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 PDFInfo
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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:
(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; (Formula 1); wherein, R 1 and R 2 are methyl or ethyl, and n is a positive integer between 0 and 10;
(式二);其中,R為苯環或萘環。 (Formula 2); Wherein, R is a benzene ring or a naphthalene ring.
(式三)。 (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:;In a specific embodiment of the present invention, the active ester compound has the following structure: ;
其中,X為苯環或萘環,R1 是CH2 或,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 , 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:,(1) Styrene-maleic anhydride copolymer with the following structure: ,
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: (2) Modified maleic anhydride copolymer with the following structure:
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:;(3) Maleic anhydride modified polyimide resin with the following structure: ;
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Df 。In 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:(Ⅰ)、(Ⅱ)以及(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): (Ⅰ), (Ⅱ) and (Ⅲ);
其中,R1 是、、、、、、或;Where R 1 is , , , , , , or ;
其中,R2 是、、或;Where R 2 is , , or ;
其中,R3 是、或CH2 CH2 OCH=CH2 ;Where R 3 is , 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 是或; 其中,m≧1;Where R 4 is or ; Among them, m≧1;
其中,R5 是或;Where R 5 is or ;
其中,R6 是、或。Where R 6 is , or .
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
[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.
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