TW201817806A - Non-halogen resin composition - Google Patents

Non-halogen resin composition Download PDF

Info

Publication number
TW201817806A
TW201817806A TW105136541A TW105136541A TW201817806A TW 201817806 A TW201817806 A TW 201817806A TW 105136541 A TW105136541 A TW 105136541A TW 105136541 A TW105136541 A TW 105136541A TW 201817806 A TW201817806 A TW 201817806A
Authority
TW
Taiwan
Prior art keywords
epoxy resin
weight
group
parts
resin
Prior art date
Application number
TW105136541A
Other languages
Chinese (zh)
Other versions
TWI632190B (en
Inventor
溫永順
吳威儀
劉來度
Original Assignee
聯茂電子股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 聯茂電子股份有限公司 filed Critical 聯茂電子股份有限公司
Priority to TW105136541A priority Critical patent/TWI632190B/en
Publication of TW201817806A publication Critical patent/TW201817806A/en
Application granted granted Critical
Publication of TWI632190B publication Critical patent/TWI632190B/en

Links

Abstract

The present invention provides anon-halogenresincomposition. Thenon-halogenresincomposition comprises: (A) 100 parts by weight of an epoxy resin; (B) 25-50 parts by weight of a maleic anhydride modified curing agent; (C) 20-60 parts by weight of a benzoxazine resin; (D) 20-65 parts by weight of a flame retardant; and (E) 0.5-20 parts by weight of a curing accelerator. Thenon-halogenresincompositioncomprises a specific composition and ratio to exhibit excellent properties of a circuit board such as high Tg, low dielectric properties, high thermal resistance, flame retardant property, and halogen free. The non-halogenresincomposition is suitable to form prepregs and a resin film that can be used in a metallic laminate and a printed circuit board.

Description

無鹵素樹脂組成物Halogen-free resin composition

本發明係有關一種無鹵素樹脂組成物，特別是指具有低介電常數之無鹵素樹脂組成物。The present invention relates to a halogen-free resin composition, and more particularly to a halogen-free resin composition having a low dielectric constant.

由於全球環保意識抬頭，加上歐盟實施RoHS環保規章，使得銅箔基板利用無鉛製程及無鹵素等環保基板，逐漸取代傳統FR-4基板。除了日系廠商外，三星電子、蘋果、戴爾、樂金等國際大廠，亦陸續將環保基板導入手機、消費性電子及筆記型電腦產品中，將帶動近年環保基板滲透率大幅成長。Due to the rise of global environmental awareness and the implementation of RoHS environmental protection regulations in the European Union, copper foil substrates have gradually replaced traditional FR-4 substrates with lead-free processes and halogen-free environmentally friendly substrates. In addition to Japanese manufacturers, Samsung Electronics, Apple, Dell, LG and other international companies have gradually introduced environmentally friendly substrates into mobile phones, consumer electronics and notebook computers, which will drive the penetration of environmentally friendly substrates in recent years.

而且，隨著無線傳輸產品的蓬勃發展及高頻傳輸技術的躍進，現有環氧樹脂及酚醛樹脂系統的材料已無法滿足進階的應用，特別是高頻印刷電路板的需求。Moreover, with the rapid development of wireless transmission products and the leap of high-frequency transmission technology, the materials of existing epoxy resin and phenolic resin systems have been unable to meet advanced applications, especially the demand for high-frequency printed circuit boards.

習知之銅箔基板(或稱銅箔積層板)製作之電路板技術中，係利用一環氧基樹脂與硬化劑作為熱固性樹脂組成物原料，將補強材(如玻璃纖維布)與該熱固性樹脂組成加熱結合形成一半固化膠片(prepreg)，再將該半固化膠片與上、下兩片銅箔於高溫高壓下壓合而成。先前技術一般使用環氧基樹脂與具有羥基(-OH)之酚醛(phenol novolac)樹脂硬化劑作為熱固性樹脂組成原料，酚醛樹脂與環氧基樹脂結合會使環氧基開環後形成另一羥基，羥基本身會提高介電常數及介電損耗值，且易與水分結合，增加吸濕性。In the circuit board technology of a conventional copper foil substrate (or copper foil laminate), an epoxy resin and a hardener are used as a raw material of a thermosetting resin composition, and a reinforcing material (such as a glass fiber cloth) and the thermosetting resin are used. The composition is combined with heat to form a semipreg film, and the prepreg film is pressed together with the upper and lower copper foils under high temperature and high pressure. In the prior art, an epoxy resin and a phenol novolac resin hardener having a hydroxyl group (-OH) are generally used as a raw material of a thermosetting resin, and the combination of the phenol resin and the epoxy resin causes the epoxy group to form another hydroxyl group after ring opening. The hydroxyl group itself increases the dielectric constant and the dielectric loss value, and is easily combined with moisture to increase hygroscopicity.

有文獻揭露一種使用氰酸酯樹脂、二環戊二烯基環氧樹脂、矽石以及熱塑性樹脂作為熱固性樹脂組成物，此種熱固性樹脂組成物具有低介電常數與低介電損耗等特性。然而此製造方法於製作時必須使用含有鹵素(如溴)成份之阻燃劑，例如四溴環己烷、六溴環癸烷以及2,4,6-三(三溴苯氧基)-1,3,5-三氮雜苯，而這些含有溴成份之阻燃劑於產品製造、使用甚至回收或丟棄時都很容易對環境造成污染。為了提升銅箔基板之耐熱難燃性、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，環氧樹脂、硬化劑及補強材的材料選擇成了主要影響因素。There is a literature disclosed in which a cyanate resin, a dicyclopentadienyl epoxy resin, vermiculite, and a thermoplastic resin are used as a thermosetting resin composition having characteristics such as low dielectric constant and low dielectric loss. However, this manufacturing method must use a flame retardant containing a halogen (such as bromine) component, such as tetrabromocyclohexane, hexabromocyclodecane, and 2,4,6-tris(tribromophenoxy)-1. , 3,5-triazabenzene, and these bromine-containing flame retardants are easily polluted by the environment when the product is manufactured, used, or even recycled or discarded. In order to improve the heat and flame resistance of the copper foil substrate, low dielectric loss, low moisture absorption, high crosslink density, high glass transition temperature, high bondability, and appropriate thermal expansion, epoxy resin, hardener and reinforcing material Material selection has become a major factor.

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 other characteristics of printed circuit boards, such as high Tg, low coefficient of thermal expansion, and low water absorption, and applied to the manufacture of high frequency printed circuit boards is At this stage, the supplier of printed circuit board materials is eager to solve the problem.

本發明之一目的，在於提供一種無鹵素樹脂組成物，藉由包含特定之組成份及比例，以使可達到高玻璃轉化溫度、低介電特性、高耐熱性、難燃性及不含鹵素等電路基板特性。It is an object of the present invention to provide a halogen-free resin composition which can achieve high glass transition temperature, low dielectric properties, high heat resistance, flame retardancy and halogen-free by containing specific component parts and ratios. Circuit board characteristics.

為了達成上述之目的，本發明係提供一種無鹵素樹脂組成物，包含：(A) 100重量份之環氧樹脂；(B) 25-50重量份之馬來酸酐改質硬化劑；(C) 20-60重量份之苯並噁嗪樹脂；(D) 20-65重量份之阻燃劑；以及(E) 0.5-20重量份之硬化促進劑。In order to achieve the above object, the present invention provides a halogen-free resin composition comprising: (A) 100 parts by weight of an epoxy resin; (B) 25-50 parts by weight of a maleic anhydride-modified hardener; (C) 20-60 parts by weight of a benzoxazine resin; (D) 20-65 parts by weight of a flame retardant; and (E) 0.5-20 parts by weight of a hardening accelerator.

本發明之一態樣，環氧樹脂係選自：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、伸茬基型環氧樹脂、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、多官能酚類及蒽等多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，及將磷化合物導入於此等中而成之含磷環氧樹脂中之一者或多者，其係具有可有效提高玻璃轉化溫度Tg(~175º)之功能。In one aspect of the invention, the epoxy resin 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 ring Oxygen resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, stilbene epoxy resin, epoxy resin containing triazine skeleton, epoxy resin containing ruthenium skeleton, trisphenol phenol methane Epoxy resin, biphenyl type epoxy resin, bismuth-based epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic ring a polyglycidyl ether compound such as an oxygen resin, a polyfunctional phenol or a polycyclic aromatic compound such as hydrazine, a trifunctional or tetrafunctional epoxy resin having three or four epoxy groups in the molecule, and a phosphorus compound introduced therein One or more of the phosphorus-containing epoxy resins obtained in the like have a function of effectively increasing the glass transition temperature Tg (~175o).

馬來酸酐改質硬化劑係選自：以下物質中之一者或多者，其係具有可有效降低耗損因數Df之功能。The maleic anhydride-modified hardener is selected from one or more of the following materials, which has a function of effectively reducing the wear factor Df.

（1）苯乙烯-馬來酸酐共聚物其中m和n為相同或不同之正整數；(1) Styrene-maleic anhydride copolymer Where m and n are the same or different positive integers;

（2）具有以下式1之改質型馬來酸酐共聚物其中m和n為正整數，可為相同或不同數， R為：其中x、y及z為0或正整數， 或具有以下式2之改質型馬來酸酐共聚物(2) a modified maleic anhydride copolymer having the following formula 1 Where m and n are positive integers, which can be the same or different numbers, and R is: Wherein x, y and z are 0 or a positive integer, or a modified maleic anhydride copolymer having the following formula 2

式2其中X、Y及n為相同或不同之正整數， R為環烯烴共聚物(cyclic olefin copolymer) ：或其中R1 、R2 、R3 為各自單獨之鹵素原子、含碳的烷基族或芳香族，m、n為相同或不同之正整數，或者R為乙酸酐（acetic anhydride)： Equation 2 Wherein X, Y and n are the same or different positive integers, and R is a cyclic olefin copolymer: or Wherein R 1 , R 2 , and R 3 are each a separate halogen atom, a carbon-containing alkyl group or an aromatic group, m and n are the same or different positive integers, or R is an acetic anhydride:

（3）具有以下式3之馬來酸酐改質聚醯亞胺樹脂其中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。(3) Maleic anhydride modified polyimine resin having the following formula 3 Wherein X is a structure representing a carbon chain group having 10 or more carbon atoms, a benzene ring-containing group or a carbon chain having 10 or more carbon atoms and a benzene ring group, and m, n and l are integers and larger than Equal to 1.

苯並噁嗪樹脂係選自：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、聚醯亞胺化苯並噁嗪（polybenzoxazine with polyimide）中之一者或多者，其係具有可有效降低介電常數Dk(1-10GHz，平均大約4.1)、耗損因數Df(1-10GHz，平均大約0.008)及提升耐熱性之功能。The benzoxazine resin is selected from the group consisting of BPA type benzoxazine, BPF type benzoxazine, BPS type benzoxazine, DDM type benzoxazine, ODA type benzoxazine, and polyamidated benzene. One or more of polybenzoxazine with polyimide, which has an effective reduction in dielectric constant Dk (1-10 GHz, average about 4.1), loss factor Df (1-10 GHz, average about 0.008), and improvement Heat resistance function.

阻燃劑例如non-dopo阻燃劑，係含有磷及/或乙烯基之化合物，如下列結構式所示者，其係具有阻燃功能；A flame retardant such as a non-dopo flame retardant, which is a compound containing phosphorus and/or a vinyl group, which has a flame retarding function as shown in the following structural formula;

式一其中R為選自：所組成組群之一或多種；Formula one Where R is selected from: One or more of the groups formed;

式二其中X為選自：所組成組群之一或多種； Y為選自：所組成組群之一或多種，n為0-500的整數；Formula 2 Where X is selected from: One or more of the group consisting of; Y is selected from: One or more of the group, n is an integer from 0 to 500;

式三其中X為選自：所組成組群之一或多種； A為選自：所組成組群之一或多種；Three Where X is selected from: One or more of the group consisting; A is selected from: One or more of the groups formed;

當n為0時，Y為： When n is 0, Y is:

當n為1-500的整數時，Y為選自：所組成組群之一或多種，m≧0；When n is an integer from 1 to 500, Y is selected from: One or more of the group consisting of m≧0;

Z為選自：所組成組群之一或多種，m≧0。Z is selected from: One or more of the group consisting of m≧0.

本發明樹脂組成物未選用9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)衍生物，係因其缺點在於DOPO結構內之P-O-C鍵結容易水解為P-OH，會使材料介電常數及低介電損失上升，故選用Non-dopo類型阻燃劑以避免提升材料之Dk/Df。The resin composition of the present invention does not use a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative because of its disadvantage that the POC bond in the DOPO structure is easily hydrolyzed to P-OH will increase the dielectric constant and low dielectric loss of the material, so Non-dopo type flame retardant is used to avoid the Dk/Df of the material.

本發明除了Non-dopo類型阻燃劑外，尚可選擇性再添加下列至少一種特定之阻燃性化合物。所選用的阻燃性化合物可為磷酸鹽化合物或含氮磷酸鹽化合物，但並不以此為限，例如：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))中之一者或多者。In addition to the non-dopo type flame retardant, the present invention may optionally further add at least one of the following specific flame retardant compounds. The flame retardant compound selected may be a phosphate compound or a nitrogen-containing phosphate compound, but is not limited thereto, for example: 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 One or more of (hydroquinone bis-(diphenyl phosphate)), bisphenol A bis-(diphenylphosphate).

硬化促進劑係選自：咪唑(imidazole)、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))與4-二甲基胺基吡啶(4-dimethylaminopyridine(DMAP))、低分子量之端溴基液體丁二烯橡膠 BTPB(terminal bromine-based liquid butadiene rubber) 中之一者或多者。The hardening accelerator is selected from the group consisting of imidazole, boron trifluoride complex, 2-ethyl-4-methylimidazole (2E4MI), and 2-methylimidazole (2). -methylimidazole (2MI)), 2-phenyl-1H-imidazole (2PZ), ethyltriphenyl phosphonium chloride, triphenylphosphine (TPP) and One or more of 4-dimethylaminopyridine (DMAP) and a terminal bromine-based liquid butadiene rubber (BTPB).

本發明之一態樣的樹脂組成物進一步可包含無機填料以增加樹脂組成物之熱傳導性、改良其熱膨脹性及機械強度等特性。無機填料較佳係均勻分佈於該樹脂組成物中。無機填料可經由矽烷偶合劑預先進行表面處理。無機填料可為球型、片狀、粒狀、柱狀、板狀、針狀或不規則狀。該無機填料可包含二氧化矽(熔融態、非熔融態、多孔質或中空型)、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、石墨烯中之一者或多者。The resin composition of one aspect of the present invention may further contain an inorganic filler to increase the thermal conductivity of the resin composition, to improve characteristics such as thermal expansion properties and mechanical strength. The inorganic filler is preferably uniformly distributed in the resin composition. The inorganic filler may be subjected to surface treatment in advance via a decane coupling agent. The inorganic filler may be in the form of a sphere, a sheet, a pellet, a column, a plate, a needle or an irregular shape. The inorganic filler may comprise cerium oxide (molten state, non-molten state, porous or hollow type), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum carbide One or more of cerium, lanthanum carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene.

為了使任何熟習相關技藝者了解本發明之技術內容並據以實施，且根據本說明書所揭露之內容、申請專利範圍及圖式，任何熟習相關技藝者可輕易地理解本發明相關之目的及優點，因此將在實施方式中詳細敘述本發明之詳細特徵以及優點。In order to make those skilled in the art understand the technical content of the present invention and implement it, and according to the disclosure, the patent scope and the drawings, the related objects and advantages of the present invention can be easily understood by those skilled in the art. The detailed features and advantages of the present invention will be described in detail in the embodiments.

為了讓本發明之上述目的和其他目的、特徵與優點能更明顯易懂，特舉數個實施例詳細說明如下：分別將實施例1至4之樹脂組成物列表於表一，比較例1至5之樹脂組成物列表於表三。In order to make the above and other objects, features and advantages of the present invention more apparent, the embodiments of the present invention are described in detail as follows. The resin compositions of Examples 1 to 4 are listed in Table 1, Comparative Example 1 to The resin composition of 5 is listed in Table 3.

實施例1(E1) 一種樹脂組成物，包括以下成份： (A)40重量份之二環戊二烯環氧樹脂(HP-7200)； (B)60重量份之聯苯環氧樹脂(NC-3000)； (C) 25重量份之苯乙烯馬來酸酐(EF-60)； (D)50重量份之苯并噁嗪樹脂(LZ 8280)； (E) 35重量份之式一阻燃劑； (F) 1.5重量份之阻燃性化合物 (PX-200)； (G)35重量份之熔融二氧化矽； (H) 1重量份之硬化促進劑(2E4MI)； (I)45重量份之甲基乙基酮溶劑(MEK)； (J)20重量份之丙二醇甲醚醋酸酯溶劑(PMA)。Example 1 (E1) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 25 parts by weight of styrene maleic anhydride (EF-60); (D) 50 parts by weight of benzoxazine resin (LZ 8280); (E) 35 parts by weight of a flame retardant (F) 1.5 parts by weight of the flame retardant compound (PX-200); (G) 35 parts by weight of molten cerium oxide; (H) 1 part by weight of a hardening accelerator (2E4MI); (I) 45 weight Methyl ethyl ketone solvent (MEK); (J) 20 parts by weight of propylene glycol methyl ether acetate solvent (PMA).

實施例2(E2) 一種樹脂組成物，包括以下成份： (A)40重量份之二環戊二烯環氧樹脂(HP-7200)； (B)60重量份之聯苯環氧樹脂(NC-3000)； (C) 15重量份之式1之改質型馬來酸酐共聚物； (D) 15重量份之式2之改質型馬來酸酐共聚物； (E) 25重量份之苯并噁嗪樹脂(LZ 8280)； (F)55重量份之式三阻燃劑； (G) 8重量份之阻燃性化合物（TCEP）； (H)42重量份之熔融二氧化矽； (I)1重量份之硬化促進劑(2E4MI)； (J)35重量份之甲基乙基酮溶劑(MEK)。Example 2 (E2) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) -3000); (C) 15 parts by weight of the modified maleic anhydride copolymer of the formula 1; (D) 15 parts by weight of the modified maleic anhydride copolymer of the formula 2; (E) 25 parts by weight of benzene And oxazin resin (LZ 8280); (F) 55 parts by weight of a three-type flame retardant; (G) 8 parts by weight of a flame retardant compound (TCEP); (H) 42 parts by weight of molten cerium oxide; I) 1 part by weight of a hardening accelerator (2E4MI); (J) 35 parts by weight of a methyl ethyl ketone solvent (MEK).

實施例3(E3) 一種樹脂組成物，包括以下成份： (A)40重量份之二環戊二烯環氧樹脂(HP-7200)； (B)60重量份之聯苯環氧樹脂(NC-3000)； (C)35重量份之式3之馬來酸酐改質聚醯亞胺樹脂； (D)37重量份之苯并噁嗪樹脂(LZ 8280)； (E) 49重量份之式二阻燃劑； (F) 7重量份之阻燃性化合物（TMP）； (G)38重量份之熔融二氧化矽； (H) 1重量份之硬化促進劑(2E4MI)； (I)77重量份之甲基乙基酮溶劑(MEK)。Example 3 (E3) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 35 parts by weight of a maleic anhydride-modified polyimine resin of the formula 3; (D) 37 parts by weight of a benzoxazine resin (LZ 8280); (E) 49 parts by weight 2 flame retardant; (F) 7 parts by weight of flame retardant compound (TMP); (G) 38 parts by weight of molten cerium oxide; (H) 1 part by weight of hardening accelerator (2E4MI); (I) 77 Parts by weight of methyl ethyl ketone solvent (MEK).

實施例4(E4) 一種樹脂組成物，包括以下成份： (A)40重量份之二環戊二烯環氧樹脂(HP-7200)； (B)60重量份之聯苯環氧樹脂(NC-3000)； (C) 10重量份之苯乙烯馬來酸酐(EF-60) ； (D) 10重量份之式1之改質型馬來酸酐共聚物； (E) 10重量份之式2之改質型馬來酸酐共聚物； (F) 20重量份之式3之馬來酸酐改質聚醯亞胺樹脂； (G) 20重量份之苯并噁嗪樹脂(LZ 8280)； (H) 22重量份之式二阻燃劑； (I) 30重量份之式三阻燃劑； (J) 1重量份之阻燃性化合物（PX-200）； (K)3.5重量份之阻燃性化合物（TCEP）； (L)1重量份之阻燃性化合物（TMP）； (M)30重量份之熔融二氧化矽； (N)10重量份之球型二氧化矽； (O)1重量份之硬化促進劑(2E4MI)； (P)58重量份之甲基乙基酮溶劑(MEK)； (Q)20重量份之丙二醇甲醚醋酸酯溶劑(PMA)。Embodiment 4 (E4) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 10 parts by weight of styrene maleic anhydride (EF-60); (D) 10 parts by weight of the modified maleic anhydride copolymer of the formula 1; (E) 10 parts by weight of the formula 2 a modified maleic anhydride copolymer; (F) 20 parts by weight of a maleic anhydride modified polyimine resin of the formula 3; (G) 20 parts by weight of a benzoxazine resin (LZ 8280); (H) 22 parts by weight of a flame retardant of formula 2; (I) 30 parts by weight of a flame retardant of formula 3; (J) 1 part by weight of a flame retardant compound (PX-200); (K) 3.5 parts by weight of flame retardant Compound (TCEP); (L) 1 part by weight of flame retardant compound (TMP); (M) 30 parts by weight of molten cerium oxide; (N) 10 parts by weight of spherical cerium oxide; (O)1 Parts by weight of a hardening accelerator (2E4MI); (P) 58 parts by weight of methyl ethyl ketone solvent (MEK); (Q) 20 parts by weight of propylene glycol methyl ether acetate solvent (PMA).

比較例1(C1) 一種樹脂組成物，包括以下成份： (A)40重量份之二環戊二烯環氧樹脂(HP-7200)； (B)60重量份之聯苯環氧樹脂(NC-3000)； (C) 30重量份之苯乙烯馬來酸酐(EF-60)； (D) 36重量份之式一阻燃劑； (E)28重量份之熔融二氧化矽； (F) 1重量份之硬化促進劑(2E4MI)； (G)42重量份之甲基乙基酮溶劑(MEK)； (H)20重量份之丙二醇甲醚醋酸酯溶劑(PMA)。Comparative Example 1 (C1) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 30 parts by weight of styrene maleic anhydride (EF-60); (D) 36 parts by weight of a flame retardant; (E) 28 parts by weight of molten cerium oxide; (F) 1 part by weight of a hardening accelerator (2E4MI); (G) 42 parts by weight of methyl ethyl ketone solvent (MEK); (H) 20 parts by weight of propylene glycol methyl ether acetate solvent (PMA).

比較例2(C2) 一種樹脂組成物，包括以下成份： (A)40重量份之二環戊二烯環氧樹脂(HP-7200)； (B)60重量份之聯苯環氧樹脂(NC-3000)； (C)60重量份之苯并噁嗪樹脂(LZ 8280)； (D)62重量份之式三阻燃劑； (E)57重量份之熔融二氧化矽； (F) 1重量份之硬化促進劑(2E4MI)； (G)80重量份之甲基乙基酮溶劑(MEK)。Comparative Example 2 (C2) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) (C) 60 parts by weight of benzoxazine resin (LZ 8280); (D) 62 parts by weight of a three-type flame retardant; (E) 57 parts by weight of molten cerium oxide; (F) 1 Parts by weight of hardening accelerator (2E4MI); (G) 80 parts by weight of methyl ethyl ketone solvent (MEK).

比較例3(C3) 一種樹脂組成物，包括以下成份： (A)40重量份之二環戊二烯環氧樹脂(HP-7200)； (B)60重量份之聯苯環氧樹脂(NC-3000)； (C) 20重量份之式1之改質型馬來酸酐共聚物； (D) 20重量份之式2之改質型馬來酸酐共聚物； (E) 60重量份之式二阻燃劑； (F)47重量份之熔融二氧化矽； (G) 1重量份之硬化促進劑(2E4MI)； (H)114重量份之甲基乙基酮溶劑(MEK)。Comparative Example 3 (C3) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) (C) 20 parts by weight of the modified maleic anhydride copolymer of the formula 1; (D) 20 parts by weight of the modified maleic anhydride copolymer of the formula 2; (E) 60 parts by weight Two flame retardants; (F) 47 parts by weight of molten cerium oxide; (G) 1 part by weight of a hardening accelerator (2E4MI); (H) 114 parts by weight of a methyl ethyl ketone solvent (MEK).

比較例4(C4) 一種樹脂組成物，包括以下成份： (A)40重量份之二環戊二烯環氧樹脂(HP-7200)； (B)60重量份之聯苯環氧樹脂(NC-3000)； (C) 40重量份之式3之馬來酸酐改質聚醯亞胺樹脂； (D)50重量份之苯并噁嗪樹脂(LZ 8280)； (E)30重量份之含溴阻燃劑(SAYTEX 8010(10Br))； (F)41重量份之熔融二氧化矽； (G) 1重量份之硬化促進劑(2E4MI)； (H)97重量份之甲基乙基酮溶劑(MEK)。Comparative Example 4 (C4) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 40 parts by weight of a maleic anhydride modified polyimine resin of the formula 3; (D) 50 parts by weight of a benzoxazine resin (LZ 8280); (E) 30 parts by weight Brominated flame retardant (SAYTEX 8010 (10Br)); (F) 41 parts by weight of molten cerium oxide; (G) 1 part by weight of hardening accelerator (2E4MI); (H) 97 parts by weight of methyl ethyl ketone Solvent (MEK).

比較例5(C5) 一種樹脂組成物，包括以下成份： (A)40重量份之二環戊二烯環氧樹脂(HP-7200)； (B)60重量份之聯苯環氧樹脂(NC-3000)； (C) 35重量份之式3之馬來酸酐改質聚醯亞胺樹脂； (D)20重量份之苯并噁嗪樹脂(LZ 8280)； (E) 30重量份之熔融二氧化矽； (F) 1重量份之硬化促進劑(2E4MI) ； (G) 56重量份之甲基乙基酮溶劑(MEK)。Comparative Example 5 (C5) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 35 parts by weight of a maleic anhydride-modified polyimine resin of the formula 3; (D) 20 parts by weight of a benzoxazine resin (LZ 8280); (E) 30 parts by weight of the melt Cerium oxide; (F) 1 part by weight of a hardening accelerator (2E4MI); (G) 56 parts by weight of a methyl ethyl ketone solvent (MEK).

將上述實施例1至4及比較例1至5之樹脂組成物，分批於攪拌槽中混合均勻後置入一含浸槽中，再將玻璃纖維布通過上述含浸槽，使樹脂組成物附著於玻璃纖維布，再進行加熱烘烤成半固化態而得半固化膠片。The resin compositions of the above Examples 1 to 4 and Comparative Examples 1 to 5 were uniformly mixed in a stirred tank, placed in a dipping tank, and the glass fiber cloth was passed through the above-mentioned impregnation tank to adhere the resin composition to the resin composition. The glass fiber cloth is heated and baked into a semi-cured state to obtain a semi-cured film.

將上述分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 semi-cured film prepared in batches above is taken from the same batch of semi-cured film four sheets and two 18 μm copper foils, which are laminated in the order of copper foil, four-ply semi-cured film and copper foil, and then vacuumed. A copper foil substrate was formed by pressing at 220 ° C for 2 hours, in which four sheets of semi-cured film were cured to form an insulating layer between the two copper foils.

分別將上述含銅箔基板及銅箔蝕刻後之不含銅基板做物性量測，物性量測項目包含玻璃轉化溫度(Tg)、含銅基板耐熱性(T288)、含銅基板浸錫測試(solder dip 288℃，10秒，測耐熱回數，S/D)、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，PCT)、銅箔與基板間拉力(peeling strength,half ounce copper foil,P/S)、介電常數(Dk越低越佳)、介電損耗(Df越低越佳)、耐燃性(flaming test，UL94，其中等級優劣排列為V-0＞V-1＞V-2)。The copper-containing substrate and the copper foil-etched copper-free substrate were respectively measured for physical properties, and the physical property measurement items included glass transition temperature (Tg), copper-containing substrate heat resistance (T288), and copper-containing substrate immersion tin test ( Solder dip 288 ° C, 10 seconds, measured heat resistance, S / D), copper-free substrate PCT moisture immersion tin test (pressure cooking at 121 ° C, after 1 hour, measured solder dip 288 ° C, 20 seconds to see if there is Explosive plate, PCT), copper foil and substrate lining copper foil (P/S), dielectric constant (the lower the Dk is better), dielectric loss (the lower the Df, the better), flame resistance (flaming test, UL94, where the ranks are ranked as V-0>V-1>V-2).

其中實施例1至4之樹脂組成物製作之基板物性量測結果列表於表二中，比較例1至5之樹脂組成物製作之基板物性量測結果列表於表四中。由表二及表四，綜合比較實施例1至4及比較例1至5可發現，依本發明所揭露之樹脂組成物之各組成份含量添加比例，可得物性皆較佳之基板，比較例1至5之基板物性皆較差。其中，實施例1至3係分別使用不同的馬來酸酐改質硬化劑，結果顯示使用式1和式2之改質型馬來酸酐共聚物搭配苯并噁嗪樹脂，可得較佳之基板耐熱性(Tg、T288、S/D)及銅箔拉力(P/S)，使用式3之馬來酸酐改質聚醯亞胺樹脂搭配苯并噁嗪樹脂，可得較佳之介電常數(Dk)及介電損耗(Df)。The substrate physical property measurement results of the resin compositions of Examples 1 to 4 are listed in Table 2, and the substrate physical property measurement results of the resin compositions of Comparative Examples 1 to 5 are listed in Table 4. From Tables 2 and 4, comparing Comparative Examples 1 to 4 and Comparative Examples 1 to 5, it can be found that, according to the content ratio of each component of the resin composition disclosed in the present invention, a substrate having better physical properties can be obtained, and a comparative example can be obtained. The substrate properties of 1 to 5 are poor. Among them, Examples 1 to 3 use different maleic anhydride modified hardeners, respectively, and the results show that the modified maleic anhydride copolymer of Formula 1 and Formula 2 is combined with the benzoxazine resin to obtain a better substrate heat resistance. Properties (Tg, T288, S/D) and copper foil tension (P/S), using a maleic anhydride modified polyimine resin of formula 3 with a benzoxazine resin, a better dielectric constant (Dk) And dielectric loss (Df).

由比較例1之結果顯示，添加苯乙烯馬來酸酐(EF60)但不含苯并噁嗪樹脂之基板，耐熱性皆較差(Tg、T288、S/D、PCT)。由比較例2之結果顯示，添加苯并噁嗪樹脂但不含馬來酸酐改質硬化劑之基板，耐熱性較差(T288、S/D)、銅箔拉力(P/S)較差、介電常數(Dk)值亦較差。由比較例3之結果顯示，添加式1和式2之改質型馬來酸酐共聚物但不含苯并噁嗪樹脂之基板，耐熱性皆較差(Tg、T288、S/D、PCT)、銅箔拉力(P/S)較差、介電常數(Dk)及介電損耗(Df)值皆較差。由比較例4之結果顯示，添加式3之馬來酸酐改質聚醯亞胺樹脂及苯并噁嗪樹脂之基板，電性值皆較差，且比較例4使用含溴化合物作為阻燃劑成份，雖可達到UL94 V-0耐燃等級，但本發明揭露之無鹵素樹脂組成物不使用含鹵素(溴)化合物，較為環保。由比較例5之結果顯示，依本發明所揭露之樹脂組成物使用式3之馬來酸酐改質聚醯亞胺樹脂搭配苯并噁嗪樹脂之基板，但不添加任何阻燃劑，其耐燃等級只有較差的UL94 V-2等級，達不到較佳的V-0等級。As a result of Comparative Example 1, it was revealed that the substrate to which styrene maleic anhydride (EF60) was added but contained no benzoxazine resin was inferior in heat resistance (Tg, T288, S/D, PCT). The results of Comparative Example 2 show that the substrate to which the benzoxazine resin is added but does not contain the maleic anhydride-modified hardener has poor heat resistance (T288, S/D), poor copper foil pull (P/S), and dielectric properties. The constant (Dk) value is also poor. The results of Comparative Example 3 show that the substrate to which the modified maleic anhydride copolymer of Formula 1 and Formula 2 is added but does not contain the benzoxazine resin is inferior in heat resistance (Tg, T288, S/D, PCT), Copper foil pull (P/S) is poor, dielectric constant (Dk) and dielectric loss (Df) values are poor. As a result of Comparative Example 4, it was revealed that the substrate of the maleic anhydride-modified polyimine resin and the benzoxazine resin of the formula 3 was added to have poor electrical properties, and Comparative Example 4 used a bromine-containing compound as a flame retardant component. Although the UL94 V-0 flame resistance rating can be achieved, the halogen-free resin composition disclosed in the present invention does not use a halogen-containing (bromine) compound and is environmentally friendly. The result of the comparative example 5 shows that the resin composition disclosed in the present invention uses the maleic anhydride modified polyimine resin of the formula 3 in combination with the substrate of the benzoxazine resin, but does not add any flame retardant, and is resistant to flame. The rating is only a poor UL94 V-2 rating and does not reach the better V-0 rating.

表一 Table I

表二 Table II

表三 Table 3

表四 Table 4

本發明之無鹵素樹脂組成物，其藉著包含特定之組成份及比例，以使可達到低介電常數、低介電損耗、高耐熱性及高耐燃性；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。The halogen-free resin composition of the present invention can be made into a semi-cured film or resin by including a specific composition and ratio so as to achieve low dielectric constant, low dielectric loss, high heat resistance and high flame resistance; The film can be applied to a copper foil substrate and a printed circuit board; in terms of industrial availability, the products derived from the present invention can fully satisfy the needs of the current market.

以上所述僅為本發明之較佳實施例，非用以限定本發明之專利範圍，其他運用本發明之專利精神之等效變化，均應俱屬本發明之專利範圍。The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the invention, and other equivalent variations of the patent spirit of the present invention are all within the scope of the invention.

無no

無no

Claims (8)

一種無鹵素樹脂組成物，包含：(A) 100重量份之環氧樹脂；(B) 25-50重量份之馬來酸酐改質硬化劑；(C) 20-60重量份之苯並噁嗪樹脂；(D) 20-65重量份之阻燃劑；以及(E) 0.5-20重量份之硬化促進劑。A halogen-free resin composition comprising: (A) 100 parts by weight of an epoxy resin; (B) 25-50 parts by weight of a maleic anhydride modified hardener; (C) 20-60 parts by weight of a benzoxazine Resin; (D) 20-65 parts by weight of a flame retardant; and (E) 0.5-20 parts by weight of a hardening accelerator. 如請求項1之無鹵素樹脂組成物，其中該環氧樹脂係選自下列群組之至少一者：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、伸茬基型環氧樹脂、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、多官能酚類及蒽等多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，及將磷化合物導入於此等中而成之含磷環氧樹脂。The halogen-free resin composition of claim 1, wherein the epoxy resin is selected from at least one of the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. , phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, stilbene type epoxy resin, epoxy resin containing triazine skeleton Epoxy resin containing ruthenium skeleton, trisphenol phenol methane type epoxy resin, biphenyl type epoxy resin, exfoliating type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, two a cyclopentadiene type epoxy resin, an alicyclic epoxy resin, a polyfunctional phenol, a polyglycidyl ether compound such as fluorene, or a trifunctional group having three or four epoxy groups in the molecule; A tetrafunctional epoxy resin and a phosphorus-containing epoxy resin obtained by introducing a phosphorus compound thereto. 如請求項1之無鹵素樹脂組成物，其中該馬來酸酐改質硬化劑係選自下列群組之至少一者： （1）苯乙烯-馬來酸酐共聚物； 其中m和n為相同或不同之正整數， （2）具有以下式1之改質型馬來酸酐共聚物其中m,n為正整數，可為相同或不同數， R為：其中x、y、z為0或正整數， 或具有以下式2之改質型馬來酸酐共聚物：其中X、Y和n為相同或不同之正整數， R為環烯烴共聚物 ：或其中R1 、R2 、R3 為各自單獨之鹵素原子、含碳的烷基族或芳香族，m、n為相同或不同之正整數，或者R為乙酸酐：（3）具有以下式3之馬來酸酐改質聚醯亞胺樹脂， 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 resin composition of claim 1, wherein the maleic anhydride-modified hardener is at least one selected from the group consisting of: (1) a styrene-maleic anhydride copolymer. Wherein m and n are the same or different positive integers, (2) a modified maleic anhydride copolymer having the following formula 1: Where m, n are positive integers, which can be the same or different numbers, and R is: Wherein x, y, z are 0 or a positive integer, or a modified maleic anhydride copolymer having the following formula 2: Wherein X, Y and n are the same or different positive integers, and R is a cyclic olefin copolymer: or Wherein R 1 , R 2 and R 3 are each a separate halogen atom, a carbon-containing alkyl group or an aromatic group, m and n are the same or different positive integers, or R is acetic anhydride: (3) Maleic anhydride modified polyimine resin having the following formula 3 Wherein X is a structure representing a carbon chain group having 10 or more carbon atoms, a benzene ring-containing group or a carbon chain having 10 or more carbon atoms and a benzene ring group, and m, n and l are integers and Greater than or equal to 1. 如請求項1之無鹵素樹脂組成物，其中該苯並噁嗪樹脂係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型苯並噁嗪及聚醯亞胺化苯並噁嗪。The halogen-free resin composition of claim 1, wherein the benzoxazine resin is selected from at least one of the group consisting of BPA type benzoxazine, BPF type benzoxazine, BPS type benzoxazine, DDM type benzoxazine, ODA type benzoxazine and polyamidated benzoxazine. 如請求項1之無鹵素樹脂組成物，其中該阻燃劑係選自具有以下結構式之阻燃劑的群組之至少一者： 式一其中R為選自：所組成組群之一或多種； 式二其中X為選自：所組成組群之一或多種； Y為選自：所組成組群之一或多種，n為0-500的整數； 式三其中X為選自：所組成組群之一或多種； A為選自：所組成組群之一或多種； 當n為0時，Y為：當n為1-500的整數時，Y為選自：所組成組群之一或多種，m≧0； Z為選自：所組成組群之一或多種，m≧0。The halogen-free resin composition of claim 1, wherein the flame retardant is selected from at least one of the group consisting of flame retardants having the following structural formula: Where R is selected from: One or more of the grouped groups; Where X is selected from: One or more of the group consisting of; Y is selected from: One or more of the group, n is an integer from 0 to 500; Where X is selected from: One or more of the group consisting; A is selected from: One or more of the groupings; when n is 0, Y is: When n is an integer from 1 to 500, Y is selected from: One or more of the group consisting of m≧0; Z is selected from: One or more of the group consisting of m≧0. 如請求項1之無鹵素樹脂組成物，更包含阻燃性化合物，選自下列群組之至少一者：間苯二酚雙二甲苯基磷酸鹽、聚磷酸三聚氰胺、三-2-羧乙基膦、三甲基磷酸鹽、三-異丙基氯-磷酸鹽、二甲基-甲基磷酸鹽、雙酚聯苯磷酸鹽、聚磷酸銨、對苯二酚-雙-聯苯基磷酸鹽及雙酚A-雙-聯苯基磷酸鹽。The halogen-free resin composition of claim 1, further comprising a flame retardant compound selected from at least one of the group consisting of resorcinol bis-xylyl phosphate, melamine polyphosphate, and tri-2-carboxyethyl group. Phosphine, trimethyl phosphate, tri-isopropyl chloride-phosphate, dimethyl-methyl phosphate, bisphenol biphenyl phosphate, ammonium polyphosphate, hydroquinone-bis-biphenyl phosphate And bisphenol A-bis-biphenyl phosphate. 如請求項1之無鹵素樹脂組成物，其中該硬化促進劑係選自下列群組之至少一者：咪唑、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、三苯基膦與4-二甲基胺基吡啶。The halogen-free resin composition of claim 1, wherein the hardening accelerator is selected from at least one of the group consisting of imidazole, boron trifluoride complex, 2-ethyl-4-methylimidazole, 2- Methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonium chloride, triphenylphosphine and 4-dimethylaminopyridine. 如請求項1之無鹵素樹脂組成物，更包含熔融二氧化矽或球型二氧化矽。The halogen-free resin composition of claim 1, further comprising molten cerium oxide or spherical cerium oxide.
TW105136541A 2016-11-10 2016-11-10 Non-halogen resin composition TWI632190B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW105136541A TWI632190B (en) 2016-11-10 2016-11-10 Non-halogen resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW105136541A TWI632190B (en) 2016-11-10 2016-11-10 Non-halogen resin composition

Publications (2)

Publication Number Publication Date
TW201817806A true TW201817806A (en) 2018-05-16
TWI632190B TWI632190B (en) 2018-08-11

Family

ID=62949396

Family Applications (1)

Application Number Title Priority Date Filing Date
TW105136541A TWI632190B (en) 2016-11-10 2016-11-10 Non-halogen resin composition

Country Status (1)

Country Link
TW (1) TWI632190B (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101845199B (en) * 2009-03-26 2012-11-28 南亚塑胶工业股份有限公司 Modified maleic anhydride-epoxy resin composite
WO2012024833A1 (en) * 2010-08-25 2012-03-01 Dow Global Technologies Llc Copolymers
TWI421297B (en) * 2011-11-04 2014-01-01 Elite Material Co Ltd Halogen-free resin composition and its application of copper foil substrate and printed circuit board

Also Published As

Publication number Publication date
TWI632190B (en) 2018-08-11

Similar Documents

Publication Publication Date Title
US9422412B2 (en) Halogen-free resin composition and copper clad laminate and printed circuit board using same
TWI460225B (en) Halogen-free resin composition and the use of its copper foil substrate and printed circuit board
TWI486393B (en) Halogen-free resin composition and copper foil substrate and printed circuit board to which the same applies
TWI476244B (en) Halogen-free resin composition
TWI491671B (en) Low dielectric halogen-free resin compositions and circuit boards for which they are used
TWI481659B (en) Halogen-free resin composition and its application of copper foil substrate and printed circuit board
US9279051B2 (en) Halogen-free resin composition, and copper clad laminate and printed circuit board using same
CN103013110B (en) Halogen-free resin composition as well as copper foil substrate and printed circuit board applying same
CN103131131B (en) Halogen-free resin composition and copper clad laminate and printed circuit board applying the same
TWI588202B (en) Low dielectric resin composition and copper foil substrate and printed circuit board using the same
TWI646142B (en) Resin composition and copper foil substrate and printed circuit board using same
KR20160106674A (en) Thermosetting resin composition and use thereof
TW201830412A (en) Non-halogen epoxy resin composition having low dielectric loss
TWI421297B (en) Halogen-free resin composition and its application of copper foil substrate and printed circuit board
TW201425446A (en) Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same
TWI435909B (en) Epoxy resin composition and the application of its low dielectric constant insulation material
CN108117718B (en) Halogen-free resin composition
TWI632190B (en) Non-halogen resin composition
TWI429344B (en) Halogen-free resin composition and its application of copper foil substrate and printed circuit board
TWI724806B (en) Halogen-free low-dielectric composition, laminated substrate and printed circuit board therof
TW202313647A (en) Halogen-free low-dielectric composition, laminated substrate and printed circuit board therof