (polybenzoxazine with polyimide). The benzoxazine resin can reduce the dielectric constant D k (1-10 GHz, about 4.1 on average), the dielectric loss factor D f (1-10 GHz, about 0.008 on average), and improve heat resistance.

於本發明的一具體實施例中,活性酯合物具有以下結構:

Figure 02_image007
;In a specific embodiment of the present invention, the active ester compound has the following structure:
Figure 02_image007

其中,X為苯環或萘環,R1 是CH2

Figure 02_image009
,R2 是選自萘酚、苯酚、聯苯酚、雙酚A、雙酚F、雙酚S以及雙環戊二烯(DCPD)所組成的群組,l、m、k為0或1,n是介於0.25至2。具體來說,活性酯合物可有效降低介電常數Dk 、耗損因數Df 及提升阻燃效果。Among them, X is a benzene ring or a naphthalene ring, and R 1 is CH 2 or
Figure 02_image009
, R 2 is selected from the group consisting of naphthol, phenol, biphenol, bisphenol A, bisphenol F, bisphenol S and dicyclopentadiene (DCPD), l, m, k are 0 or 1, n It is between 0.25 and 2. Specifically, the active ester compound can effectively reduce the dielectric constant D k , the dissipation factor D f and enhance the flame retardant effect.

於本發明的一具體實施例中,馬來酸酐改質硬化劑選自下列群組之至少一者:In a specific embodiment of the present invention, the maleic anhydride modified hardener is selected from at least one of the following groups:

(1)具有以下結構的苯乙烯-馬來酸酐共聚物:

Figure 02_image011
,(1) Styrene-maleic anhydride copolymer with the following structure:
Figure 02_image011
,

其中m和n為相同或不同之正整數;Where m and n are the same or different positive integers;

(2)具有以下結構的改質型馬來酸酐共聚物:

Figure 02_image013
(2) Modified maleic anhydride copolymer with the following structure:
Figure 02_image013

其中,X、Y和n為相同或不同之正整數, R為乙酸酐;或Wherein, X, Y and n are the same or different positive integers, and R is acetic anhydride; or

(3)具有以下結構的馬來酸酐改質聚醯亞胺樹脂:

Figure 02_image015
;(3) Maleic anhydride modified polyimide resin with the following structure:
Figure 02_image015

其中,X為表示含10個以上碳原子的碳鏈基團、含苯環的基團或者含10個以上碳原子的碳鏈與苯環基團的結構,m、n與l皆為整數且大於等於1。Wherein, X represents a carbon chain group containing more than 10 carbon atoms, a group containing a benzene ring, or the structure of a carbon chain containing more than 10 carbon atoms and a benzene ring group, m, n, and l are all integers and Greater than or equal to 1.

具體來說,馬來酸酐改質硬化劑可降低介電耗損因數Df (1-10GHz,平均大約0.008)及提升耐熱性。Specifically, maleic anhydride modified hardener can reduce the dielectric loss factor D f (1-10 GHz, average about 0.008) and improve heat resistance.

於本發明的一具體實施例中,本發明的阻燃劑使用非DOPO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介電常數Dk 以及介電耗損DfIn a specific embodiment of the present invention, the flame retardant of the present invention uses a non-DOPO flame retardant, which means that it does not contain 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ( DOPO) derivatives. In detail, the POC bond in the DOPO structure is easily hydrolyzed into 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 dielectric constant D k and the dielectric constant of the material. Depletion D f .

更詳細來說,非DOPO阻燃劑可選自結構式(I)、結構式(II)以及結構式(III)的化合物所組成的群組:

Figure 02_image017
(Ⅰ)、
Figure 02_image019
(Ⅱ)以及
Figure 02_image021
(Ⅲ);In more detail, the non-DOPO flame retardant can be selected from the group consisting of compounds of structural formula (I), structural formula (II) and structural formula (III):
Figure 02_image017
(Ⅰ),
Figure 02_image019
(Ⅱ) and
Figure 02_image021
(Ⅲ);

其中,R1

Figure 02_image023
Figure 02_image025
Figure 02_image027
Figure 02_image029
Figure 02_image031
Figure 02_image033
Figure 02_image035
Figure 02_image037
;Where R 1 is
Figure 02_image023
,
Figure 02_image025
,
Figure 02_image027
,
Figure 02_image029
,
Figure 02_image031
,
Figure 02_image033
,
Figure 02_image035
or
Figure 02_image037

其中,R2

Figure 02_image039
Figure 02_image041
Figure 02_image043
Figure 02_image045
;Where R 2 is
Figure 02_image039
,
Figure 02_image041
,
Figure 02_image043
or
Figure 02_image045

其中,R3

Figure 02_image047
Figure 02_image049
或CH2 CH2 OCH=CH2 ;Where R 3 is
Figure 02_image047
,
Figure 02_image049
Or CH 2 CH 2 OCH=CH 2 ;

其中,n是0至500的整數;Wherein, n is an integer from 0 to 500;

其中,R4

Figure 02_image051
Figure 02_image053
; 其中,m≧1;Where R 4 is
Figure 02_image051
or
Figure 02_image053
; Among them, m≧1;

其中,R5

Figure 02_image055
Figure 02_image057
;Where R 5 is
Figure 02_image055
or
Figure 02_image057

其中,R6

Figure 02_image059
Figure 02_image061
Figure 02_image063
。Where R 6 is
Figure 02_image059
,
Figure 02_image061
or
Figure 02_image063
.

詳細來說,非DOPO阻燃劑可選自磷酸鹽化合物或含氮磷酸鹽化合物,舉例而言,可以是選自間苯二酚雙二甲苯基磷酸鹽(resorcinol dixylenylphosphate,RDXP(如PX-200))、聚磷酸三聚氰胺(melamine polyphosphate)、三(2-羧乙基)膦(tri(2-carboxyethyl)phosphine,TCEP)、三甲基磷酸鹽(trimethyl phosphate,TMP)、三(異丙基氯)磷酸鹽、二甲基-甲基磷酸鹽(dimethyl methyl phosphonate,DMMP)、雙酚聯苯磷酸鹽(bisphenol diphenyl phosphate)、聚磷酸銨(ammonium polyphosphate)、對苯二酚-雙-(聯苯基磷酸鹽)(hydroquinone bis-(diphenyl phosphate))、雙酚A-雙-(聯苯基磷酸鹽)(bisphenol A bis-(diphenylphosphate))以及 磷腈化合物(Phosphazene,如SPB-100 )所組成的群組。In detail, the non-DOPO flame retardant can be selected from phosphate compounds or nitrogen-containing phosphate compounds, for example, can be selected from resorcinol dixylenyl phosphate (resorcinol dixylenyl phosphate, RDXP (such as PX-200) )), melamine polyphosphate, tri(2-carboxyethyl)phosphine (TCEP), trimethyl phosphate (TMP), tris(isopropyl chloride) ) Phosphate, dimethyl methyl phosphonate (DMMP), bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis-(biphenyl) Hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenylphosphate), and Phosphazene (such as SPB-100) 'S group.

較佳地,本發明硬化促進劑可選自咪唑、金屬鹽、三級胺或呱啶類化合物所組成的群組的至少一者或其混合,更進一步的可選自三氟化硼胺複合物、2-乙基-4-甲基咪唑(2-ethyl-4-methylimidazole,2E4MI)、2-甲基咪唑(2-methylimidazole,2MI)、2-苯基咪唑(2-phenyl-1H-imidazole,2PZ)、氯化乙基三苯基鏻(ethyltriphenyl phosphonium chloride)、三苯基膦(triphenylphosphine,TPP)、乙醯丙酮鈷(Ⅱ)(cobalt(Ⅱ) acetylacetonate)與4-二甲基胺基吡啶(4-dimethylaminopyridine,DMAP)、低分子量的端溴基液體丁二烯橡膠(terminal bromine-based liquid butadiene rubber,BTPB),有機金屬鹽如雙乙醯丙酮鈷(Ⅱ)、三乙醯丙酮鈷(Ⅲ),三級胺類如三乙胺、三丁胺等以及二氮雜雙環[2,2,2]辛烷等。更佳地,硬化促進劑是4-二甲基胺基吡啶(4-dimethylaminopyridine)。具體而言,咪唑類化合物對樹脂成分具有尤佳之相容性,藉此可獲得均勻性高之硬化物。較佳地,硬化促進劑的添加量可以是以100重量份的環氧樹脂為基準的1%。Preferably, the hardening accelerator of the present invention can be selected from at least one of the group consisting of imidazole, metal salt, tertiary amine or piperidine compound, or a mixture thereof, and further can be selected from boron trifluoride amine compound Compounds, 2-ethyl-4-methylimidazole (2E4MI), 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2-phenyl-1H-imidazole) , 2PZ), ethyltriphenyl phosphonium chloride (ethyltriphenyl phosphonium chloride), triphenylphosphine (TPP), cobalt(Ⅱ) acetylacetonate and 4-dimethylamino Pyridine (4-dimethylaminopyridine, DMAP), low-molecular-weight terminal bromine-based liquid butadiene rubber (BTPB), organic metal salts such as cobalt diacetone acetone (Ⅱ), cobalt triacetone acetone (Ⅲ), tertiary amines such as triethylamine, tributylamine, etc., and diazabicyclo[2,2,2]octane, etc. More preferably, the hardening accelerator is 4-dimethylaminopyridine. Specifically, the imidazole compound has particularly good compatibility with the resin component, so that a cured product with high uniformity can be obtained. Preferably, the addition amount of the hardening accelerator may be 1% based on 100 parts by weight of epoxy resin.

另一方面,無機填料可增加無鹵低介電組成物的熱傳導性,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100至120重量份。On the other hand, the inorganic filler can increase the thermal conductivity of the halogen-free low-dielectric composition and improve its thermal expansion and mechanical strength. Preferably, the inorganic filler is uniformly distributed in the halogen-free low-dielectric composition. Preferably, the inorganic filler can be surface-treated in advance with a silane coupling agent. Preferably, the inorganic filler may be spherical, flake, granular, columnar, plate, needle or irregular inorganic filler. Preferably, the inorganic filler is selected from silica (such as molten, non-molten, porous or hollow silica), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, nitriding 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, graphene. Preferably, the addition amount of the inorganic filler may be 100 to 120 parts by weight based on 100 parts by weight of epoxy resin.

此外,本發明的無鹵低介電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25至35重量份的丁酮(MEK)以及20至30重量份的丙二醇甲醚醋酸酯(PMA)的組合或其他溶劑等的組合。In addition, the halogen-free low-dielectric 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 acetone, The group consisting of butanone, propylene glycol methyl ether, propylene glycol methyl ether acetate, dimethylacetamide and cyclohexanone. For example, the solvent may be selected from a combination of 25 to 35 parts by weight of methyl ethyl ketone (MEK) and 20 to 30 parts by weight of propylene glycol methyl ether acetate (PMA) or a combination of other solvents and the like.

更進一步地,本發明的無鹵低介電組成物視需求進一步包括增韌劑,如核殼聚合物,用以提高板材韌性,同時也提升耐熱性能。較佳地,增韌劑可選自環氧樹脂型增韌劑,如KANEKA 的MX系列產品及Metablen 的W系列產品,添加量可以是以100重量份的環氧樹脂為基準的2重量份。具體來說,上述核殼聚合物之體積平均粒徑為0.01至1μm,較佳為0.1至0.5μm,且上述核殼聚合物之核部的玻璃轉化溫度(Tg)未達0℃,且上述核殼聚合物之殼部的玻璃轉化溫度(Tg)未達20℃,更詳細來說,上述核殼聚合物於核部與殼部之間含有中間層,該中間層含有30至100重量%的多官能性單體及0至70重量%的乙烯系單體,且上述核殼聚合物之殼部含有具有環氧基單體,透過核殼聚合物之環氧基單體與環氧樹脂環氧基的結合可以更加提升本發明組合物的耐熱性能。Furthermore, the halogen-free low-dielectric composition of the present invention may further include a toughening agent, such as a core-shell polymer, as required, to improve the toughness of the board and also improve the heat resistance. Preferably, the toughening agent can be selected from epoxy resin toughening agents, such as KANEKA's MX series products and Metablen's W series products, and the addition amount can be 2 parts by weight based on 100 parts by weight of epoxy resin. Specifically, the volume average particle diameter of the core-shell polymer is 0.01 to 1 μm, preferably 0.1 to 0.5 μm, and the glass transition temperature (Tg) of the core portion of the core-shell polymer is less than 0°C, and The glass transition temperature (Tg) of the shell part of the core-shell polymer is less than 20°C. More specifically, the core-shell polymer contains an intermediate layer between the core and the shell, and the intermediate layer contains 30 to 100% by weight Polyfunctional monomers and 0 to 70% by weight of vinyl monomers, and the shell part of the core-shell polymer contains epoxy monomers through the core-shell polymer epoxy monomers and epoxy resin The combination of epoxy groups can further improve the heat resistance of the composition of the present invention.

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,且每一個所述半固化膠片由一玻璃纖維布經塗覆如本發明的無鹵低介電組成物所製成;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 is a laminated board, which includes: (a) a resin substrate, which includes a plurality of semi-cured films, and each of the semi-cured films is coated with a glass fiber cloth as in the present invention It is made of a halogen-free low-dielectric composition; and (b) a metal foil layer, which is arranged on at least one surface of the resin substrate, or the metal foil layer can be arranged on the resin substrate 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。In addition, the present invention provides another technical solution which is a printed circuit board, which includes the laminated board of the present invention.

[實施例][Example]

以下實施例E1~E5是使用本發明的無鹵低介電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。 表1 組成份 E1 E2 E3 E4 E5 環氧樹脂 DCPD epoxy 30 30 25 25 25 Cresol novolac epoxy 55 55 50 50 50 Multi-functional epoxy 15 15 15 0 0 Hydantion epoxy 0 0 0 15 15 硬化劑 DOPO-BPAN (DOPO-雙酚A線型酚醛樹脂) 25 25 25 15 15  苯並噁嗪樹脂 10 15 10 10 10 活性酯化物 (HPC-8000) 110 100 110 100 100 Anhydride modified hardener 10 15 10 20 20 阻燃劑 Resorcinol dixylenylphosphate 10 15 10 10 10 Cyclic phosphazene 20 15 20 20 20 增韌劑 核殼聚合物 (Core shell rubber ) 2 2 2 2 2 無機填料 熔融二氧化矽 90 90 90 90 90 球型二氧化矽 10 10 10 10 10 促進劑 DMAP(4-二甲基胺基吡啶) 1 1 1 1 1 溶劑 MEK(丁酮) 30 30 30 30 30 PMA(丙二醇甲醚乙脂) 20 20 20 20 20 PM(丙二醇甲醚) 15 15 15 15 15 Toluene (甲苯) 30 30 30 30 30 [比較例] 依據下述表2的比較例C1至C5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。 表2 組成份 C1 C2 C3 C4 環氧樹脂 HP-7200 40 40 40 40 NC-3000 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 苯並噁嗪樹脂 LZ8280 - 60 - 50 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 硬化促進劑 2E4MI (2-乙基-4-甲基咪唑) 1 1 1 1 溶劑 MEK(丁酮) 42 80 114 97 PMA(丙二醇甲醚乙脂) 20 - - - * HP-7200:DCPD(二環戊二烯型)型環氧樹脂 * NC-3000:日本化藥公司聯苯型環氧樹脂 [物性測試] 分別將上述實施例E1至E5及比較例C1至C5的銅箔積層板進行物性測試,並紀錄測試結果於表3: (1)       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。 (2)       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。 (3)       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。 (4)       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)。 (5)       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)。 (6)       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。 (7)       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。 (8)       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。 (9)       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。 性質測試 測試方法 E1 E2 E3 E4 E5 C1 C2 C3 C4 玻璃轉化溫度(Tg) DSC 159 162 151 158 250 161 168 147 171 含銅基板耐熱性(T288) TMA >60 >60 >60 >60 >60 5 22 32 >70 S/D dip cycles >20 >20 >20 >20 >20 3 18 8 >20 PCT (dip minute) 20 s/288℃ 合格 合格 合格 合格 合格 不合格 合格 不合格 合格 P/S (lb/min) Hoz Cu foil 6.7 6.3 6.8 6.2 8.1 5.2 5.8 5.5 6.1 Dk @10GHz 10GHz 3.98 4.05 4.02 3.96 4.62 3.93 4.14 4.25 4.21 Df @10GHz 10GHz 0.007 0.007 0.007 0.008 0.007 0.015 0.009 0.012 0.013 耐燃性 UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 其他 PP外觀 表3The following examples E1 to E5 use the halogen-free low-dielectric composition of the present invention to manufacture semi-cured films in a continuous process. Usually glass fiber cloth is used as the base material. The roll-shaped glass fiber cloth continuously passes through a series of rollers into the gluing tank, and the halogen-free low-dielectric composition of the present invention is installed in the tank. In the gluing tank, the glass fiber cloth is fully infiltrated by the resin, and then the excess resin is scraped off by the metering roller, and then it enters the gluing furnace for a certain period of time to allow the solvent to evaporate and solidify the resin to a certain extent, cool, and rewind to form a half Curing the film, and then take the prepregs made in the above batches, take four prepregs of the same batch and two 18 μm copper foils, and stack them in the order of copper foil, four prepregs, and copper foil, and then The copper foil substrate was formed by pressing at 220°C for 2 hours under vacuum conditions, and four sheets of semi-cured film were cured to form an insulating layer between the two copper foils. Table 1 Component E1 E2 E3 E4 E5 Epoxy resin DCPD epoxy 30 30 25 25 25 Cresol novolac epoxy 55 55 50 50 50 Multi-functional epoxy 15 15 15 0 0 Hydantion epoxy 0 0 0 15 15 hardener DOPO-BPAN (DOPO-bisphenol A novolac resin) 25 25 25 15 15 Benzoxazine resin 10 15 10 10 10 Active ester compound (HPC-8000) 110 100 110 100 100 Anhydride modified hardener 10 15 10 20 20 Flame retardant Resorcinol dixylenylphosphate 10 15 10 10 10 Cyclic phosphazene 20 15 20 20 20 Toughener Core shell rubber 2 2 2 2 2 Inorganic filler Fused silica 90 90 90 90 90 Spherical silica 10 10 10 10 10 Accelerator DMAP (4-dimethylaminopyridine) 1 1 1 1 1 Solvent MEK (butanone) 30 30 30 30 30 PMA (Propylene Glycol Methyl Ether Ethyl) 20 20 20 20 20 PM (Propylene Glycol Methyl Ether) 15 15 15 15 15 Toluene (toluene) 30 30 30 30 30 [Comparative Example] A prepreg film was manufactured in a continuous process according to the components and ratios of Comparative Examples C1 to C5 in Table 2 below. Usually glass fiber cloth is used as the base material. The roll-shaped glass fiber cloth continuously passes through a series of rollers into the gluing tank, and the halogen-free low-dielectric composition of the present invention is installed in the tank. In the gluing tank, the glass fiber cloth is fully infiltrated by the resin, and then the excess resin is scraped off by the metering roller, and then it enters the gluing furnace for a certain period of time to allow the solvent to evaporate and solidify the resin to a certain extent, cool, and rewind to form a half Curing the film, and then take the prepregs made in the above batches, take four prepregs of the same batch and two 18 μm copper foils, and stack them in the order of copper foil, four prepregs, and copper foil, and then The copper foil substrate was formed by pressing at 220°C for 2 hours under vacuum conditions, and four sheets of semi-cured film were cured to form an insulating layer between the two copper foils. Table 2 Component C1 C2 C3 C4 Epoxy resin HP-7200 40 40 40 40 NC-3000 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 Benzoxazine resin LZ8280 - 60 - 50 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 Hardening accelerator 2E4MI (2-ethyl-4-methylimidazole) 1 1 1 1 Solvent MEK (butanone) 42 80 114 97 PMA (Propylene Glycol Methyl Ether Ethyl) 20 - - - * HP-7200: DCPD (dicyclopentadiene type) type epoxy resin * NC-3000: Nippon Kayaku Co., Ltd. biphenyl type epoxy resin [Physical Property Test] The above Examples E1 to E5 and Comparative Examples C1 to The physical properties of the C5 copper foil laminated board are tested, and the test results are recorded in Table 3: (1) Glass transition temperature (Tg): According to differential scanning calorimetry (DSC), according to IPC-TM-650 2.4.25 The DSC method is used for the determination. (2) Copper foil laminated board heat resistance (T288): also known as "tin bleaching result", the heat resistance test is based on the industry standard IPC-TM-650 2.4.24.1, the copper foil laminated board is immersed in a 288℃ tin furnace until the board bursts The time required. (3) Test of immersion tin after moisture absorption of copper-clad laminates: heat resistance (T288) test using semi-cured film with copper-foil layer, and immerse the copper-clad laminates in accordance with the industry standard IPC-TM-650 2.4.24.1 The time required for the tin furnace to burst at 288°C. (4) Copper foil laminated board heat resistance (S/D) test: copper-containing substrate immersion tin test (solder dip 288°C, 10 seconds, measuring the number of heat resistance cycles). (5) Copper-clad laminate heat resistance (PCT) test: PCT moisture absorption test after non-copper substrate PCT (pressure cooking at 121°C, 1 hour later, test solder dip at 288°C, 20 seconds to see if there is any cracking). (6) Peeling strength, half ounce copper foil (P/S) between the copper foil and the substrate: Measured according to the IPC-TM-650 2.4.1 testing specification. (7) Dielectric constant (D k ): Measured in accordance with IPC-TM-650 2.5.5 testing specifications. The dielectric constant represents the electrical insulation properties of the film. The lower the value, the better the electrical insulation properties. (8) Dielectric loss (D f ): Measured in accordance with IPC-TM-650 2.5.5 testing specifications. Dielectric loss indicates the ability of a substance to absorb microwaves of a certain frequency at a certain temperature, usually in the specifications of communication products , The dielectric loss value needs to be as low as possible. (9) Flaming test (UL94): Measured in accordance with the UL94 vertical combustion method, which uses the spontaneous combustion time, spontaneous combustion speed, and the state of falling particles to determine the flame resistance level of the plastic material after a standard test piece of plastic material is burned. . According to the fire resistance grade, it is HB, V-2, V-1, V-0, and the highest is 5V. The UL 94 test method refers to that the plastic material burns on the 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 burning time (T1) of the test piece after it is removed; Step 2: When the test piece flames After extinguishing, put it in 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 T1+T2 total. The requirement of UL 94 V-0 is that the average of T1 and T2 of a single burning time of the test piece must not exceed 10 seconds, and the total of T1 and T2 must not exceed 50 seconds to meet the requirements of UL 94 V-0. . Nature test Test Methods E1 E2 E3 E4 E5 C1 C2 C3 C4 Glass transition temperature (Tg) DSC 159 162 151 158 250 161 168 147 171 Heat resistance of copper-containing substrate (T288) TMA >60 >60 >60 >60 >60 5 twenty two 32 >70 S/D dip cycles >20 >20 >20 >20 >20 3 18 8 >20 PCT (dip minute) 20 s/288℃ qualified qualified qualified qualified qualified Unqualified qualified Unqualified qualified P/S (lb/min) Hoz Cu foil 6.7 6.3 6.8 6.2 8.1 5.2 5.8 5.5 6.1 D k @10GHz 10GHz 3.98 4.05 4.02 3.96 4.62 3.93 4.14 4.25 4.21 D f @10GHz 10GHz 0.007 0.007 0.007 0.008 0.007 0.015 0.009 0.012 0.013 Flame resistance UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 other PP appearance good good good good good good Difference Difference good table 3

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

本發明的其中一有益效果在於,本發明的無鹵低介電組成物藉著特定之組成份及比例,可提供不含鹵素的環氧樹脂組成物,且其具有高玻璃轉化溫度、低介電常數、低介電損耗、高耐熱性及高儲存模數的特性。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 low-dielectric composition of the present invention can provide a halogen-free epoxy resin composition with a specific composition and ratio, and it has a high glass transition temperature and a low dielectric. The characteristics of electric constant, low dielectric loss, high heat resistance and high storage modulus. It can be made into semi-cured film or resin film to achieve the purpose of being applicable to copper foil substrates and printed circuit boards; in terms of industrial applicability, the products derived from the present invention can fully satisfy the current market need.

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 content disclosed above is only the preferred and feasible embodiments of the present invention, and does not limit the scope of the patent application of the present invention. Therefore, all equivalent technical changes made using the description and schematic content of the present invention are included in the application of the present invention. Within the scope of the patent.

without

without

Claims (14)

一種無鹵低介電組成物,其包括: (a)   100重量份的環氧樹脂; (b)   10至25重量份的DOPO改質硬化劑; (c)   10至20重量份的苯並噁嗪樹脂; (d)   100至120重量份的活性酯合物; (e)   10至20重量份的馬來酸酐改質硬化劑;以及 (f)    20至45重量份的非DOPO阻燃劑。A halogen-free low-dielectric composition comprising: (a) 100 parts by weight of epoxy resin; (b) 10 to 25 parts by weight of DOPO modified hardener; (c) 10 to 20 parts by weight of benzoxazine resin; (d) 100 to 120 parts by weight of active ester compound; (e) 10 to 20 parts by weight of maleic anhydride modified hardener; and (f) 20 to 45 parts by weight of non-DOPO flame retardant. 如請求項1所述的無鹵低介電組成物,其中,所述環氧樹脂是選自由雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、雙酚A酚醛型環氧樹脂、雙酚F酚醛型環氧樹脂、二苯乙烯型環氧樹脂、含三嗪骨架之環氧樹脂、含芴骨架之環氧樹脂、三酚酚甲烷型環氧樹脂、聯苯型環氧樹脂、亞二甲苯基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂、脂環式環氧樹脂、多官能酚類及稠環芳香族類之二縮水甘油醚化合物、分子內具有3個或4個環氧基的三官能及四官能環氧樹脂以及含磷環氧樹脂所組成的群組之至少一者。The halogen-free low-dielectric composition according to claim 1, wherein the epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and phenol Phenolic epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, stilbene epoxy resin, epoxy resin containing triazine skeleton, containing Epoxy resin with fluorene skeleton, triphenol phenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, bicyclic Pentadiene epoxy resins, alicyclic epoxy resins, polyfunctional phenols and fused-ring aromatic diglycidyl ether compounds, trifunctional and tetrafunctional rings with 3 or 4 epoxy groups in the molecule At least one of the group consisting of oxygen resin and phosphorus-containing epoxy resin. 如請求項1所述的無鹵低介電組成物,其中,所述DOPO改質硬化劑是選自DOPO-對苯二酚樹脂、DOPO-萘二醇樹脂、DOPO-酚醛清漆樹脂以及DOPO-雙酚酚醛樹脂所組成的群組。The halogen-free low-dielectric composition according to claim 1, wherein the DOPO modified hardener is selected from the group consisting of DOPO-hydroquinone resin, DOPO-naphthalene glycol resin, DOPO-novolac resin, and DOPO- A group of bisphenol phenolic resins. 如請求項1所述的無鹵低介電組成物,其中,所述苯並噁嗪樹脂是選自下列群組之至少一者:BPA型苯並噁嗪、BPF型苯並噁嗪、BPS型苯並噁嗪、DDM型苯並噁嗪、ODA型苯並噁嗪以及聚醯亞胺化苯並噁嗪。The halogen-free low-dielectric composition according to claim 1, wherein the benzoxazine resin is at least one selected from the following group: BPA-type benzoxazine, BPF-type benzoxazine, BPS Type benzoxazine, DDM type benzoxazine, ODA type benzoxazine and polyimide benzoxazine. 如請求項1所述的無鹵低介電組成物,其中,所述活性酯合物具有以下結構:
Figure 03_image065
其中,X為苯環或萘環,R1 是CH2
Figure 03_image009
,R2 是選自萘酚、苯酚、聯苯酚、雙酚A、雙酚F、雙酚S以及雙環戊二烯(DCPD)所組成的群組, l、m、k為0或1,n是介於0.25至2。
The halogen-free low-dielectric composition according to claim 1, wherein the active ester compound has the following structure:
Figure 03_image065
Among them, X is a benzene ring or a naphthalene ring, and R 1 is CH 2 or
Figure 03_image009
, R 2 is selected from the group consisting of naphthol, phenol, biphenol, bisphenol A, bisphenol F, bisphenol S and dicyclopentadiene (DCPD), l, m, k are 0 or 1, n It is between 0.25 and 2.
如請求項1所述的無鹵低介電組成物,其中所述馬來酸酐改質硬化劑是選自下列群組之至少一者: (1)具有以下結構的苯乙烯-馬來酸酐共聚物;
Figure 03_image011
其中m和n為相同或不同之正整數; (2)具有以下結構的改質型馬來酸酐共聚物:
Figure 03_image069
其中X、Y和n為相同或不同之正整數, R為乙酸酐;或 (3)具有以下結構的馬來酸酐改質聚醯亞胺樹脂:
Figure 03_image071
其中X為表示含10個以上碳原子的碳鏈基團、含苯環的基團或者含10個以上碳原子的碳鏈與苯環基團的結構,m、n與l皆為整數且大於等於1。
The halogen-free low-dielectric composition according to claim 1, wherein the maleic anhydride modifying hardener is at least one selected from the following groups: (1) styrene-maleic anhydride copolymer having the following structure Thing
Figure 03_image011
Wherein m and n are the same or different positive integers; (2) Modified maleic anhydride copolymer with the following structure:
Figure 03_image069
Wherein X, Y and n are the same or different positive integers, R is acetic anhydride; or (3) Maleic anhydride modified polyimide resin with the following structure:
Figure 03_image071
Where X represents the structure of a carbon chain group containing more than 10 carbon atoms, a group containing a benzene ring, or a carbon chain containing more than 10 carbon atoms and a benzene ring group, m, n, and l are all integers and greater than Equal to 1.
如請求項1所述的無鹵低介電組成物,還進一步包括:一硬化促進劑,所述硬化促進劑是選自三氟化硼胺複合物、2-乙基-4-甲基咪唑、2-甲基咪唑、2-苯基咪唑、氯化乙基三苯基鏻、三苯基膦、乙醯丙酮鈷(II)、4-二甲基胺基吡啶、端溴基液體丁二烯橡膠、雙乙醯丙酮鈷(Ⅱ)、三乙醯丙酮鈷(Ⅲ)、三乙胺、三丁胺、二氮雜雙環[2,2,2]辛烷所組成的群組。The halogen-free low-dielectric composition according to claim 1, further comprising: a hardening accelerator, the hardening accelerator is selected from boron trifluoride amine complex, 2-ethyl-4-methylimidazole , 2-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonium chloride, triphenylphosphine, cobalt(II) acetone acetone, 4-dimethylaminopyridine, bromo-terminated liquid butanedi A group consisting of olefin rubber, cobalt diacetylacetone (Ⅱ), cobalt triacetone (Ⅲ), triethylamine, tributylamine, diazabicyclo[2,2,2]octane. 如請求項1所述的無鹵低介電組成物,還進一步包括: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 low-dielectric composition according to claim 1, further comprising: an inorganic filler, the inorganic filler is selected from silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, 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. 如請求項1所述的無鹵低介電組成物,還進一步包括:一溶劑,且所述溶劑是選自丙酮、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。The halogen-free low-dielectric composition according to claim 1, further comprising: a solvent, and the solvent is selected from the group consisting of acetone, methyl ethyl ketone, propylene glycol methyl ether, propylene glycol methyl ether acetate, and dimethyl acetamide And the group consisting of cyclohexanone. 如請求項1所述的無鹵低介電組成物,還進一步包括:一增韌劑,所述增韌劑是體積平均粒徑為0.01至1μm的一核殼聚合物。The halogen-free low-dielectric composition according to claim 1, further comprising: a toughening agent, and the toughening agent is a core-shell polymer with a volume average particle diameter of 0.01 to 1 μm. 如請求項10所述的無鹵低介電組成物,所述核殼聚合物進一步包括一核部以及一核殼,且所述核部的玻璃轉化溫度低於0℃,以及所述核殼的玻璃轉化溫度低於20℃。The halogen-free low-dielectric composition according to claim 10, wherein the core-shell polymer further includes a core part and a core-shell, and the glass transition temperature of the core part is lower than 0°C, and the core-shell The glass transition temperature is below 20°C. 如請求項11所述的無鹵低介電組成物,所述核殼聚合物還進一步包括一中間層,且所述中間層包括30至100重量%的多官能性單體以及0至70重量%的乙烯系單體;其中,所述核殼聚合物的所述殼部包括環氧基單體。The halogen-free low-dielectric composition according to claim 11, wherein the core-shell polymer further includes an intermediate layer, and the intermediate layer includes 30 to 100% by weight of a multifunctional monomer and 0 to 70% by weight % Of vinyl monomers; wherein the shell portion of the core-shell polymer includes epoxy monomers. 一種積層板,其包括: 一樹脂基板,其包括多個半固化膠片,且每一個所述半固化膠片由一玻璃纖維布經塗覆如請求項1所述的無鹵低介電組成物所製成;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 laminated board, which includes: A resin substrate comprising a plurality of semi-cured films, and each of the semi-cured films is made of a glass fiber cloth coated with the halogen-free low-dielectric composition according to claim 1; and A metal foil layer is arranged on at least one surface of the resin substrate. 一種印刷電路板,其包括如請求項13所述的積層板。A printed circuit board including the build-up board according to claim 13.
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