TWI706997B - Halogen-free flame-retardant thermosetting resin composition, prepreg for printed circuit and metal-clad laminate - Google Patents

Halogen-free flame-retardant thermosetting resin composition, prepreg for printed circuit and metal-clad laminate Download PDF

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Publication number
TWI706997B
TWI706997B TW108119163A TW108119163A TWI706997B TW I706997 B TWI706997 B TW I706997B TW 108119163 A TW108119163 A TW 108119163A TW 108119163 A TW108119163 A TW 108119163A TW I706997 B TWI706997 B TW I706997B
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Taiwan
Prior art keywords
halogen
resin composition
free flame
thermosetting resin
prepreg
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TW108119163A
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Chinese (zh)
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TW202033662A (en
Inventor
潘子洲
方克洪
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大陸商廣東生益科技股份有限公司
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    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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Abstract

本發明提供一種無鹵阻燃熱固性樹脂組合物、印刷電路用預浸料及覆金屬層壓板。所述無鹵阻燃熱固性樹脂組合物包含：改性雙馬來醯亞胺預聚物；苯並噁嗪樹脂；含磷環氧樹脂；酸酐類化合物；和固化促進劑。通過使用無鹵阻燃熱固性樹脂組合物，製得的覆金屬層壓板可以至少具有黏結性好，高耐熱性、高玻璃化轉變溫度（Tg）、阻燃性、低介電常數與損耗等特性中的一個。The invention provides a halogen-free flame-retardant thermosetting resin composition, a prepreg for printed circuits, and a metal-clad laminate. The halogen-free flame-retardant thermosetting resin composition includes: a modified bismaleimide prepolymer; a benzoxazine resin; a phosphorus-containing epoxy resin; an acid anhydride compound; and a curing accelerator. By using a halogen-free flame-retardant thermosetting resin composition, the metal-clad laminate can at least have good adhesion, high heat resistance, high glass transition temperature (Tg), flame retardancy, low dielectric constant and loss characteristics. one of the.

Description

無鹵阻燃熱固性樹脂組合物、印刷電路用預浸料及覆金屬層壓板Halogen-free flame-retardant thermosetting resin composition, prepreg for printed circuit and metal-clad laminate

本發明涉及印刷電路板技術領域。具體地，本發明涉及一種無鹵阻燃熱固性樹脂組合物、印刷電路用預浸料及覆金屬層壓板。The invention relates to the technical field of printed circuit boards. Specifically, the present invention relates to a halogen-free flame-retardant thermosetting resin composition, a prepreg for printed circuits, and a metal-clad laminate.

覆金屬層壓板是將電子玻璃纖維布或其它增強材料浸以樹脂液，一面或雙面覆以金屬箔並經熱壓而製成的一種板狀材料，被稱為覆金屬箔層壓板，簡稱為覆金屬層壓板或覆金屬板，例如覆銅層壓板或覆銅板（Copper Clad Laminate，CCL）。覆金屬層壓板如覆銅板是製造印刷電路板（Printed Circuit Board，簡稱PCB）的基層壓板料，PCB是電子工業的重要部件之一。幾乎每種電子設備，小到電子手錶、計算器，大到電腦，通訊電子設備，軍用武器系統，只要有積體電路等電子元器件，為了它們之間的電氣互連，都要使用印刷板。覆金屬層壓板在整個印刷電路板上，主要擔負著導電、絕緣和支撐三個方面的功能。Metal-clad laminate is a plate-shaped material made by immersing electronic glass fiber cloth or other reinforcing materials with resin liquid, covering one or both sides with metal foil and hot pressing. It is called metal-clad laminate, abbreviated as It is a metal clad laminate or a metal clad laminate, such as a copper clad laminate or a copper clad laminate (Copper Clad Laminate, CCL). Metal-clad laminates, such as copper-clad laminates, are the base laminate materials used to manufacture printed circuit boards (PCBs), and PCBs are one of the important components in the electronics industry. Almost every kind of electronic equipment, from electronic watches, calculators, to computers, communication electronic equipment, military weapon systems, as long as there are electronic components such as integrated circuits, printed boards are used for electrical interconnection between them. . The metal-clad laminate is mainly responsible for the three functions of conduction, insulation and support on the entire printed circuit board.

隨著電子技術的快速進步，無線通訊與網路正深入到社會每個角落，為應對人們對資訊獲取的快回應與大容量的需求，通信設備、基站、伺服器、路由器等的網路基礎設施、大型電腦等的信號傳輸在不斷向高速化及大容量化發展。隨之，要求搭載在這些電子設備的印刷線路板具備高頻傳輸、低傳輸損耗的特性，而對應基板材料則需要有低的介電常數與低介電損耗角正切。另外，由於電子資訊設備的高性能及小型化，其PCB的線路日趨高密度與高多層化，從而要求板材具有較高的回流焊耐熱性、通孔可靠性，反映到材料性能指標上，要求玻璃化轉變溫度在190℃以上、甚至更高；熱膨脹率更低，Tg以下Z軸CTE在45ppm/℃以下、甚至在40ppm/℃以下；而考慮到環境保護問題，此類型產品發展最終趨勢走向無鹵化發展。With the rapid advancement of electronic technology, wireless communications and networks are reaching every corner of society. In response to people’s demand for quick response to information acquisition and large capacity, the network foundation of communication equipment, base stations, servers, routers, etc. The signal transmission of facilities, large computers, etc. is continuously developing towards high speed and large capacity. As a result, printed circuit boards mounted on these electronic devices are required to have high-frequency transmission and low transmission loss characteristics, and corresponding substrate materials need to have low dielectric constant and low dielectric loss tangent. In addition, due to the high performance and miniaturization of electronic information equipment, the PCB circuit is becoming more dense and multi-layered, which requires the plate to have higher reflow heat resistance and through-hole reliability, which is reflected in the material performance index. The glass transition temperature is above 190℃ or even higher; the thermal expansion rate is lower, and the Z-axis CTE below Tg is below 45ppm/℃, even below 40ppm/℃; and considering environmental protection issues, the final development trend of this type of product Halogen-free development.

以往，作為要求低傳送損失的印刷線路板所使用的樹脂組合物，在中國專利CN103131131A，披露了有採用苯乙烯馬來酸酐共聚物配合環氧樹脂、苯並噁嗪樹脂的做法，但所製成的板材玻璃化溫度只有170℃，熱膨脹係數（CTE）大，另外，板材吸水性大，多層板的耐熱性不佳。在中國專利CN201510106304中，以胺改性的雙馬來醯亞胺、苯並噁嗪樹脂以及環氧樹脂的組合，利用雙馬來醯亞胺的優點，可得到高玻璃化溫度、低CTE的效果，但板材的介電常數偏高，不利於高頻下的PCB中信號傳輸。In the past, as a resin composition used for printed wiring boards requiring low transmission loss, Chinese Patent CN103131131A discloses the use of styrene maleic anhydride copolymer in combination with epoxy resin and benzoxazine resin. The glass transition temperature of the finished sheet is only 170℃, and the coefficient of thermal expansion (CTE) is large. In addition, the sheet has high water absorption and the heat resistance of the multilayer board is poor. In Chinese patent CN201510106304, the combination of amine-modified bismaleimide, benzoxazine resin and epoxy resin, using the advantages of bismaleimide, can obtain a high glass transition temperature, low CTE Effective, but the dielectric constant of the plate is too high, which is not conducive to signal transmission in the PCB at high frequencies.

本發明的一個目的在於提供一種無鹵阻燃熱固性樹脂組合物、通過用增強材料如玻璃纖維布（簡稱玻纖布）浸潤所述無鹵阻燃熱固性樹脂組合物得到的印刷電路用預浸料以及包含所述印刷電路用預浸料的覆金屬層壓板，使得覆金屬層壓板至少具有黏結性好，高耐熱性、高玻璃化轉變溫度（Tg）、阻燃性、低介電常數與損耗等特性中的一個。An object of the present invention is to provide a halogen-free flame-retardant thermosetting resin composition, a prepreg for printed circuits obtained by impregnating the halogen-free flame-retardant thermosetting resin composition with a reinforcing material such as glass fiber cloth (referred to as glass fiber cloth) And the metal-clad laminate containing the prepreg for printed circuits, so that the metal-clad laminate has at least good adhesion, high heat resistance, high glass transition temperature (Tg), flame retardancy, low dielectric constant and loss One of the other characteristics.

本發明的另一個目的在於提供一種包含所述印刷電路用預浸料的絕緣板和包含所述印刷電路用預浸料、所述絕緣板或所述覆金屬層壓板的印刷電路板，其中所述絕緣板或覆金屬層壓板具有黏結性好，高耐熱性、高玻璃化轉變溫度（Tg）、阻燃性、低介電常數與損耗等特性中的一個。Another object of the present invention is to provide an insulating board containing the prepreg for printed circuits and a printed circuit board containing the prepreg for printed circuits, the insulating board, or the metal-clad laminate, wherein The insulating board or metal-clad laminate has one of the characteristics of good adhesion, high heat resistance, high glass transition temperature (Tg), flame retardancy, low dielectric constant and loss.

為達此目的，本發明採用以下技術方案：To achieve this goal, the present invention adopts the following technical solutions:

第一方面，本發明提供了一種無鹵阻燃熱固性樹脂組合物，所述無鹵阻燃熱固性樹脂組合物包含如下組分：改性雙馬來醯亞胺預聚物、苯並噁嗪樹脂、含磷環氧樹脂、酸酐類化合物、固化促進劑。In the first aspect, the present invention provides a halogen-free flame-retardant thermosetting resin composition. The halogen-free flame-retardant thermosetting resin composition comprises the following components: modified bismaleimide prepolymer, benzoxazine resin , Phosphorus-containing epoxy resin, acid anhydride compound, curing accelerator.

具體地，本發明提供了一種無鹵阻燃熱固性樹脂組合物，所述無鹵阻燃熱固性樹脂組合物包含： 改性雙馬來醯亞胺預聚物：10至50重量份； 苯並噁嗪樹脂：5至50重量份； 含磷環氧樹脂：30至90重量份； 酸酐類化合物：10至50重量份；和 固化促進劑：0.01至1重量份， 其中所述改性雙馬來醯亞胺預聚物由分子結構中具有至少兩個N-取代馬來醯亞胺基的馬來醯亞胺、芳香二胺及含羥基芳香胺預聚而成。 Specifically, the present invention provides a halogen-free flame-retardant thermosetting resin composition, the halogen-free flame-retardant thermosetting resin composition comprising: Modified bismaleimide prepolymer: 10 to 50 parts by weight; Benzoxazine resin: 5 to 50 parts by weight; Phosphorus-containing epoxy resin: 30 to 90 parts by weight; Acid anhydride compound: 10 to 50 parts by weight; and Curing accelerator: 0.01 to 1 part by weight, Wherein the modified bismaleimide prepolymer is prepolymerized by maleimine, aromatic diamine and hydroxyl-containing aromatic amine having at least two N-substituted maleimide groups in the molecular structure .

第二方面，本發明提供了一種樹脂膠液，所述樹脂膠液包含：如第一方面所述的熱固性樹脂組合物和溶劑。In a second aspect, the present invention provides a resin glue solution, the resin glue solution comprising: the thermosetting resin composition as described in the first aspect and a solvent.

第三方面，本發明提供了一種印刷電路用預浸料，所述印刷電路用預浸料包括增強材料及通過浸潤乾燥後附著在其上的如第一方面所述的無鹵阻燃熱固性樹脂組合物。In a third aspect, the present invention provides a prepreg for a printed circuit, the prepreg for a printed circuit comprising a reinforcing material and the halogen-free flame-retardant thermosetting resin as described in the first aspect attached to it after being dried by infiltration combination.

第四方面，本發明提供了一種絕緣板，所述絕緣板含有如第三方面所述的印刷電路用預浸料。In a fourth aspect, the present invention provides an insulating board containing the prepreg for printed circuits as described in the third aspect.

第五方面，本發明提供了一種覆金屬層壓板，所述覆金屬層壓板包括如第三方面所述的印刷電路用預浸料和覆於所述預浸料外側的一側或兩側的金屬箔。In a fifth aspect, the present invention provides a metal-clad laminate, the metal-clad laminate comprising the prepreg for printed circuits as described in the third aspect and a prepreg coated on one or both sides of the outer side of the prepreg. Metal foil.

第六方面，本發明提供了一種印刷電路板，所述印刷電路板包含：至少一張如第三方面所述的印刷電路用預浸料，或如第四方面所述的絕緣板，或如第五方面所述的覆金屬層壓板。In a sixth aspect, the present invention provides a printed circuit board, the printed circuit board comprising: at least one prepreg for a printed circuit as described in the third aspect, or an insulating board as described in the fourth aspect, or as The metal-clad laminate of the fifth aspect.

根據本發明，①無鹵阻燃熱固性樹脂組合物中含有改性雙馬來醯亞胺預聚物，利用固化後雙馬來醯亞胺具有高剛性分子鏈的特點，可帶來較高的Tg及耐熱性，同時活性的酚羥基能與環氧樹脂反應，從而帶來更高的韌性與黏結性；②該無鹵阻燃熱固性樹脂組合物中含有含磷環氧樹脂，不僅提供較好的黏結性，而且還帶來阻燃效果；③該無鹵阻燃熱固性樹脂組合物中含有酸酐類化合物，能給體系帶來較好的介電性能。另外，優選地，④該無鹵阻燃熱固性樹脂組合物中含有無機填料，可大大降低無鹵阻燃熱固性樹脂組合物的膨脹係數，同時亦可降低成本和提升難燃性。因此使用該組合物製成的適用於無鹵高多層的覆銅箔層壓板，具有黏結性好，高耐熱性、高玻璃化轉變溫度（Tg）、阻燃性、低介電常數與損耗等特性。According to the present invention, ① The halogen-free flame-retardant thermosetting resin composition contains modified bismaleimide prepolymer. After curing, the bismaleimide has the characteristics of high rigidity molecular chain, which can bring higher Tg and heat resistance. At the same time, the active phenolic hydroxyl group can react with epoxy resin to bring higher toughness and adhesion; ②The halogen-free flame-retardant thermosetting resin composition contains phosphorus-containing epoxy resin, which not only provides better The adhesiveness of the halogen-free flame-retardant thermosetting resin composition also has a flame-retardant effect; ③The halogen-free flame-retardant thermosetting resin composition contains acid anhydride compounds, which can bring better dielectric properties to the system. In addition, preferably, (4) The halogen-free flame-retardant thermosetting resin composition contains inorganic fillers, which can greatly reduce the expansion coefficient of the halogen-free flame-retardant thermosetting resin composition, while also reducing costs and improving flame retardancy. Therefore, the use of this composition is suitable for halogen-free high multilayer copper clad laminates, which have good adhesion, high heat resistance, high glass transition temperature (Tg), flame retardancy, low dielectric constant and loss, etc. characteristic.

因此，根據本發明，可以提供一種無鹵阻燃熱固性樹脂組合物、通過用增強材料浸潤所述無鹵阻燃熱固性樹脂組合物得到的印刷電路用預浸料及包含所述印刷電路用預浸料的覆金屬層壓板或絕緣板，以及包含所述印刷電路用預浸料、所述絕緣板或所述覆金屬層壓板的印刷電路板，使得覆金屬層壓板可以至少具有黏結性好，高耐熱性、高玻璃化轉變溫度（Tg）、阻燃性、低介電常數與損耗等特性中的一個，優選具有上述特性中的至少兩個，並且更優選具有上述特性中的全部。Therefore, according to the present invention, it is possible to provide a halogen-free flame-retardant thermosetting resin composition, a prepreg for a printed circuit obtained by impregnating the halogen-free flame-retardant thermosetting resin composition with a reinforcing material, and a prepreg containing the printed circuit The metal-clad laminate or insulating board, and the printed circuit board containing the printed circuit prepreg, the insulating board or the metal-clad laminate, so that the metal-clad laminate can at least have good adhesion and high heat resistance It is preferable to have at least two of the above-mentioned properties, and more preferably have all of the above-mentioned properties, one of properties such as chemical resistance, high glass transition temperature (Tg), flame retardancy, low dielectric constant, and loss.

下面將結合本發明的具體實施方案，對本發明實施例中的技術方案進行清楚、完整地描述，顯然，所描述的實施方案和/或實施例僅僅是本發明一部分實施方案和/或實施例，而不是全部的實施方案和/或實施例。基於本發明中的實施方案和/或實施例，本領域普通技術人員在沒有做出創造性勞動前提下所獲得的所有其他實施方案和/或所有其他實施例，都屬於本發明保護的範圍。The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the specific embodiments of the present invention. Obviously, the described embodiments and/or examples are only a part of the embodiments and/or examples of the present invention. Not all embodiments and/or examples. Based on the embodiments and/or examples of the present invention, all other embodiments and/or all other examples obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

本發明中，所有數值特徵都指在測量的誤差範圍之內，例如在所限定的數值的±10%之內，或±5%之內，或±1%之內。In the present invention, all numerical features refer to within the error range of the measurement, such as within ±10%, or within ±5%, or within ±1% of the defined value.

本發明所述的“包含”、“包括”或“含有”，意指其除所述組分外，還可以具有其他組分，這些其他組分賦予所述預浸料不同的特性。除此之外，本發明所述的“包含”、“包括”或“含有”，還可以包括“基本上由……組成”，並且可以替換為“為”或“由……組成”。The "comprising", "including" or "containing" as used in the present invention means that in addition to the components, they may also have other components, which impart different characteristics to the prepreg. In addition, the "comprising", "including" or "containing" in the present invention can also include "essentially consisting of", and can be replaced with "for" or "consisting of".

在本發明中，如果沒有具體指明，量、比例等是按重量計的。In the present invention, unless otherwise specified, the amount, ratio, etc. are by weight.

對於本發明而言，術語“無鹵阻燃”表示本發明的組合物不含有有意添加的含鹵素阻燃劑。For the present invention, the term "halogen-free flame retardant" means that the composition of the present invention does not contain intentionally added halogen-containing flame retardants.

如上所述，本發明可以提供一種無鹵阻燃熱固性樹脂組合物，所述無鹵阻燃熱固性樹脂組合物包含： 改性雙馬來醯亞胺預聚物：10至50重量份； 苯並噁嗪樹脂：5至50重量份； 含磷環氧樹脂：30至90重量份； 酸酐類化合物：10至50重量份；和 固化促進劑：0.01至1重量份， 其中所述改性雙馬來醯亞胺預聚物由分子結構中具有至少兩個N-取代馬來醯亞胺基的馬來醯亞胺、芳香二胺及含羥基芳香胺預聚而成。 As described above, the present invention can provide a halogen-free flame-retardant thermosetting resin composition, the halogen-free flame-retardant thermosetting resin composition comprising: Modified bismaleimide prepolymer: 10 to 50 parts by weight; Benzoxazine resin: 5 to 50 parts by weight; Phosphorus-containing epoxy resin: 30 to 90 parts by weight; Acid anhydride compound: 10 to 50 parts by weight; and Curing accelerator: 0.01 to 1 part by weight, Wherein the modified bismaleimide prepolymer is prepolymerized by maleimine, aromatic diamine and hydroxyl-containing aromatic amine having at least two N-substituted maleimide groups in the molecular structure .

改性雙馬來醯亞胺預聚物Modified bismaleimide prepolymer

如上所述，所述改性雙馬來醯亞胺預聚物可以由分子結構中具有至少兩個N-取代馬來醯亞胺基的馬來醯亞胺、芳香二胺及含羥基芳香胺預聚而成。As described above, the modified bismaleimide prepolymer can be composed of maleimines, aromatic diamines, and hydroxyl-containing aromatic amines having at least two N-substituted maleimine groups in the molecular structure. Pre-polymerized.

分子結構中具有至少兩個N-取代馬來醯亞胺基的馬來醯亞胺的實例可以由下式（I）或（II）表示：

Figure 02_image001
， （I）
Figure 02_image004
（II） 其中R為
Figure 02_image006
，
Figure 02_image008
，
Figure 02_image010
，
Figure 02_image012
，
Figure 02_image014
或
Figure 02_image016
；R 1和R 2各自獨立地為H或C1至C4的烷基；II式中n為1至8的整數。 Examples of maleimines having at least two N-substituted maleimine groups in the molecular structure can be represented by the following formula (I) or (II):
Figure 02_image001
, (I)
Figure 02_image004
(II) where R is
Figure 02_image006
,
Figure 02_image008
,
Figure 02_image010
,
Figure 02_image012
,
Figure 02_image014
or
Figure 02_image016
; R 1 and R 2 are each independently H or a C1 to C4 alkyl group; in formula II, n is an integer from 1 to 8.

所述含羥基芳香胺可以選自下列中的一項或任何兩項或更多項的組合：

Figure 02_image018
，
Figure 02_image020
，
Figure 02_image022
，
Figure 02_image024
，
Figure 02_image026
或
Figure 02_image028
； 其中R 1和R 2各自獨立地為H或C1至C4的烷基。 The hydroxyl-containing aromatic amine can be selected from one or a combination of any two or more of the following:
Figure 02_image018
,
Figure 02_image020
,
Figure 02_image022
,
Figure 02_image024
,
Figure 02_image026
or
Figure 02_image028
; Wherein R 1 and R 2 are each independently H or a C1 to C4 alkyl group.

C1至C4的烷基的實例可以包括甲基、乙基、正丙基、異丙基、正丁基、異丁基和叔丁基。Examples of the C1 to C4 alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

在本發明中，對取代基R 1和R 2的取代位置沒有限定。例如，在一個苯環具有一個取代基R 1或R 2的情況下，取代基R 1或R 2可以位於任何可能的位置。在一個苯環具有兩個取代基R 1和R 2的情況下，取代基R 1和R 2可以位於任何可能的位置，並且相互可以處於鄰位、間位或對位。對於萘環的情況，也適用。 In the present invention, the substitution positions of the substituents R 1 and R 2 are not limited. For example, in the case where a benzene ring has a substituent R 1 or R 2 , the substituent R 1 or R 2 can be located in any possible position. In the case where a benzene ring has two substituents R 1 and R 2 , the substituents R 1 and R 2 can be located in any possible positions, and can be in the ortho, meta or para positions with each other. This also applies to the case of the naphthalene ring.

所述芳香二胺可以為具有2個以上且4個以下芳環的芳香二胺。所述芳香二胺的實例可以選自下列中的一項或任何兩項或更多項的組合：4,4’-二氨基二苯甲烷、4,4’-二氨基二苯丙烷、4,4’-二氨基二苯基醚、4,4’-二氨基二苯碸、3,3’-二氨基二苯碸、1,5-二氨基萘、2,6-二氨基萘、4,4’-二氨基-3,3’-二乙基-5,5’-二甲基二苯基甲烷、4,4’-二氨基-3,3’-二甲基-5,5’-二乙基二苯甲烷、4,4’-二氨基-3,3’-二乙基二苯基甲烷和4,4’-二氨基-3,3’,5,5’-四乙基二苯基甲烷、4,4-二氨基聯苯、4-二氨基苯甲醚、3,3’-二甲氧基聯苯胺或3,3’-二甲基聯苯胺。The aromatic diamine may be an aromatic diamine having 2 or more and 4 or less aromatic rings. Examples of the aromatic diamine can be selected from one or a combination of any two or more of the following: 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4, 4'-Diamino-3,3'-Diethyl-5,5'-Dimethyldiphenylmethane, 4,4'-Diamino-3,3'-Dimethyl-5,5'- Diethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane and 4,4'-diamino-3,3',5,5'-tetraethyldi Phenylmethane, 4,4-diaminobiphenyl, 4-diaminoanisole, 3,3'-dimethoxybenzidine or 3,3'-dimethylbenzidine.

所述改性雙馬來醯亞胺預聚物可以按以下預聚方法製備得到：將分子結構中具有至少兩個N-取代馬來醯亞胺基的馬來醯亞胺、含羥基芳香胺、芳香二胺和有機溶劑按比例混合，在逐步升溫加熱和攪拌下形成溶液，通氮氣氣氛和繼續攪拌，並保持反應溫度在約100至150℃回流反應，反應時間為約0.5至8h，反應完成後，停止加熱和冷卻，得到含胺基和酚羥基結構的改性雙馬來醯亞胺預聚物溶液。The modified bismaleimide prepolymer can be prepared by the following prepolymerization method: a maleimide having at least two N-substituted maleimide groups in the molecular structure, and a hydroxyl-containing aromatic amine , Aromatic diamine and organic solvent are mixed in proportion, and a solution is formed under gradually heating and stirring. A nitrogen atmosphere is passed through and stirring is continued, and the reaction temperature is maintained at about 100 to 150 ℃ for reflux reaction. The reaction time is about 0.5 to 8 hours. After completion, the heating and cooling are stopped, and a modified bismaleimide prepolymer solution containing an amine group and a phenolic hydroxyl structure is obtained.

在所述改性雙馬來醯亞胺預聚物中，衍生自所述分子結構中具有至少兩個N-取代馬來醯亞胺基的馬來醯亞胺的結構單元、衍生自所述芳香二胺的結構單元及衍生自的所述含羥基芳香胺的重量比為約（6至12）:（0.5至3）:（0.5至3）。In the modified bismaleimide prepolymer, the structural unit derived from the maleimine having at least two N-substituted maleimine groups in the molecular structure is derived from the The weight ratio of the structural unit of the aromatic diamine to the hydroxyl-containing aromatic amine derived from is about (6 to 12): (0.5 to 3): (0.5 to 3).

所述改性雙馬來醯亞胺預聚物的分子量為約500至2500，優選分子量的下限為600、750、900、1000或1200。通過控制投料重量比來控制預聚反應封端，得到所述改性雙馬來醯亞胺預聚物。分子量小於約500時，無鹵阻燃熱固性樹脂組合物的流動性變大，會導致覆金屬層壓板的厚度均勻性變差。分子量超過約2500時，會導致預浸料浸潤性變差，降低絕緣層、覆金屬層壓板或印刷線路板的絕緣可靠性。分子量可以按照GB/T 21863-2008凝膠滲透色譜法（GPC）用四氫呋喃做淋洗液所規定的測試方法進行測量。The molecular weight of the modified bismaleimide prepolymer is about 500 to 2500, and the lower limit of the molecular weight is preferably 600, 750, 900, 1000 or 1200. By controlling the feed weight ratio to control the end capping of the prepolymerization reaction, the modified bismaleimide prepolymer is obtained. When the molecular weight is less than about 500, the fluidity of the halogen-free flame-retardant thermosetting resin composition becomes larger, which may result in poor thickness uniformity of the metal-clad laminate. When the molecular weight exceeds about 2500, the wettability of the prepreg will deteriorate and the insulation reliability of the insulating layer, metal-clad laminate or printed circuit board will be reduced. The molecular weight can be measured according to the test method specified in GB/T 21863-2008 Gel Permeation Chromatography (GPC) using tetrahydrofuran as eluent.

苯並噁嗪樹脂Benzoxazine resin

所述苯並噁嗪樹脂的實例可以包括雙酚A型苯並噁嗪樹脂、雙酚F型苯並噁嗪樹脂、二胺型苯並噁嗪樹脂、酚酞型苯並噁嗪樹脂、雙環戊二烯型苯並噁嗪樹脂或雙酚芴型苯並噁嗪樹脂中的任意一種或者至少兩種的混合物，優選包括雙酚F型苯並噁嗪樹脂、二胺型苯並噁嗪樹脂、酚酞型苯並噁嗪樹脂或雙酚芴型苯並噁嗪樹脂中的任意一種或者至少兩種的混合物。Examples of the benzoxazine resin may include bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, diamine type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentane Any one or a mixture of at least two of diene type benzoxazine resins or bisphenol fluorene type benzoxazine resins, preferably including bisphenol F type benzoxazine resins, diamine type benzoxazine resins, Any one or a mixture of at least two of phenolphthalein type benzoxazine resin or bisphenol fluorene type benzoxazine resin.

在本發明中，苯並噁嗪起到固化劑的作用，其在高溫下會開環產生羥基，羥基可與改性雙馬來醯亞胺及環氧樹脂反應形成交聯網絡，可賦予相應固化物的良好的綜合性能。In the present invention, benzoxazine acts as a curing agent, which will open the ring at high temperature to generate hydroxyl groups. The hydroxyl groups can react with modified bismaleimide and epoxy resin to form a cross-linked network, which can give corresponding Good overall performance of the cured product.

含磷環樹脂Phosphorus ring resin

所述含磷環樹脂的實例可以選自：含有9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10-(2,5-二羥基苯基)-9,10-二氫-9-氧雜-10-膦菲-10-氧化物或10-(2,5-二羥基萘基)-10-氫-9-氧雜-10-磷雜菲-10-氧化物結構的多官能環氧樹脂中的任意一種或至少兩種的混合物。Examples of the phosphorus-containing ring resin may be selected from: containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 10-(2,5-dihydroxynaphthyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10 -Any one or a mixture of at least two of the multifunctional epoxy resins of oxide structure.

所述含磷環樹脂的分子量為約800至2500。分子量可以按照GB/T 21863-2008凝膠滲透色譜法（GPC）用四氫呋喃做淋洗液所規定的測試方法進行測量。The molecular weight of the phosphorus-containing ring resin is about 800 to 2500. The molecular weight can be measured according to the test method specified in GB/T 21863-2008 Gel Permeation Chromatography (GPC) using tetrahydrofuran as eluent.

根據本發明，在無鹵阻燃熱固性樹脂組合物中，除了含磷環氧樹脂之外，還可以包含其他的多官能環氧樹脂，以進一步提升樹脂組合物的交聯密度，提高Tg，可列舉的其他的多官能環氧樹脂的實例包括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、苯酚芳烷基型環氧樹脂、萘酚酚醛型環氧樹脂、萘酚芳烷基型環氧樹脂等含萘骨架型環氧樹脂、聯苯芳烷基型環氧樹脂、二環戊二烯型環氧樹脂、二氫蒽型環氧樹脂等。它們可以單獨使用一種，也可以並用二種以上。從高頻特性、耐熱性、熱膨脹特性及阻燃性的觀點出發，優選使用含萘骨架型、聯苯與芳烷基型環氧樹脂。According to the present invention, in the halogen-free flame-retardant thermosetting resin composition, in addition to the phosphorus-containing epoxy resin, other multifunctional epoxy resins can also be included to further increase the crosslinking density of the resin composition and increase the Tg. Examples of other polyfunctional epoxy resins listed include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, phenol aralkyl type epoxy resins, and naphthol novolac type epoxy resins. Oxygen resins, naphthol aralkyl epoxy resins and other naphthalene skeleton-containing epoxy resins, biphenyl aralkyl epoxy resins, dicyclopentadiene epoxy resins, dihydroanthracene epoxy resins, etc. These may be used individually by 1 type, and may use 2 or more types together. From the viewpoints of high frequency characteristics, heat resistance, thermal expansion characteristics, and flame retardancy, it is preferable to use naphthalene skeleton-containing type, biphenyl and aralkyl type epoxy resins.

酸酐類化合物Anhydride compounds

所述酸酐類化合物包含分子結構中含有不少於兩個酸酐基團的化合物。The acid anhydride compound includes a compound containing no less than two acid anhydride groups in the molecular structure.

所述酸酐類化合物的實例可以選自苯乙烯-馬來酸酐共聚物，苯丙烯-馬來酸酐共聚物，3,3’,4,4’-二苯醚四酸二酐，2,3,3’,4’-二苯醚四甲酸二酐，3,3’,4,4’-聯苯四甲酸二酐，2,3,3’,4’-聯苯四甲酸二酐，3,3’,4,4’-二苯酮四酸二酐或1,2,4,5-均苯四酸二酐中的任意一種或至少兩種的混合物。Examples of the acid anhydride compound may be selected from styrene-maleic anhydride copolymer, styrene-propylene-maleic anhydride copolymer, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3, 3',4'-Diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3, Any one or a mixture of at least two of 3',4,4'-benzophenonetetracarboxylic dianhydride or 1,2,4,5-pyromellitic dianhydride.

苯乙烯-馬來酸酐與苯丙烯-馬來酸酐共聚物中，苯乙烯或苯丙烯和馬來酸酐的共聚比按莫耳計可以為約1:10至10:1，優選約1:5至5:1，更優選約1:2至2:1。In the copolymer of styrene-maleic anhydride and styrene-propylene-maleic anhydride, the copolymerization ratio of styrene or styrene-propylene and maleic anhydride can be about 1:10 to 10:1, preferably about 1:5 to 5:1, more preferably about 1:2 to 2:1.

固化促進劑Curing accelerator

固化促進劑的實例為叔胺、咪唑類、4-二甲氨基吡啶、三苯基膦或三氟化硼單乙胺的任意一種或者至少兩種的混合物。Examples of curing accelerators are any one or a mixture of at least two of tertiary amines, imidazoles, 4-dimethylaminopyridine, triphenylphosphine, or boron trifluoride monoethylamine.

叔胺的實例可以包括三乙胺、苄基二甲胺、2,4,6-三(二甲基氨基甲基)苯酚及其鹽。Examples of tertiary amines may include triethylamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol and salts thereof.

咪唑類的實例可以包括2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰乙基-2-甲基咪唑和1-氰乙基-2-苯基咪唑。Examples of imidazoles may include 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole , 1-cyanoethyl-2-methylimidazole and 1-cyanoethyl-2-phenylimidazole.

所述無鹵阻燃熱固性樹脂組合物還可以包含無機填料。The halogen-free flame-retardant thermosetting resin composition may further include an inorganic filler.

所述無機填料佔所述無鹵阻燃熱固性樹脂組合物總重量的30%至70%。The inorganic filler accounts for 30% to 70% of the total weight of the halogen-free flame-retardant thermosetting resin composition.

所述無機填料選自：二氧化矽、軟性玻璃粉、滑石粉、高嶺土、雲母粉、勃母石、水滑石、硼酸鋅、氫氧化鋁、氫氧化鎂、氧化鋁、氮化硼、氮化鋁、硫酸鋇或矽灰石中的任意一種或至少兩種的混合物。所述二氧化矽為球型二氧化矽、熔融二氧化矽或結晶二氧化矽中的任意一種或者至少兩種的混合物。The inorganic filler is selected from: silicon dioxide, soft glass powder, talc powder, kaolin, mica powder, boehmite, hydrotalcite, zinc borate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, boron nitride, and nitride Any one or a mixture of at least two of aluminum, barium sulfate, or wollastonite. The silicon dioxide is any one or a mixture of at least two of spherical silicon dioxide, fused silicon dioxide or crystalline silicon dioxide.

對無機填料的粒徑有一定的限制，使用粒徑優選為約0.01至30μm、更優選為約0.1至15μm的無機填料。There are certain restrictions on the particle size of the inorganic filler, and an inorganic filler having a particle size of preferably about 0.01 to 30 μm, more preferably about 0.1 to 15 μm is used.

無機填料的粒徑小於約0.01μm時，無鹵阻燃熱固性樹脂組合物的流動性下降，因此，製作預浸料及覆金屬層壓板時的成型性變差，容易產生空隙等，或其表面積變大，因此，金屬和樹脂的黏接面積減少，會導致印刷線路板的剝離強度下降，因此不優選。另一方面，粒徑超過約30μm 時，會導致印刷線路板的配線間或絕緣層的絕緣可靠性下降，因此不優選。When the particle size of the inorganic filler is less than about 0.01 μm, the fluidity of the halogen-free flame-retardant thermosetting resin composition decreases. Therefore, the moldability during the production of prepregs and metal-clad laminates deteriorates, voids, etc., or the surface area thereof is increased. Therefore, the bonding area between the metal and the resin is reduced, and the peel strength of the printed wiring board is decreased, which is not preferable. On the other hand, when the particle size exceeds about 30 μm, the insulation reliability of the wiring compartment or the insulating layer of the printed wiring board decreases, which is not preferable.

在本發明中，為了進一步提高阻燃效果，還可以引入其他含磷結構的阻燃劑，如含磷酚醛、磷腈化合物、聚磷酸銨、三(2-羧乙基)膦、三(異丙基氯)磷酸鹽、三甲基磷酸鹽、二甲基-甲基磷酸鹽、間苯二酚雙二甲苯基磷酸鹽、聚磷酸三聚氰胺、三聚氰胺氰脲酸酯或三-羥乙基異氰尿酸酯中的任意一種或者至少兩種的組合。In the present invention, in order to further improve the flame retardant effect, other flame retardants with phosphorus-containing structure can also be introduced, such as phosphorus-containing phenolic aldehydes, phosphazene compounds, ammonium polyphosphate, tris(2-carboxyethyl)phosphine, tris(iso) Propyl chloride) phosphate, trimethyl phosphate, dimethyl-methyl phosphate, resorcinol bis-xylyl phosphate, melamine polyphosphate, melamine cyanurate or tris-hydroxyethyl isocyanate Any one or a combination of at least two urates.

在含有其他含磷結構的阻燃劑的情況下，其他含磷結構的阻燃劑在無鹵阻燃熱固性樹脂組合物中的含量可以為約1至60重量%，優選為約2至40重量%。In the case of the flame retardant containing other phosphorus-containing structure, the content of the flame retardant of other phosphorus-containing structure in the halogen-free flame-retardant thermosetting resin composition may be about 1 to 60% by weight, preferably about 2 to 40% by weight %.

無鹵阻燃熱固性樹脂組合物還可以包含溶劑。溶劑的實例可以選自丙酮、丁酮、環已酮、N,N- 二甲基甲醯胺、N,N- 二甲基乙醯胺、乙二醇甲醚、丙二醇甲醚、丙二醇甲醚醋酸酯、二甲基碸中的一種或幾種的混合物。在含有溶劑的情況下，溶劑在無鹵阻燃熱固性樹脂組合物中的含量可以為10-99.5重量%，優選約20-99重量%。The halogen-free flame-retardant thermosetting resin composition may further include a solvent. Examples of solvents can be selected from acetone, methyl ethyl ketone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether One or a mixture of acetate and dimethyl sulfide. In the case of containing a solvent, the content of the solvent in the halogen-free flame-retardant thermosetting resin composition may be 10-99.5 wt%, preferably about 20-99 wt%.

包含溶劑的無鹵阻燃熱固性樹脂組合物在本發明中可以稱為樹脂膠液。樹脂膠液可以通過將上面所述的無鹵阻燃熱固性樹脂組合物溶解或分散在溶劑中得到。The halogen-free flame-retardant thermosetting resin composition containing a solvent can be referred to as a resin glue in the present invention. The resin glue solution can be obtained by dissolving or dispersing the halogen-free flame-retardant thermosetting resin composition described above in a solvent.

另外，無鹵阻燃熱固性樹脂組合物還可以還含有各種助劑。作為助劑的具體例，可以舉出填料分散劑、消泡劑、抗氧劑、熱穩定劑、抗靜電劑、紫外線吸收劑、顏料、著色劑、潤滑劑等。這些助劑可以單獨使用，也可以任何兩種或者更多種混合使用。In addition, the halogen-free flame-retardant thermosetting resin composition may further contain various additives. Specific examples of auxiliary agents include filler dispersants, defoamers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and the like. These auxiliaries can be used alone or in combination of any two or more.

本發明的無鹵阻燃熱固性樹脂組合物可以通過公知的方法如配合、攪拌、混合改性雙馬來醯亞胺預聚物、苯並噁嗪樹脂、含磷環氧樹脂、酸酐類化合物和固化促進劑；以及任選的溶劑、填料、阻燃劑、分散劑、消泡劑、抗氧劑、熱穩定劑、抗靜電劑、紫外線吸收劑、顏料、著色劑和潤滑劑中的任意一種或至少兩種的混合物來製備。The halogen-free flame-retardant thermosetting resin composition of the present invention can be modified bismaleimide prepolymer, benzoxazine resin, phosphorus-containing epoxy resin, acid anhydride compound and Curing accelerator; and optional solvents, fillers, flame retardants, dispersants, defoamers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, and lubricants Or a mixture of at least two.

通過機械攪拌、乳化或球磨分散，將無鹵阻燃熱固性樹脂組合物配製成樹脂膠液，然後採用該樹脂膠液浸潤增強材料，經烘乾得預浸料。將該預浸料和金屬箔如銅箔或鋁箔在真空壓機中熱壓可以製備覆金屬層壓板。Through mechanical stirring, emulsification or ball milling dispersion, the halogen-free flame-retardant thermosetting resin composition is formulated into a resin glue solution, and then the resin glue solution is used to infiltrate the reinforcing material and dried to obtain a prepreg. The prepreg and metal foil such as copper foil or aluminum foil are hot pressed in a vacuum press to prepare a metal-clad laminate.

增強材料的實例可以包括：玻璃纖維布、玻纖無紡布以及有機無紡布等。Examples of reinforcing materials may include glass fiber cloth, glass fiber non-woven fabric, organic non-woven fabric, and the like.

為了降低樹脂膠液的黏度，可以在加熱下進行浸潤。進行加熱使得樹脂膠液的溫度小於所用溶劑的沸點，優選浸潤時樹脂膠液的溫度為約20-90℃，進一步優選約25-55℃。In order to reduce the viscosity of the resin glue, it can be infiltrated under heating. Heating is performed so that the temperature of the resin glue solution is lower than the boiling point of the solvent used. Preferably, the temperature of the resin glue solution during infiltration is about 20-90°C, more preferably about 25-55°C.

在另一方面，本發明還可以提供一種印刷電路用預浸料，所述印刷電路用預浸料包括增強材料及通過浸潤乾燥後附著在其上的上面中任何一項所述的無鹵阻燃熱固性樹脂組合物。In another aspect, the present invention can also provide a prepreg for a printed circuit, the prepreg for a printed circuit includes a reinforcing material and any one of the halogen-free resists attached to it after being dried by infiltration. Combustion thermosetting resin composition.

在再一方面，本發明還可以提供一種絕緣板或覆金屬層壓板，所述絕緣板或覆金屬層壓板含有至少一張如上面所述的印刷電路用預浸料。例如，所述覆金屬層壓板可以包括至少一張上面所述的印刷電路用預浸料和覆於所述預浸料外側的一側或兩側的金屬箔。In still another aspect, the present invention can also provide an insulating board or metal-clad laminate containing at least one prepreg for printed circuits as described above. For example, the metal-clad laminate may include at least one sheet of the above-mentioned printed circuit prepreg and metal foils covering one or both sides of the outer side of the prepreg.

在又一方面，本發明還可以提供一種印刷電路板，所述印刷電路板包含：至少一張如上面所述的印刷電路用預浸料，或至少一張如上面所述的絕緣板，或至少一張如上面所述的覆金屬層壓板。In yet another aspect, the present invention can also provide a printed circuit board, the printed circuit board comprising: at least one prepreg for a printed circuit as described above, or at least one insulating board as described above, or At least one metal-clad laminate as described above.

根據本發明，可以提供一種無鹵阻燃熱固性樹脂組合物、通過用增強材料浸潤所述無鹵阻燃熱固性樹脂組合物得到的印刷電路用預浸料及包含所述印刷電路用預浸料的覆金屬層壓板或絕緣板，以及包含所述印刷電路用預浸料、所述絕緣板或所述覆金屬層壓板的印刷電路板，使得覆金屬層壓板可以至少具有黏結性好，高耐熱性、高玻璃化轉變溫度（Tg）、阻燃性、低介電常數與損耗等特性中的一個。According to the present invention, it is possible to provide a halogen-free flame-retardant thermosetting resin composition, a printed circuit prepreg obtained by impregnating the halogen-free flame-retardant thermosetting resin composition with a reinforcing material, and a coating containing the printed circuit prepreg The metal laminate or insulating board, and the printed circuit board containing the printed circuit prepreg, the insulating board or the metal-clad laminate, so that the metal-clad laminate can at least have good adhesion, high heat resistance, One of the characteristics of high glass transition temperature (Tg), flame retardancy, low dielectric constant and loss.

實施例Example

下面通過具體實施方式來進一步說明本發明的技術方案。但是，這些實施例是為了舉例說明本發明，而不應當理解為限制本發明。The technical solutions of the present invention will be further explained through specific implementations below. However, these examples are to illustrate the present invention, and should not be construed as limiting the present invention.

製備實施例Preparation examples

改性雙馬來醯亞胺預聚物的製備Preparation of modified bismaleimide prepolymer

(1) 預聚物A-1的製備(1) Preparation of prepolymer A-1

將4,4’-雙馬來醯亞胺二苯甲烷、間氨基苯酚與4,4’-二氨基-3,3’-二甲基-5,5’-二乙基二苯甲烷按重量比10：1：1（即：4,4’-雙馬來醯亞胺二苯甲烷10重量份，間氨基苯酚1重量份，並且4,4’-二氨基-3,3’-二甲基-5,5’-二乙基二苯甲烷1重量份）投料，將其加入三口燒瓶中，再加入12重量份二甲基甲醯胺溶劑攪拌分散，通氮氣，邊攪拌邊逐步升溫進一步溶解，並將溫度保持在150℃，回流反應4小時，之後冷卻，得到改性雙馬來醯亞胺預聚物A-1的溶液，溶液顏色為棕黑色，溶液的固體含量為50%，溶液黏度為52.5cP。Combine 4,4'-bismaleimide diphenylmethane, m-aminophenol and 4,4'-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane by weight Ratio 10:1:1 (ie: 10 parts by weight of 4,4'-bismaleimide diphenylmethane, 1 part by weight of m-aminophenol, and 4,4'-diamino-3,3'-dimethyl 1 part by weight of 5,5'-diethyldiphenylmethane), put it into a three-necked flask, and then add 12 parts by weight of dimethylformamide solvent, stir and disperse, blow nitrogen, and gradually increase the temperature while stirring. Dissolve, keep the temperature at 150°C, reflux for 4 hours, and then cool to obtain a solution of modified bismaleimide prepolymer A-1. The color of the solution is brown and black, and the solid content of the solution is 50%. The viscosity of the solution is 52.5cP.

黏度採用LVDV-E型號的數顯黏度計測試，測試時將溶液充滿錐盤，繼續增加溶液直至轉子液面標誌（轉子桿上的凹槽）和溶液液面成一平面。Viscosity is tested with a digital display viscometer of LVDV-E model. When testing, fill the cone with the solution, and continue to increase the solution until the rotor liquid level mark (the groove on the rotor rod) and the solution liquid level form a plane.

按照GB/T 21863-2008凝膠滲透色譜法（GPC）用四氫呋喃做淋洗液所規定的測試方法測量，A-1的分子量為500至2500。According to the test method specified in GB/T 21863-2008 Gel Permeation Chromatography (GPC) using tetrahydrofuran as eluent, the molecular weight of A-1 is 500 to 2500.

(2) 預聚物A-2的製備(2) Preparation of prepolymer A-2

將4,4’-雙馬來醯亞胺二苯甲烷、4-氨基萘酚與4,4’-二氨基二苯碸按重量比10：1：1（即：4,4’-雙馬來醯亞胺二苯甲烷10重量份，4-氨基萘酚1重量份，並且4,4’-二氨基二苯碸1重量份）投料，將其加入三口燒瓶中，再加入12重量份的二甲基甲醯胺溶劑攪拌分散，通氮氣，邊攪拌邊逐步升溫進一步溶解，並將溫度保持在150℃，回流反應4 小時，之後冷卻，得到改性雙馬來醯亞胺A-2的溶液，溶液顏色為棕黑色，溶液的固體含量為50%，溶液黏度為55.4cP。Combine 4,4'-bismaleimide diphenylmethane, 4-aminonaphthol and 4,4'-diaminodiphenyl sulfide in a weight ratio of 10:1:1 (ie: 4,4'-two horse 10 parts by weight of lenalimidyl diphenylmethane, 1 part by weight of 4-aminonaphthol, and 1 part by weight of 4,4'-diaminodiphenylmethane) were added to the three-necked flask, and 12 parts by weight of The dimethylformamide solvent was stirred and dispersed, and nitrogen was passed through. The temperature was gradually raised while stirring to further dissolve, and the temperature was kept at 150°C. The reaction was refluxed for 4 hours, and then cooled to obtain modified bismaleimide A-2. Solution, the color of the solution is brown-black, the solid content of the solution is 50%, and the solution viscosity is 55.4cP.

黏度採用LVDV-E型號的數顯黏度計測試，測試時將溶液充滿錐盤，繼續增加溶液直至轉子液面標誌（轉子桿上的凹槽）和溶液液面成一平面。Viscosity is tested with a digital display viscometer of LVDV-E model. When testing, fill the cone with the solution, and continue to increase the solution until the rotor liquid level mark (the groove on the rotor rod) and the solution liquid level form a plane.

按照GB/T 21863-2008凝膠滲透色譜法（GPC）用四氫呋喃做淋洗液所規定的測試方法測量，A-2的分子量為500至2500。According to the test method specified in GB/T 21863-2008 Gel Permeation Chromatography (GPC) using tetrahydrofuran as eluent, the molecular weight of A-2 is 500 to 2500.

實施例1-9和比較例1-5Examples 1-9 and Comparative Examples 1-5

實施例1-9和比較例1-5的熱固性樹脂組合物的組成和固體量如表1或表2中所示。The composition and solid content of the thermosetting resin compositions of Examples 1-9 and Comparative Examples 1-5 are as shown in Table 1 or Table 2.

覆銅板的製備Preparation of copper clad laminate

按照表1或2中所示的組成和量（重量份），將實施例1-9和比較例1-5各自的熱固性樹脂組合物的組分放入容器中，攪拌使其混合均勻，製成實施例1-9和比較例1-5各自的熱固性樹脂組合物，向其中加入丁酮溶劑並且混合均勻，使得固體含量為60%而製成膠液，即得到實施例1-9和比較例1-5各自的樹脂膠液。用2116電子級玻纖布浸漬樹脂膠液，經烘箱在150℃下烘烤成實施例1-9和比較例1-5各自的2116預浸料。取6張實施例1-9和比較例1-5各自的2116預浸料，雙面再覆上18μm厚電解銅箔，在熱壓機作真空層壓，固化溫度200℃，時間120min，製成實施例1-9和比較例1-5各自的覆銅板。According to the composition and amount (parts by weight) shown in Table 1 or 2, put the components of the thermosetting resin composition of each of Examples 1-9 and Comparative Examples 1-5 into a container, and stir to make them evenly mixed to prepare The thermosetting resin composition of each of Examples 1-9 and Comparative Examples 1-5 was added, and methyl ethyl ketone solvent was added and mixed uniformly, so that the solid content was 60% to make a glue solution, that is, examples 1-9 and comparison were obtained. Examples 1-5 respective resin glue solution. The 2116 electronic grade glass fiber cloth was impregnated with resin glue and baked at 150° C. into 2116 prepregs of Examples 1-9 and Comparative Examples 1-5. Take 6 2116 prepregs of each of Examples 1-9 and Comparative Examples 1-5, and cover them with 18μm thick electrolytic copper foil on both sides, and vacuum laminate them on a hot press. The curing temperature is 200°C and the time is 120min. The copper clad laminates of Examples 1-9 and Comparative Examples 1-5 were prepared.

性能測試Performance Testing

1)玻璃化轉溫度Tg：使用動態熱機械分析（DMA）測試，按照IPC-TM-650 2.4.24所規定的DMA測試方法；1) Glass transition temperature Tg: Use dynamic thermomechanical analysis (DMA) test, in accordance with the DMA test method specified in IPC-TM-650 2.4.24;

2) 剝離強度：按照GB/T 4722-2017 7.2.1所規定的測試方法；2) Peel strength: in accordance with the test method specified in GB/T 4722-2017 7.2.1;

3) 燃燒性：按照UL94“50W （20mm）垂直燃燒試驗：V-0、V-1和V-2”測試方法測試，認定V-0為阻燃；3) Flammability: According to UL94 "50W (20mm) vertical burning test: V-0, V-1 and V-2" test method, V-0 is recognized as flame retardant;

4) 帶銅箔的耐浸焊時間：取雙面帶銅箔的板材樣品，100mm×100mm尺寸三塊，分別浸288℃焊錫中，取其不發生分層爆板時間的平均值；4) Resistance to immersion soldering time with copper foil: Take a sample of the plate with copper foil on both sides, three pieces of 100mm×100mm in size, and dip them in 288℃ solder respectively, and take the average of the time without delamination and explosion;

5) Z軸膨脹（取Tg前的熱膨脹係數α1）：測試採用靜態熱分析儀 （TMA）測試，測試按照標準IPC-TM-650 2.4.24，其中Z軸表示層壓板樣品的厚度方向；5) Z-axis expansion (take the thermal expansion coefficient α1 before Tg): The test uses a static thermal analyzer (TMA) test, and the test is in accordance with the standard IPC-TM-650 2.4.24, where the Z-axis represents the thickness direction of the laminate sample;

6) PCT壓力容器熱應力試驗：取蝕去銅箔的板材，100mm×100mm尺寸三塊，置於105±3 KPa壓力下高壓鍋蒸煮2小時，取出，將板浸入288℃焊錫中，取其不發生分層爆板時間的平均值；6) Thermal stress test of PCT pressure vessel: Take three sheets of 100mm×100mm size from which the copper foil has been etched, and place them in a pressure cooker at 105±3 KPa for 2 hours, take it out, and immerse the board in 288℃ solder, whichever is not The average value of the delamination burst time;

7) 吸水率：取蝕去銅箔的板材，100mm×100mm尺寸三塊，稱重，置於105±3 KPa壓力下高壓鍋蒸煮2小時，取出再稱重，計算重量的增加比例；7) Water absorption: Take three pieces of 100mm×100mm size 100mm×100mm, weigh them, place them in a pressure cooker at 105±3 KPa for 2 hours, take them out and weigh them, and calculate the weight increase ratio;

8) 電性能Dk/Df：在1GHz下，使用平板電容法測定，按照標準IPC-TM-650 2.4.24；8) Electrical performance Dk/Df: at 1GHz, measured using the plate capacitance method, according to standard IPC-TM-650 2.4.24;

9)分子量：按照GB/T 21863-2008凝膠滲透色譜法（GPC）用四氫呋喃做淋洗液所規定的測試方法。9) Molecular weight: According to the test method specified in GB/T 21863-2008 Gel Permeation Chromatography (GPC) using tetrahydrofuran as eluent.

實施例及比較例中所用各組分詳述如下：The components used in the examples and comparative examples are detailed as follows:

A、改性雙馬來醯亞胺預聚物A. Modified bismaleimide prepolymer

(A-1)上面製備實施例製備的預聚物A-1(A-1) Prepolymer A-1 prepared in the above preparation example

(A-2)上面製備實施例製備的預聚物A-2(A-2) Prepolymer A-2 prepared in the above preparation example

(A-3) BMI樹脂（4,4’-雙馬來醯亞胺二苯甲烷，洪湖雙馬樹脂公司）(A-3) BMI resin (4,4’-bismaleimide diphenylmethane, Honghu Shuangma Resin Company)

B、環氧樹脂B, epoxy resin

(B-1) KDP-555MC80（DOPO-HQ改性環氧樹脂，韓國國都化學公司）(B-1) KDP-555MC80 (DOPO-HQ modified epoxy resin, Korea Kukdo Chemical Company)

(B-2) HP-7200H（DCPD-苯酚型環氧樹脂，日本DIC公司）(B-2) HP-7200H (DCPD-phenol type epoxy resin, Japan DIC company)

(B-3) NC-3000H（聯苯-苯酚型環氧樹脂，日本化藥公司）(B-3) NC-3000H (Biphenyl-phenol type epoxy resin, Nippon Kayaku Corporation)

C、苯並噁嗪樹脂C, benzoxazine resin

(C-1) D125（二胺型苯並噁嗪樹脂，四川東材科技有限公司）(C-1) D125 (Diamine benzoxazine resin, Sichuan Dongcai Technology Co., Ltd.)

(C-2) LZ8270（酚酞型苯並噁嗪樹脂，美國亨斯曼先進材料公司）(C-2) LZ8270 (phenolphthalein benzoxazine resin, Huntsman Advanced Materials, USA)

D、SMA-EF40（苯乙烯-馬來酸酐低聚物，美國克雷威爾公司）D, SMA-EF40 (styrene-maleic anhydride oligomer, Créwell, USA)

E、XZ92741（含磷酚醛樹脂，美國OLIN化學公司）E, XZ92741 (phosphorus-containing phenolic resin, OLIN Chemical Company, USA)

F、SPB-100 （磷腈樹脂，日本大塚化學公司）F, SPB-100 (phosphazene resin, Otsuka Chemical Company, Japan)

G、2E4MZ（2-乙基-4-甲基咪唑，日本四國化成公司）G, 2E4MZ (2-ethyl-4-methylimidazole, Shikoku Chemical Co., Ltd.)

H、MEGASIL525（熔融二氧化矽，矽比科公司，粒徑D50為2.6μm，D100小於15μm）H. MEGASIL525 (fused silica, Sibelco, particle size D50 is 2.6μm, D100 is less than 15μm)

表1 組分 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 A-1 48 48 35 35 35 A-2 50 40 40 40 C-1 25 25 35 25 25 C-2 35 35 25 25 B-1 75 60 40 40 40 60 35 35 35 B-2 35 35 30 30 B-3 35 30 D 33 27 30 41 45 33 15 15 42 E 10 6 24 24 F 15 12.7 10 15 G 0.06 0.06 0.06 0.06 0.08 0.06 0.1 0.15 0.15 H 182 139 172 158 168 168 170 170 154 Table 1 Component Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 A-1 48 48 35 35 35 A-2 50 40 40 40 C-1 25 25 35 25 25 C-2 35 35 25 25 B-1 75 60 40 40 40 60 35 35 35 B-2 35 35 30 30 B-3 35 30 D 33 27 30 41 45 33 15 15 42 E 10 6 twenty four twenty four F 15 12.7 10 15 G 0.06 0.06 0.06 0.06 0.08 0.06 0.1 0.15 0.15 H 182 139 172 158 168 168 170 170 154

表2 組分 比較例1 比較例2 比較例3 比較例4 比較例5 A-1 35 5 50 35 A-3 48 C-1 25 50 50 25 C-2 B-1 75 60 40 30 B-2 35 30 60 D 33 5 25 35 30 E 30 6 F 15 20 G 0.06 0.06 0.06 0.1 0.06 H 182 112 142 145 145 Table 2 Component Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 A-1 35 5 50 35 A-3 48 C-1 25 50 50 25 C-2 B-1 75 60 40 30 B-2 35 30 60 D 33 5 25 35 30 E 30 6 F 15 20 G 0.06 0.06 0.06 0.1 0.06 H 182 112 142 145 145

實施例1-5和6-9分別使用不同的預聚物，其中實施例1-5使用預聚物A-1，而實施例6-9使用預聚物A-2。Examples 1-5 and 6-9 use different prepolymers, respectively, where Examples 1-5 use prepolymer A-1, and Examples 6-9 use prepolymer A-2.

實施例2在實施例1的基礎下減少無機填料與含磷環氧樹脂的量，引入含磷酚醛樹脂。Example 2 On the basis of Example 1, the amount of inorganic filler and phosphorus-containing epoxy resin was reduced, and phosphorus-containing phenolic resin was introduced.

實施例3、4和5圍繞著預聚物A-1使用不同類型環氧樹脂和不同類型苯並噁嗪樹脂。Examples 3, 4 and 5 used different types of epoxy resins and different types of benzoxazine resins around the prepolymer A-1.

實施例6在實施例1的基礎上，用預聚物A-2替換預聚物A-1。In Example 6, on the basis of Example 1, prepolymer A-2 was used to replace prepolymer A-1.

實施例7、8和9則圍繞著預聚物A-2使用不同類型環氧樹脂和不同類型苯並噁嗪樹脂。Examples 7, 8 and 9 used different types of epoxy resins and different types of benzoxazine resins around the prepolymer A-2.

比較例1使用的是無改性的雙馬來醯亞胺單體；比較例2減少使用苯乙烯馬來酸酐共聚物，增加二胺型苯並噁嗪樹脂的使用量；比較例3減少使用改性雙馬來醯亞胺預聚物，增加二胺型苯並噁嗪樹脂的使用量；比較例4不使用苯並噁嗪樹脂，增加雙馬來醯亞胺預聚物的使用量；而比較例5不使用含磷環氧樹脂，使用磷腈樹脂來提升磷含量。Comparative Example 1 uses unmodified bismaleimide monomer; Comparative Example 2 reduces the use of styrene maleic anhydride copolymer and increases the amount of diamine benzoxazine resin used; Comparative Example 3 reduces the use Modified bismaleimide prepolymer to increase the usage amount of diamine-type benzoxazine resin; Comparative Example 4 does not use benzoxazine resin, and increases the usage amount of bismaleimide prepolymer; In Comparative Example 5, phosphorus-containing epoxy resin was not used, and phosphazene resin was used to increase the phosphorus content.

實施例和比較例的性能分別如表3和4中所示。The performance of the examples and comparative examples are shown in Tables 3 and 4, respectively.

表3 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 Tg（DMA），℃ 203 201 199 205 201 219 215 219 224 剝離強度，N/mm 0.84 0.82 0.88 0.86 0.75 0.86 0.84 0.82 0.78 燃燒性，UL94 V0 V0 V0 V0 V0 V0 V0 V0 V0 耐浸焊（帶銅288℃極限），s ＞300 ＞300 ＞300 ＞300 ＞300 ＞300 ＞300 ＞300 ＞300 Z軸α1，ppm/℃ 38.91 41.65 34.32 31.84 35.67 42.53 34.11 36.68 39.94 PCT（2h，288℃極限），s ＞300 285 ＞300 ＞300 ＞300 285 ＞300 ＞300 280 PCT（2h） 吸水率 0.43% 0.55% 0.46% 0.45% 0.40% 0.48% 0.43% 0.45% 0.43% Df（1GHz） 0.0072 0.0079 0.0062 0.0068 0.0055 0.0091 0.0085 0.0082 0.0088 Dk（1GHz） 3.87 3.89 3.87 3.89 3.83 4.02 3.95 3.95 3.99 table 3 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Tg (DMA), ℃ 203 201 199 205 201 219 215 219 224 Peel strength, N/mm 0.84 0.82 0.88 0.86 0.75 0.86 0.84 0.82 0.78 Flammability, UL94 V0 V0 V0 V0 V0 V0 V0 V0 V0 Resistance to dip soldering (with copper 288℃ limit), s ＞300 ＞300 ＞300 ＞300 ＞300 ＞300 ＞300 ＞300 ＞300 Z axis α1, ppm/℃ 38.91 41.65 34.32 31.84 35.67 42.53 34.11 36.68 39.94 PCT (2h, 288℃ limit), s ＞300 285 ＞300 ＞300 ＞300 285 ＞300 ＞300 280 PCT (2h) water absorption 0.43% 0.55% 0.46% 0.45% 0.40% 0.48% 0.43% 0.45% 0.43% Df (1GHz) 0.0072 0.0079 0.0062 0.0068 0.0055 0.0091 0.0085 0.0082 0.0088 Dk (1GHz) 3.87 3.89 3.87 3.89 3.83 4.02 3.95 3.95 3.99

表4 比較例1 比較例2 比較例3 比較例4 比較例5 Tg（DMA），℃ 176 195 178 195 175 剝離強度，N/mm 0.65 0.88 0.84 0.76 0.75 燃燒性，UL94 V1 V1 V0 V1 V1 耐浸焊（帶銅288℃極限），s 3 ＞300 175 15 155 Z軸α1，ppm/℃ / 38.64 45.11 46.28 35.64 PCT（2h，288℃極限），s 5 ＞300 5 5 5 PCT（2h） 吸水率 0.74% 0.35% 0.56% 0.75% 0.64% Df（1GHz） / 0.012 0.0091 0.0092 0.0094 Dk（1GHz） / 4.42 4.12 4.25 4.17 Table 4 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Tg (DMA), ℃ 176 195 178 195 175 Peel strength, N/mm 0.65 0.88 0.84 0.76 0.75 Flammability, UL94 V1 V1 V0 V1 V1 Resistance to dip soldering (with copper 288℃ limit), s 3 ＞300 175 15 155 Z axis α1, ppm/℃ / 38.64 45.11 46.28 35.64 PCT (2h, 288℃ limit), s 5 ＞300 5 5 5 PCT (2h) water absorption 0.74% 0.35% 0.56% 0.75% 0.64% Df (1GHz) / 0.012 0.0091 0.0092 0.0094 Dk (1GHz) / 4.42 4.12 4.25 4.17

從實施例1、6和比較例1可以看出，雙馬來醯亞胺經過預聚改性後，與樹脂混合物相容性提升，反應性提升、性能明顯較好，而未經過預聚的雙馬來醯亞胺單體相容性較差，容易在樹脂混合物中析出，板材的性能較差且部分性能指標無法測試。From Examples 1, 6 and Comparative Example 1, it can be seen that the compatibility of bismaleimide with the resin mixture is improved, the reactivity is improved, and the performance is significantly better after the prepolymerization modification. The bismaleimide monomer has poor compatibility and is easy to precipitate in the resin mixture. The performance of the board is poor and some performance indicators cannot be tested.

實施例2引入含磷酚醛，降低無機填料含量，Tg和介電性能稍有下降。In Example 2, phosphorus-containing phenolic aldehyde was introduced to reduce the content of inorganic fillers, and Tg and dielectric properties decreased slightly.

實施例3、4和5則圍繞預聚物A-1對比不同類型環氧樹脂和苯並噁嗪樹脂。實施例4使用酚酞型苯並噁嗪樹脂8270比實施例3的二胺型苯並噁嗪樹脂D125的Tg（DMA）稍高，但介電性能不及D125。實施例5使用聯苯環氧樹脂NC-3000H比實施例4使用DCPD環氧樹脂HP-7200H能得到較好的介電性能，但聯苯環氧的成本相對較高。Examples 3, 4, and 5 compare different types of epoxy resins and benzoxazine resins around prepolymer A-1. The Tg (DMA) of the phenolphthalein benzoxazine resin 8270 used in Example 4 is slightly higher than that of the diamine benzoxazine resin D125 of Example 3, but the dielectric properties are not as good as D125. The use of biphenyl epoxy resin NC-3000H in Example 5 can obtain better dielectric properties than the use of DCPD epoxy resin HP-7200H in Example 4, but the cost of biphenyl epoxy is relatively higher.

實施例7、8和9則圍繞預聚物A-2展開，設計思路與預聚物A-1相同，由於A-2預聚時使用的含羥基芳香胺帶有萘環結構，實施例7、8和9的Tg均高於實施例3、4和5，但介電性能實施例3、4和5更優，其他性能如PCT、吸水率、耐浸焊等差異不大。Examples 7, 8 and 9 are developed around prepolymer A-2, and the design idea is the same as that of prepolymer A-1. Because the hydroxyl-containing aromatic amine used in the prepolymerization of A-2 has a naphthalene ring structure, Example 7 The Tgs of, 8 and 9 are all higher than those of Examples 3, 4 and 5, but Examples 3, 4 and 5 have better dielectric properties, and other properties such as PCT, water absorption, and dip soldering resistance have little difference.

比較例2減少使用苯乙烯馬來酸酐共聚物至5重量份EF40，增加二胺型苯並噁嗪樹脂D125的使用量，介電性能明顯降低；比較例3減少使用改性雙馬來醯亞胺預聚物至5份，增加二胺型苯並噁嗪樹脂D125的使用量，板材Tg降低至178℃，PCT測試出現爆板分層，同時Z軸α1升高；比較例4去除苯並噁嗪樹脂，增加改性雙馬來醯亞胺預聚物和苯乙烯-馬來酸酐低聚物，板材的吸水率升高，PCT測試出現爆板分層；比較例5去除含磷環氧樹脂，並引入20份磷腈使體系磷含量提升以實現阻燃，但板材Tg下降，吸水率提高，PCT測試出現爆板分層。In Comparative Example 2, the use of styrene maleic anhydride copolymer was reduced to 5 parts by weight of EF40, and the use of diamine-type benzoxazine resin D125 was increased, and the dielectric properties were significantly reduced; Comparative Example 3 reduced the use of modified bismaleic acid Amine prepolymer to 5 parts, increase the usage of diamine-type benzoxazine resin D125, the board Tg decreased to 178 ℃, the PCT test appeared to burst delamination, and the Z axis α1 increased; Comparative Example 4 removes benzoxazine Oxazine resin, modified bismaleimide prepolymer and styrene-maleic anhydride oligomer were added, the water absorption rate of the board increased, and the PCT test appeared to explode and delamination; Comparative Example 5 removed phosphorus-containing epoxy Resin, and the introduction of 20 parts of phosphazene to increase the phosphorus content of the system to achieve flame retardancy, but the plate Tg decreased, the water absorption rate increased, and the PCT test appeared to burst delamination.

因此，根據本發明，①無鹵阻燃熱固性樹脂組合物中含有改性雙馬來醯亞胺預聚物，利用固化後雙馬來醯亞胺具有高剛性分子鏈的特點，可帶來較高的Tg及耐熱性，同時活性的酚羥基能與環氧樹脂反應，從而帶來更高的韌性與黏結性；②該無鹵阻燃熱固性樹脂組合物中含有含磷環氧樹脂，不僅提供較好的黏結性，而且還帶來阻燃效果；③該無鹵阻燃熱固性樹脂組合物中含有酸酐類化合物，能給體系帶來較好的介電性能。另外，優選地，④該無鹵阻燃熱固性樹脂組合物中含有無機填料，可大大降低無鹵阻燃熱固性樹脂組合物的膨脹係數，同時亦可降低成本和提升難燃性。因此使用該組合物製成的適用於無鹵高多層的覆銅箔層壓板，具有黏結性好，高耐熱性、高玻璃化轉變溫度（Tg）、阻燃性、低介電常數與損耗等特性。Therefore, according to the present invention, (1) the halogen-free flame retardant thermosetting resin composition contains modified bismaleimide prepolymer, and after curing, the bismaleimide has the characteristics of high rigidity molecular chain, which can bring better High Tg and heat resistance. At the same time, the active phenolic hydroxyl group can react with epoxy resin to bring higher toughness and adhesion; ②The halogen-free flame retardant thermosetting resin composition contains phosphorous epoxy resin, which not only provides Good adhesion and flame retardant effect; ③The halogen-free flame retardant thermosetting resin composition contains acid anhydride compounds, which can bring better dielectric properties to the system. In addition, preferably, (4) The halogen-free flame-retardant thermosetting resin composition contains inorganic fillers, which can greatly reduce the expansion coefficient of the halogen-free flame-retardant thermosetting resin composition, while also reducing costs and improving flame retardancy. Therefore, the use of this composition is suitable for halogen-free high multilayer copper clad laminates, which have good adhesion, high heat resistance, high glass transition temperature (Tg), flame retardancy, low dielectric constant and loss, etc. characteristic.

根據本發明，可以提供一種無鹵阻燃熱固性樹脂組合物、通過用增強材料浸潤所述無鹵阻燃熱固性樹脂組合物得到的印刷電路用預浸料及包含所述印刷電路用預浸料的覆金屬層壓板或絕緣板，以及包含所述印刷電路用預浸料、所述絕緣板或所述覆金屬層壓板的印刷電路板，使得覆金屬層壓板可以至少具有黏結性好，高耐熱性、高玻璃化轉變溫度（Tg）、阻燃性、低介電常數與損耗等特性中的一個，優選具有上述特性中的至少兩個，並且更優選具有上述特性中的全部。According to the present invention, it is possible to provide a halogen-free flame-retardant thermosetting resin composition, a printed circuit prepreg obtained by impregnating the halogen-free flame-retardant thermosetting resin composition with a reinforcing material, and a coating containing the printed circuit prepreg The metal laminate or insulating board, and the printed circuit board containing the printed circuit prepreg, the insulating board or the metal-clad laminate, so that the metal-clad laminate can at least have good adhesion, high heat resistance, One of characteristics such as high glass transition temperature (Tg), flame retardancy, low dielectric constant, and loss, preferably has at least two of the above characteristics, and more preferably has all of the above characteristics.

顯然，本領域的技術人員可以對本發明實施例進行各種改動和變型而不脫離本發明的精神和範圍。這樣，倘若本發明的這些修改和變型屬於本發明申請專利範圍及其等同技術的範圍之內，則本發明也意圖包含這些改動和變型在內。Obviously, those skilled in the art can make various changes and modifications to the embodiments of the present invention without departing from the spirit and scope of the present invention. In this way, if these modifications and variations of the present invention fall within the scope of the patent application of the present invention and the equivalent technology, the present invention also intends to include these modifications and variations.

Figure 01_image001
Figure 01_image001

Claims (10)

一種無鹵阻燃熱固性樹脂組合物，所述無鹵阻燃熱固性樹脂組合物包含：改性雙馬來醯亞胺預聚物：10至50重量份；苯並噁嗪樹脂：5至50重量份；含磷環氧樹脂：30至90重量份；酸酐類化合物：10至50重量份；和固化促進劑：0.01至1重量份，其中所述改性雙馬來醯亞胺預聚物由分子結構中具有至少兩個N-取代馬來醯亞胺基的馬來醯亞胺、芳香二胺及含羥基芳香胺預聚而成。 A halogen-free flame-retardant thermosetting resin composition, the halogen-free flame-retardant thermosetting resin composition comprising: modified bismaleimide prepolymer: 10 to 50 parts by weight; benzoxazine resin: 5 to 50 parts by weight Parts; phosphorus-containing epoxy resin: 30 to 90 parts by weight; acid anhydride compound: 10 to 50 parts by weight; and curing accelerator: 0.01 to 1 part by weight, wherein the modified bismaleimide prepolymer is composed of Maleimines, aromatic diamines and hydroxyl-containing aromatic amines with at least two N-substituted maleimine groups in the molecular structure are prepolymerized. 根據請求項1所述的無鹵阻燃熱固性樹脂組合物，其中所述分子結構中具有至少兩個N-取代馬來醯亞胺基的馬來醯亞胺由下式(I)或(II)表示：
Figure 108119163-A0305-02-0024-1
Figure 108119163-A0305-02-0024-2
 其中R為
Figure 108119163-A0305-02-0025-3
，
Figure 108119163-A0305-02-0025-4
，-O-，
Figure 108119163-A0305-02-0025-5
，
Figure 108119163-A0305-02-0025-6
或
Figure 108119163-A0305-02-0025-7
；R1和R2各自獨立地為H或C1至C4的烷基；所述式(II)中n為1至8的整數。 The halogen-free flame-retardant thermosetting resin composition according to claim 1, wherein the maleimide having at least two N-substituted maleimide groups in the molecular structure is represented by the following formula (I) or (II) ) Means:
Figure 108119163-A0305-02-0024-1
Figure 108119163-A0305-02-0024-2
 Where R is
Figure 108119163-A0305-02-0025-3
,
Figure 108119163-A0305-02-0025-4
, -O-,
Figure 108119163-A0305-02-0025-5
,
Figure 108119163-A0305-02-0025-6
or
Figure 108119163-A0305-02-0025-7
R 1 and R 2 are each independently H or C1 to C4 alkyl; in the formula (II), n is an integer of 1 to 8. 根據請求項1所述的無鹵阻燃熱固性樹脂組合物，其中所述含羥基芳香胺選自下列中的一項或任何兩項或更多項的組合：
Figure 108119163-A0305-02-0025-8
 其中R1和R2各自獨立地為H或C1至C4的烷基；所述芳香二胺為具有2個以上且4個以下芳環的芳香二胺。 The halogen-free flame-retardant thermosetting resin composition according to claim 1, wherein the hydroxyl-containing aromatic amine is selected from one or a combination of any two or more of the following:
Figure 108119163-A0305-02-0025-8
 Wherein R 1 and R 2 are each independently H or a C1 to C4 alkyl group; the aromatic diamine is an aromatic diamine having 2 or more and 4 or less aromatic rings. 根據請求項1所述的無鹵阻燃熱固性樹脂組合物，其中在所述改性雙馬來醯亞胺預聚物中，衍生自所述分子結構中具有至少兩個N-取代馬來醯亞胺基的馬來醯亞胺的結構單元、衍生自所述芳香二胺的結構單元及衍生自的所述含羥基芳香胺的重量比為(6至12)：(0.5至3)：(0.5至3)。 The halogen-free flame-retardant thermosetting resin composition according to claim 1, wherein in the modified bismaleimide prepolymer, it is derived from having at least two N-substituted maleimide in the molecular structure The weight ratio of the structural unit of the maleimine of the imino group, the structural unit derived from the aromatic diamine and the hydroxyl-containing aromatic amine derived from is (6 to 12): (0.5 to 3): ( 0.5 to 3). 根據請求項1所述的無鹵阻燃熱固性樹脂組合物，其中所述苯並噁嗪樹脂包括雙酚A型苯並噁嗪樹脂、雙酚F型苯並噁嗪樹脂、二胺型苯並噁嗪樹脂、酚酞型苯並噁嗪樹脂、雙環戊二烯型苯並噁嗪樹脂或雙酚芴型苯並噁嗪樹脂中的任意一種或者至少兩種的混合物； 所述含磷環氧樹脂選自：含有9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10-(2,5-二羥基苯基)-9,10-二氫-9-氧雜-10-膦菲-10-氧化物或10-(2,5-二羥基萘基)-10-氫-9-氧雜-10-磷雜菲-10-氧化物結構的多官能環氧樹脂中的任意一種或至少兩種的混合物；所述酸酐類化合物包含分子結構中含有不少於兩個酸酐基團的化合物；所述固化促進劑為叔胺、咪唑類、4-二甲氨基吡啶、三苯基膦或三氟化硼單乙胺的任意一種或者至少兩種的混合物。 The halogen-free flame-retardant thermosetting resin composition according to claim 1, wherein the benzoxazine resin includes bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, and diamine type benzoxazine resin. Any one or a mixture of at least two of oxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene type benzoxazine resin or bisphenol fluorene type benzoxazine resin; The phosphorus-containing epoxy resin is selected from: containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 10-(2,5-dihydroxynaphthyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide Any one or a mixture of at least two of the polyfunctional epoxy resins of the structure; the acid anhydride compound includes a compound containing no less than two acid anhydride groups in the molecular structure; the curing accelerator is a tertiary amine, imidazole Any one or a mixture of at least two of the two species, 4-dimethylaminopyridine, triphenylphosphine, or boron trifluoride monoethylamine. 一種樹脂膠液，所述樹脂膠液包含：請求項1至5任何一項所述的無鹵阻燃熱固性樹脂組合物；和溶劑。 A resin glue liquid comprising: the halogen-free flame-retardant thermosetting resin composition according to any one of claims 1 to 5; and a solvent. 一種印刷電路用預浸料，所述印刷電路用預浸料包括增強材料及通過浸潤乾燥後附著在其上的如請求項1至5中任何一項所述的無鹵阻燃熱固性樹脂組合物。 A prepreg for a printed circuit, the prepreg for a printed circuit comprising a reinforcing material and the halogen-free flame-retardant thermosetting resin composition according to any one of claims 1 to 5 attached to it after being dried by infiltration . 一種絕緣板，所述絕緣板含有至少一張如請求項7所述的印刷電路用預浸料。 An insulating board containing at least one prepreg for a printed circuit according to claim 7. 一種覆金屬層壓板，所述覆金屬層壓板包括至少一張如請求項7所述的印刷電路用預浸料和覆於所述預浸料外側的一側或兩側的金屬箔。 A metal-clad laminate comprising at least one prepreg for printed circuits as described in claim 7 and metal foils covering one or both sides of the outside of the prepreg. 一種印製電路板，所述印製電路板包含：至少一張如請求項7所述的印刷電路用預浸料，或至少一張如請求項8所述的絕緣板，或至少一張如請求項9所述的覆金屬層壓板。A printed circuit board comprising: at least one printed circuit prepreg as described in claim 7, or at least one insulating board as described in claim 8, or at least one such as The metal-clad laminate according to claim 9.
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WO2020177167A1 (en) 2020-09-10
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CN111635616A (en) 2020-09-08

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