TWI612130B - Phosphorus-containing flame retardant composition and phosphorus-containing polyphenylene ether resin composition, prepreg and laminate using same - Google Patents
Phosphorus-containing flame retardant composition and phosphorus-containing polyphenylene ether resin composition, prepreg and laminate using same Download PDFInfo
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- TWI612130B TWI612130B TW104133268A TW104133268A TWI612130B TW I612130 B TWI612130 B TW I612130B TW 104133268 A TW104133268 A TW 104133268A TW 104133268 A TW104133268 A TW 104133268A TW I612130 B TWI612130 B TW I612130B
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- 0 *C*P1(Oc2ccccc2-c2c1cccc2)=O Chemical compound *C*P1(Oc2ccccc2-c2c1cccc2)=O 0.000 description 2
- VBQRUYIOTHNGOP-UHFFFAOYSA-N O=P1Oc2ccccc2-c2c1cccc2 Chemical compound O=P1Oc2ccccc2-c2c1cccc2 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
Abstract
本發明提供一種含磷阻燃組合物，包含：次磷酸鹽化合物、DOPO衍生物及聚磷腈化合物，使用該組合物作為阻燃，可發揮幾種含磷化合物之間之協同效果，在較少之添加量下，實現無鹵阻燃，達到V-0級別。本發明亦提供一種包含上述含磷阻燃組合物之聚苯醚樹脂組合物及使用其製作之預浸料及覆銅箔層壓板。該聚苯醚樹脂組合物固化後，在不適用鹵素阻燃劑之條件下實現阻燃V-0級別，且保持了聚苯醚樹脂良好的介電特性及耐熱性，由其製作之預浸料及覆銅箔層壓板，具有良好之介電特性及耐熱性，在保證優異耐熱性及介電性能的同時實現無鹵阻燃，阻燃達到UL 94-V0級別；適合高頻高速印刷電路板領域使用，符合未來的綠色環保要求。 The invention provides a phosphorus-containing flame retardant composition, which includes: a hypophosphite compound, a DOPO derivative, and a polyphosphazene compound. Using the composition as a flame retardant, a synergistic effect between several phosphorus-containing compounds can be exerted. With a small amount of addition, it achieves halogen-free flame retardant and reaches V-0 level. The present invention also provides a polyphenylene ether resin composition containing the above-mentioned phosphorus-containing flame-retardant composition, and a prepreg and a copper-clad laminate made using the same. After the polyphenylene ether resin composition is cured, the flame retardant V-0 level is achieved without the use of a halogen flame retardant, and the good dielectric properties and heat resistance of the polyphenylene ether resin are maintained. Materials and copper-clad laminates, which have good dielectric properties and heat resistance, while ensuring excellent heat resistance and dielectric properties, realize halogen-free flame retardant, flame retardance reaches UL 94-V0 level; suitable for high-frequency high-speed printed circuit boards Field use, in line with future green environmental protection requirements.
Description
本發明屬於覆銅板技術領域，涉及一種含磷組合物以及使用其之含磷聚苯醚樹脂組合物、預浸料及層壓板。 The invention belongs to the technical field of copper clad laminates, and relates to a phosphorus-containing composition and a phosphorus-containing polyphenylene ether resin composition, a prepreg and a laminate using the same.
近年來，隨著電腦及資訊通訊設備高性能化、高功能化以及網路化之發展，為了高速傳輸及處理大容量資訊，操作訊號趨向於高頻化，因而對電路基板之材料提出了要求，尤其是在那些使用寬頻之電子設備如移動通信裝置上有迅速之發展。 In recent years, with the development of high-performance, high-functionality, and networking of computers and information communication equipment, in order to transmit and process large-capacity information at high speed, the operating signals tend to be high-frequency, so the requirements for the materials of circuit substrates There has been rapid development, especially in those electronic devices that use broadband, such as mobile communication devices.
習知用於印製電路基板之材料中，廣泛使用黏接特性優異之環氧樹脂。然而，環氧樹脂電路基板一般介電常數及介質損耗角正切較高(介電常數大於4，介質損耗角正切約在0.02)，高頻特性不充分，不能適應訊號高頻化之要求。因此，必須研製介電特性優異之樹脂，即介電常數及介質損耗角正切低之樹脂。長期以來本領域之技術人員對介電性能良好之熱固性的氰酸酯、雙馬來醯亞胺樹脂、碳氫樹脂等進行研究；此外，聚苯醚樹脂由於具有良好之介電性能、耐熱性，亦被廣大技術人員作為高頻高速材料進行了大量研究，惟由於其熔點高、流動性差而在應用上受到許多限制，預浸料之熔融黏度大，無法滿足多層印刷電路板之工藝製作要求。 藉由降低聚苯醚樹脂之分子量，可有效降低其熔融溫度、改善流動性，惟此亦犧牲聚苯醚樹脂之耐熱性。 Conventionally, epoxy resins having excellent adhesion characteristics are widely used as materials for printed circuit boards. However, the epoxy resin circuit board generally has a high dielectric constant and a high dielectric loss tangent (dielectric constant greater than 4, and a dielectric loss tangent is about 0.02). The high-frequency characteristics are insufficient and cannot meet the requirements of high-frequency signals. Therefore, it is necessary to develop a resin having excellent dielectric characteristics, that is, a resin having a low dielectric constant and a low dielectric loss tangent. Those skilled in the art have long studied thermosetting cyanate esters, bismaleimide resins, and hydrocarbon resins with good dielectric properties. In addition, polyphenylene ether resins have good dielectric properties and heat resistance. It has also been extensively studied by the vast number of technicians as high-frequency and high-speed materials. However, due to its high melting point and poor fluidity, it has been limited in many applications. The prepreg has a large melt viscosity and cannot meet the requirements of the multilayer printed circuit board. . By reducing the molecular weight of the polyphenylene ether resin, it can effectively reduce its melting temperature and improve the fluidity, but this also sacrifices the heat resistance of the polyphenylene ether resin.
CN1745142A使用一種端基含有乙烯苯基和間乙烯苯基之聚苯醚樹脂作為主體樹脂，利用異氰脲酸三烯酯作為交聯固化劑，必要時亦可加入無機填料、阻燃劑得到一種聚苯醚樹脂組合物，接著，浸漬NE型玻璃纖維織物，得到具有優異介電特性，具有較高玻璃化轉變溫度之預浸料及層壓板，但是由於該組合物中使用異氰脲酸三烯酯作為交聯固化劑，其分子量較低，在預浸料製作過程中容易揮發，從而不利於穩定的製作預浸料及層壓板材。即使該專利中有提及為改善耐熱性，黏結性及尺寸穩定性，除PPE之外，必要時，可使用烯烴樹脂作為相容劑，惟並未提及其對固化物的各項性能進行研究。 CN1745142A uses a polyphenylene ether resin containing vinylphenyl and m-vinylphenyl groups as the main resin, and uses trienyl isocyanurate as a cross-linking curing agent. If necessary, an inorganic filler and a flame retardant can be added to obtain a The polyphenylene ether resin composition is then impregnated with NE-type glass fiber fabric to obtain a prepreg and a laminate having excellent dielectric characteristics and a high glass transition temperature, but because isocyanuric triene is used in the composition As a cross-linking curing agent, the ester has a low molecular weight and is easily volatile during the preparation of prepreg, which is not conducive to the stable production of prepreg and laminated sheet. Even though the patent mentions that in order to improve heat resistance, adhesion and dimensional stability, in addition to PPE, olefin resin can be used as a compatibilizer if necessary, but it does not mention the performance of the cured product. the study.
US2009/0247032採用一種乙烯基雙官能度之聚苯醚樹脂作為主體，以及帶有萘環結構之氰酸酯、雙酚A型氰酸酯、溴化阻燃劑及無機填料，得到一種具有良好流動性、並可在保證良好介電性能之前提下得到良好剝離強度，耐濕熱性及阻燃性。 US2009 / 0247032 uses a vinyl difunctional polyphenylene ether resin as a main body, and a cyanate ester having a naphthalene ring structure, a bisphenol A-type cyanate ester, a brominated flame retardant, and an inorganic filler. Flowability, and can be improved to obtain good peel strength, humidity and heat resistance and flame retardance before ensuring good dielectric properties.
WO2006/023371A1提供一種雙官能化之聚苯醚樹脂及不飽和烯烴單體之組合物，可改進聚苯醚樹脂之流動性及固化後性能，惟並未指出雙官能化聚苯醚樹脂用於層壓板領域時之性能優勢，且使用之不飽和烯烴單體係低分子量化合物，在高溫下亦容易揮發，工藝性差。 WO2006 / 023371A1 provides a composition of a bifunctionalized polyphenylene ether resin and an unsaturated olefin monomer, which can improve the fluidity and cured properties of the polyphenylene ether resin, but does not indicate that the difunctionalized polyphenylene ether resin is used for The performance advantages in the field of laminates, and the unsaturated olefin single system low molecular weight compounds are also easy to volatilize at high temperatures, and the processability is poor.
由上述可知，藉由對低分子量之官能化係解決聚苯醚分子量降低帶來之耐熱性下降之問題，惟對於在層壓板領域之具體應用時，如何選擇合適之固化交聯及體現官能化聚苯醚樹脂之性能優勢，仍須進一步研 究。 From the above, it can be seen that the problem of lowering the heat resistance caused by the reduction of the molecular weight of polyphenylene ether is solved by the functionalization of low molecular weight. However, for specific applications in the field of laminates, how to choose a suitable curing crosslink and reflect the functionalization The performance advantages of polyphenylene ether resins need further study Study.
此外，隨著社會對環保意識的加強，電子產品之環保問題也日益突出，因此如何實現基板材料之無鹵化，亦是今年本技術領域人員研究之重點，目前實現無鹵阻燃之技術手段主要引入磷元素進行阻燃，常見物質有含磷環氧樹脂、含磷酚醛樹脂、磷酸酯類化合物及聚磷酸酯化合物、磷腈化合物、次磷酸鹽類化合物，然而，由於這些材料本身特性之限制，單獨使用皆無法滿足高速材料領域對耐熱性及介電性能之要求，如含磷環氧樹脂、含磷酚醛樹脂部分材料雖可達到良好之阻燃效果，惟由於在介電性能方面表現不佳，同時過多地磷引入帶來耐濕熱性能之惡化，無法滿足高多層PCB之可靠性要求；添加型之次膦酸鹽單獨使用之阻燃效果不佳，特別係在成炭較低之樹脂體系；聚磷腈化合物由於本地之熔點較低，增塑性強，大量添加帶來耐熱性大幅下降如玻璃化轉變溫度降低，同時單獨使用時，即使大量添加，亦難以達到阻燃V-0之級別。其他磷酸酯類化合物亦同樣存有類似問題。 In addition, with the strengthening of society's awareness of environmental protection, the environmental protection issues of electronic products have become increasingly prominent. Therefore, how to achieve halogen-free substrate materials is also the focus of research in this technical field this year. Currently, the main technical means to achieve halogen-free flame retardant Phosphorus is introduced for flame retardation. Common materials include phosphorus-containing epoxy resins, phosphorus-containing phenolic resins, phosphate ester compounds and polyphosphate compounds, phosphazene compounds, and hypophosphite compounds. However, due to the limitations of the characteristics of these materials themselves However, it cannot meet the requirements of heat resistance and dielectric properties in the field of high-speed materials. For example, some materials such as phosphorus-containing epoxy resin and phosphorus-containing phenolic resin can achieve good flame retardancy, but due to their poor performance in terms of dielectric properties At the same time, the excessive introduction of phosphorus brings about the deterioration of the moisture and heat resistance, which cannot meet the reliability requirements of high-layer PCBs; the added type of phosphinate alone has a poor flame retardant effect, especially for resins with low carbon formation. System; Polyphosphazene compounds have low local melting point and strong plasticity, and a large amount of addition brings a significant decrease in heat resistance such as glass Transformation temperature is lowered, while when used alone, even if a large amount, it would be difficult to achieve the level of V-0 flame retardancy. Similar problems also exist with other phosphate compounds.
綜上所述，如何實現同時滿足高速基板材料要求之優異介電性能，如低的介電常數及介質損耗正切值，又能實現無鹵阻燃之新技術係未來本領域研究的重點方向之一。 In summary, how to achieve excellent dielectric properties that meet the requirements of high-speed substrate materials at the same time, such as low dielectric constant and dielectric loss tangent value, and new technologies that can achieve halogen-free flame retardant are the focus of future research in this field. One.
針對習知技術之問題，本發明之目的係一種含磷阻燃組合物，其可在較低之添加量下達到無鹵阻燃，達到UL 94V-0。本發明之目的亦在提供一種含磷聚苯醚樹脂組合物，其既能保持聚苯醚樹脂良好之介電 特性及耐熱性，且實現無鹵阻燃，阻燃劑達到UL 94V-0。本發明之另一目的亦在提供一種使用上述含磷聚苯醚樹脂組合物製作之預浸料及覆銅箔層壓板，具有良好之介電特性及耐熱性，且實現無鹵阻燃，阻燃劑達到UL 94V-0。 Aiming at the problems of the conventional technology, the object of the present invention is a phosphorus-containing flame retardant composition, which can achieve halogen-free flame retardant at a relatively low addition amount, reaching UL 94V-0. The object of the present invention is also to provide a phosphorus-containing polyphenylene ether resin composition which can maintain the good dielectric properties of the polyphenylene ether resin. Characteristics and heat resistance, and achieve halogen-free flame retardant, flame retardants reach UL 94V-0. Another object of the present invention is also to provide a prepreg and a copper-clad laminate made by using the above-mentioned phosphorus-containing polyphenylene ether resin composition, which has good dielectric properties and heat resistance, and realizes halogen-free flame retardance and flame retardancy. The agent reaches UL 94V-0.
為了實現上述目的，本發明採用如下技術手段：一種含磷阻燃組合物，所述阻燃組合物包含：(A)式(1)所示之DOPO衍生物，100重量份；(B)次磷酸鹽化合物，5~50重量份；(C)聚磷腈化合物，10~50重量份 In order to achieve the above object, the present invention adopts the following technical means: a phosphorus-containing flame retardant composition, the flame retardant composition comprises: (A) a DOPO derivative represented by formula (1), 100 parts by weight; (B) times Phosphate compound, 5-50 parts by weight; (C) Polyphosphazene compound, 10-50 parts by weight
R1係C2~C20之亞烷烴或亞芳香烴中之一種。 R1 is one of C2 ~ C20 alkylene or aromatic hydrocarbon.
所述次磷酸鹽化合物之含量例如係10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份或45重量份。 The content of the hypophosphite compound is, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or 45 parts by weight.
所述聚磷腈化合物之含量例如係10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份或45重量份。 The content of the polyphosphazene compound is, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or 45 parts by weight.
本發明中，使用上述含磷組合物作為阻燃劑，可發揮三種含磷化合物之間之協同效果，在較少之添加量下，實現無鹵阻燃，達到V-0級別。 In the present invention, using the above-mentioned phosphorus-containing composition as a flame retardant, the synergistic effect between the three phosphorus-containing compounds can be exerted, and halogen-free flame retardant can be achieved with a relatively small amount of addition, reaching V-0 level.
本發明中，所述組分(A)DOPO衍生物可由如下方法合成而得到，具體係：由化合物DOPO及二元醇在催化劑之作用下，反應溫度係50~300℃，反應時間係0.5~48小時，反應得到，具體反應式如下：
式中n係2~20之整數。 In the formula, n is an integer of 2-20.
上述所述之反應通過DOPO之活潑氫原子，在催化劑作用下與二元醇化合物發生脫水縮合反應得到；其中DOPO及二元醇之摩爾投料比控制在0.5~100，較佳係0.5~10，更佳係0.5~5，若摩爾比太低，將會導致DOPO轉化率低，若摩爾比太高，又會帶來二元醇後續之回收困難。 The above-mentioned reaction is obtained by the active hydrogen atom of DOPO and dehydration condensation reaction with the diol compound under the action of the catalyst; wherein the molar feeding ratio of DOPO and diol is controlled to 0.5 to 100, preferably 0.5 to 10, More preferably, it is 0.5 to 5. If the molar ratio is too low, the DOPO conversion rate will be low. If the molar ratio is too high, the subsequent recovery of the glycol will be difficult.
所述之催化劑無特別限制，任何可促進脫水反應和Arbuzov反應之催化劑皆可使用，可選擇之催化劑有烷基鹵化物，鹼金屬，鹼土金屬鹵化物，過渡金屬及其鹵代物，酸，Arbuzov催化劑，其中較佳係Arbuzov催化劑。 The catalyst is not particularly limited, and any catalyst that can promote the dehydration reaction and the Arbuzov reaction can be used. The catalysts to be selected are alkyl halides, alkali metals, alkaline earth metal halides, transition metals and their halides, acids, Arbuzov The catalyst is preferably an Arbuzov catalyst.
舉例而言，所述之DOPO之衍生物可係如下結構式：
較佳地，所述組分(B)次磷酸鹽化合物具有如下結構：
其中m係2或3；R3及R4獨立地為碳原子數係1~6之烷烴基或芳烴基，M係金屬原子，該金屬原子選自鈉、鈣、鎂、鋁、砷、鋅或鐵中任一種。從降低其吸水率及提高其磷含量之角度考慮，M較佳係鋁或鈉，惟若是進一步考慮盡可能降低含磷組合物加入對樹脂組合物固化後之介電性能之影響，M更佳係鋁。 Where m is 2 or 3; R3 and R4 are independently alkane or aromatic hydrocarbon groups having 1 to 6 carbon atoms, and M is a metal atom selected from sodium, calcium, magnesium, aluminum, arsenic, zinc, or iron Any of them. From the perspective of reducing its water absorption and increasing its phosphorus content, M is preferably aluminum or sodium, but if further consideration is made to reduce the influence of the phosphorus-containing composition as much as possible on the dielectric properties of the resin composition after curing, M is better. Department of aluminum.
更具體而言，本發明中所述次磷酸鹽化合物係
本發明中所述之組份(C)係聚磷腈化合物。聚磷腈化合物係一種全磷氮雜環非共軛化合物，具有優異之光穩定性及熱穩定性，高極限氧指數，低排煙量且有良好之耐化學特性，耐水性及耐溶劑性。 The component (C) described in the present invention is a polyphosphazene compound. Polyphosphazene compound is a kind of non-conjugated compound with complete phosphorus and nitrogen heterocycles. It has excellent light and thermal stability, high limiting oxygen index, low smoke emission and good chemical resistance, water resistance and solvent resistance. .
本發明中之聚磷腈化合物具有如下結構式：
其中n係3~100之整數，例如5、10、20、30、40、50、60、70、80或90。 Where n is an integer from 3 to 100, such as 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90.
其中R係苯氧基、碳原子數係1~10之烷基、乙烯基苯氧基或烯丙基苯氧基中任一種；
或，
其中q係3~25之整數，例如4、6、7、10、13、16、19或22；R係苯氧基、碳原子數係1~10之烷基、乙烯基苯氧基或烯丙基苯氧基中任一種。 Where q is an integer from 3 to 25, such as 4, 6, 7, 10, 13, 16, 19, or 22; R is phenoxy, alkyl having 1 to 10 carbon atoms, vinylphenoxy, or olefin Any of propylphenoxy.
本發明亦提供一種含磷聚苯醚樹脂組合物，其包含如上述之含磷組合物及端基官能化聚苯醚樹脂。 The present invention also provides a phosphorus-containing polyphenylene ether resin composition comprising the phosphorus-containing composition as described above and a terminal-functionalized polyphenylene ether resin.
本發明中，所述端基官能化聚苯醚樹脂係端羥基化聚苯醚樹脂、環氧化聚苯醚樹脂、乙烯基化聚苯醚樹脂或氰基化聚苯醚樹脂中任一種或至少兩種之混合物，較佳係乙烯基化聚苯醚樹脂或/及氰基化聚苯醚樹脂，更佳係乙烯基化聚苯醚樹脂。 In the present invention, any one or at least one of the terminal functionalized polyphenylene ether resins is a hydroxylated terminal polyphenylene ether resin, an epoxidized polyphenylene ether resin, a vinylated polyphenylene ether resin, or a cyanated polyphenylene ether resin. A mixture of the two is preferably a vinylated polyphenylene ether resin or / and a cyanated polyphenylene ether resin, and more preferably a vinylated polyphenylene ether resin.
本發明中，所述端基官能化聚苯醚樹脂結構式如式(2)所示：
式(2)中，a及b獨立地為1~30之整數，例如2、5、8、11、14、17、20、23、26或29，Z係式(3)或(4)所示之結構，-(-O-Y-)-為式(5)所示之結構，-(-O-X-O-)-為式(6)所示之結構：
式(4)中，A為亞芳香基、羰基或碳原子數係1~10(例如2、3、4、5、6、7、8或9)之亞烷基，m係0~10(例如1、2、3、4、5、6、7、8或9)之整數，R1、R2與R3相同或不同，獨立地為氫或碳原子數10以下之烷基；
式(5)中，R4與R6相同或不同，獨立地為氫原子、鹵素原子、碳原子數8以下之烷基或碳原子數8以下之苯基，R5與R7相同或不同，獨立地為鹵素原子、碳原子數8以下之烷基或碳原子數8以下之苯基；
式(6)中，R8、R9、R10、R11、R12、R13、R14及R15之間相同或不同，獨立地為氫原子、鹵素原子、碳原子數8以下之烷基或碳原子數8以下之苯基，B
係碳原子數20以下之亞烴基、
更具體而言，所述端基官能化聚苯醚樹脂係式(7)或(8)所示之結構：
式(7)中，R1~R3相同或不同，獨立地為氫或碳原子數10以下之烷基；R4與R6相同或不同，獨立地為氫原子、鹵素原子、碳原子數8以下之烷基或苯基；R5與R7相同或不同，獨立地為鹵素原子、碳原子數8以下之烷基或碳原子數8以下之苯基；R8、R9、R10、R11、R12、R13、R14及R15之間相同或不同，獨立地為氫原子、鹵素原子、碳原子數8以下之烷基或碳原子數8以下之苯基；a和b獨立地為1~30之整數，例如2、5、8、11、14、17、20、23、26或29，
B係碳原子數20以下之亞烴基、
式(8)中，R4與R6相同或不同，獨立地為氫原子、鹵素原子、碳原子數8以下之烷基或苯基；R5與R7相同或不同，係鹵素原子、碳原子數8以下 之烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之間相同或不同，係氫原子、鹵素原子、碳原子數8以下之烷基或苯基；a和b獨立地為1~30之整數；B係碳原子數20以下之亞烴基，n係0或者1。 In formula (8), R4 and R6 are the same or different, and are independently a hydrogen atom, a halogen atom, or an alkyl group having a carbon number of 8 or less; R5 is the same as or different from R7, and is a halogen atom or a carbon number of 8 or less Alkyl or phenyl; R8, R9, R10, R11, R12, R13, R14, and R15 are the same or different, and are hydrogen or halogen atoms, alkyl or phenyl groups with a carbon number of 8 or less; a and b It is independently an integer of 1 to 30; B is a hydrocarbon group having 20 or less carbon atoms, and n is 0 or 1.
更進一步，所述端基官能化聚苯醚樹脂亦可係式(9)至(13)所示之結構：
式(9)中，R1~R3相同或不同，為氫或碳原子數10以下之烷基；R4與R6相同或不同，為氫原子、鹵素原子、碳原子數8以下之烷基或苯基；R5與R7相同或不同，係鹵素原子、碳原子數8以下之烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之間相同或不同，係氫原子、鹵素原子、碳原子數8以下之烷基或苯基；a及b獨立地為1~30之整數。 In formula (9), R1 to R3 are the same or different and are hydrogen or an alkyl group having 10 or less carbon atoms; R4 and R6 are the same or different and are a hydrogen atom, a halogen atom, or an alkyl group having 8 or less carbon atoms or a phenyl group ; R5 and R7 are the same or different, and are halogen atoms, alkyl groups or phenyl groups with a carbon number of 8 or less; R8, R9, R10, R11, R12, R13, R14, and R15 are the same or different, and are hydrogen atoms, halogens An atom or an alkyl group having a carbon number of 8 or less; a and b are independently an integer of 1 to 30.
式(10)中，R1~R3相同或不同，係氫或碳原子數10以下之烷基；R4與R6相同或不同，係氫原子、鹵素原子、碳原子數8以下之烷基或苯基；R5與R7相同或不同，係鹵素原子、碳原子數8以下之烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之間相同或不同，係氫原子、鹵素原子、碳原子數8以下之烷基或苯基；a及b獨立地為1~30之整數。 In formula (10), R1 to R3 are the same or different and are hydrogen or an alkyl group having 10 or less carbon atoms; R4 and R6 are the same or different and are a hydrogen atom, a halogen atom, or an alkyl or phenyl group having 8 or less carbon atoms ; R5 and R7 are the same or different, and are halogen atoms, alkyl groups or phenyl groups with a carbon number of 8 or less; R8, R9, R10, R11, R12, R13, R14, and R15 are the same or different, and are hydrogen atoms, halogens An atom or an alkyl group having a carbon number of 8 or less; a and b are independently an integer of 1 to 30.
式(11)中，R1~R3相同或不同，係氫或碳原子數10以下之烷基；R4與R6相同或不同，係氫原子、鹵素原子、碳原子數8以下之烷基或苯基；R5與R7相同或不同，係鹵素原子、碳原子數8以下之烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之間相同或不同，係氫原子、鹵素原子、碳原子數8以下之烷基或苯基；a及b獨立地為1~30之整數。 In formula (11), R1 to R3 are the same or different and are hydrogen or an alkyl group having 10 or less carbon atoms; R4 and R6 are the same or different and are a hydrogen atom, a halogen atom, or an alkyl group having 8 or less carbon atoms ; R5 and R7 are the same or different, and are halogen atoms, alkyl groups or phenyl groups with a carbon number of 8 or less; R8, R9, R10, R11, R12, R13, R14, and R15 are the same or different, and are hydrogen atoms, halogens An atom or an alkyl group having a carbon number of 8 or less; a and b are independently an integer of 1 to 30.
式(12)中，R4與R6相同或不同，係氫原子、鹵素原子、碳原子數8以下之烷基或苯基；R5與R7相同或不同，係鹵素原子、碳原子數8以下之烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之間相同或不同，係氫原子、鹵素原子、碳原子數8以下之烷基或苯基；a及b獨立地為1~30之整數。 In formula (12), R4 and R6 are the same or different, and are a hydrogen atom, a halogen atom, and an alkyl group having a carbon number of 8 or less; R5 and R7 are the same or different and are a halogen atom and an alkyl group having a carbon number of 8 or less Or phenyl; R8, R9, R10, R11, R12, R13, R14, and R15 are the same or different and are a hydrogen atom, a halogen atom, or an alkyl or phenyl group having a carbon number of 8 or less; a and b are independently It is an integer from 1 to 30.
式(13)中，R4與R6相同或不同，係氫原子、鹵素原子、碳原子數8以下之烷基或苯基；R5與R7相同或不同，係鹵素原子、碳原子數8以下之烷基或苯基；R8、R9、R10、R11、R12、R13、R14及R15之間相同或不同， 係氫原子、鹵素原子、碳原子數8以下之烷基或苯基；a及b獨立地為1~30之整數。 In formula (13), R4 and R6 are the same or different, and are a hydrogen atom, a halogen atom, and an alkyl group having a carbon number of 8 or less; R5 and R7 are the same or different and are a halogen atom and an alkyl group having a carbon number of 8 or less Or phenyl; R8, R9, R10, R11, R12, R13, R14, and R15 are the same or different, It is a hydrogen atom, a halogen atom, an alkyl group or a phenyl group having 8 or less carbon atoms; a and b are independently integers of 1 to 30.
理想地，在含磷聚苯醚樹脂組合物中，以所述端基官能化聚苯醚樹脂係100重量份計，含磷阻燃組合物之添加量係15~60重量份，例如25重量份、30重量份、35重量份、40重量份、45重量份、50重量份或55重量份，較佳係20~50重量份，更佳係25~40重量份。藉由添加含磷阻燃組合物，發揮含磷組合物之間之協同效果，使固化後之聚苯醚樹脂組合物可達到良好之阻燃。惟含量阻燃組合物之添加量小於15重量份時，體系之阻燃達不到V-0級別，到添加量超過60份時，雖可充分地保證固化後之聚苯醚樹脂組合物達到良好之阻燃，惟由於含磷阻燃組合物本身吸水偏大，導致體系之耐熱性、介電性能會大幅惡化。 Ideally, in the phosphorus-containing polyphenylene ether resin composition, based on 100 parts by weight of the end-functionalized polyphenylene ether resin system, the addition amount of the phosphorus-containing flame retardant composition is 15-60 parts by weight, for example, 25 weight Parts, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, or 55 parts by weight, preferably 20 to 50 parts by weight, and more preferably 25 to 40 parts by weight. By adding a phosphorus-containing flame retardant composition, the synergistic effect between the phosphorus-containing compositions is exerted, so that the cured polyphenylene ether resin composition can achieve good flame retardancy. However, when the content of the flame retardant composition is less than 15 parts by weight, the flame retardance of the system cannot reach V-0 level. When the amount of the flame retardant composition exceeds 60 parts, it can fully ensure that the cured polyphenylene ether resin composition reaches Good flame retardant, but because the phosphorus-containing flame retardant composition itself absorbs too much water, the heat resistance and dielectric properties of the system will be greatly deteriorated.
本發明中，所述含磷聚苯醚樹脂組合物亦包含交聯劑，所述交聯劑係帶有不飽和雙鍵之聚烯烴樹脂，所述帶有不飽和雙鍵之聚烯烴樹脂係聚丁二烯及其接枝改性聚合物如馬來酸酐接枝該性聚丁二烯聚合物、丙烯酸改性丁二烯聚合物、丁二烯-苯乙烯共聚物、丁二烯-苯乙烯-二乙烯基苯共聚物或環烯烴共聚物中之任一種或者至少兩種之混合物。 In the present invention, the phosphorus-containing polyphenylene ether resin composition also includes a cross-linking agent. The cross-linking agent is a polyolefin resin having an unsaturated double bond, and the polyolefin resin having an unsaturated double bond. Polybutadiene and its graft-modified polymers such as maleic anhydride, grafted polybutadiene polymers, acrylic-modified butadiene polymers, butadiene-styrene copolymers, butadiene-benzene Either an ethylene-divinylbenzene copolymer or a cycloolefin copolymer or a mixture of at least two of them.
以端基官能化聚苯醚樹脂係100重量份計，所述帶有不飽和雙鍵之聚烯烴樹脂之添加量係10~100重量份，例如15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份或95重量份。由於烯烴樹脂之介電性能優異，因此添加合適比例之烯烴樹脂可進一步改善固化體系之介電性能如Dk/Df，同時由於烯烴樹脂 中帶有之不飽和雙鍵可與聚苯醚樹脂進一步交聯固化，可進一步提高耐熱性。當添加量小於10份時，烯烴樹脂中引入之不飽和雙鍵量太少，無法產生有效交聯之效果，無法達到提高耐熱性及介電性能之目的；若是烯烴樹脂量超過100份，則由於烯烴樹脂本身之剛性太差，膨脹係數大之原因亦會導致固化物之耐熱性巨大下降。 Based on 100 parts by weight of the terminal functionalized polyphenylene ether resin, the added amount of the polyolefin resin with unsaturated double bonds is 10 to 100 parts by weight, such as 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight Parts or 95 parts by weight. Due to the excellent dielectric properties of olefin resins, adding appropriate proportions of olefin resins can further improve the dielectric properties of curing systems such as Dk / Df. The unsaturated double bond contained in it can be further cross-linked and cured with polyphenylene ether resin, which can further improve heat resistance. When the added amount is less than 10 parts, the amount of unsaturated double bonds introduced into the olefin resin is too small to produce the effect of effective cross-linking, and the purpose of improving heat resistance and dielectric properties cannot be achieved; if the amount of the olefin resin exceeds 100 parts, Because the rigidity of the olefin resin itself is too poor, the large expansion coefficient will also cause the heat resistance of the cured product to decrease greatly.
理想地，所述端基官能化聚苯醚樹脂之數均分子量係500~5000，較佳之數均分子量係500~3000，更佳之數均分子量係800~2500。當使用數均分子量超過5000之端基官能化聚苯醚樹脂時，在加工過程中溶解性變差，無法使用常規之層壓板工藝進行上膠，需要加溫，使在覆銅板加工過程中工藝困難，操作危險，且流動性亦隨之下降，使多層板加工困難；而當數均分子量小於500時，其耐熱性、介電性能會下降，不利於製得高耐熱性之樹脂組合物及層壓板材料，同時介電特性亦會降低。當所述端基官能化聚苯醚樹脂進一步與交聯劑混合時，具有較小數均分子量之官能化聚苯醚樹脂能更佳地改善與交聯劑之間之相容性，即分子量越小，混合組分之間之相容性更好，儲存穩定性更好。此外，較低之分子量可提供更好之流動性，有利於在多層板加工過程中提供更良好之填膠性。 Ideally, the number-average molecular weight of the end-functionalized polyphenylene ether resin is 500-5000, preferably the number-average molecular weight is 500-3000, and more preferably the number-average molecular weight is 800-2500. When using a terminal-functionalized polyphenylene ether resin with a number average molecular weight of more than 5000, the solubility becomes poor during processing, and the conventional laminating process cannot be used for gluing. It is necessary to heat the process during the processing of copper-clad laminates. Difficult, dangerous operation, and the fluidity will be reduced, making the processing of multilayer boards difficult; and when the number average molecular weight is less than 500, its heat resistance and dielectric properties will be reduced, which is not conducive to the preparation of high heat resistance resin compositions and Laminate material, at the same time, the dielectric properties will be reduced. When the terminal functionalized polyphenylene ether resin is further mixed with a crosslinking agent, a functionalized polyphenylene ether resin having a smaller number average molecular weight can better improve compatibility with the crosslinking agent, that is, molecular weight The smaller, the better the compatibility between the mixed components and the better the storage stability. In addition, lower molecular weight can provide better fluidity, which is conducive to providing better filling performance during multilayer board processing.
本發明中，所述含磷聚苯醚樹脂組合物亦包含共交聯劑，所述共交聯劑係雙馬來醯亞胺樹脂或/及多官能團丙烯酸酯化合物，較佳係馬來醯亞胺樹脂。 In the present invention, the phosphorus-containing polyphenylene ether resin composition also includes a co-crosslinking agent, and the co-crosslinking agent is a bismaleimide imine resin or / and a polyfunctional acrylate compound, and is preferably a maleimide. Imine resin.
以端基官能化聚苯醚樹脂為100重量份計，所述共交聯劑之添加量係5~50重量份，例如7重量份、10重量份、13重量份、16重量份、19重量份、22重量份、25重量份、28重量份、31重量份、35重量份、38重量 份、41重量份、44重量份或47重量份。所述共交聯劑之引入，主要目的係出於進一步提高聚苯醚固化產物之耐熱性角度出發，由於馬來醯亞胺樹脂可係與端基官能化聚苯醚樹脂及烯烴樹脂之不飽和雙鍵發生固化交聯反應，形成一個由三者共同組成之交聯網狀結構，體系具有更佳之耐熱穩定性；馬來醯亞胺樹脂添加量太少無法達到改善交聯密度，提高耐熱性之目的，若是量太多雖可有效提高體系之交聯密度，惟由於馬來醯亞胺本身結構之極性較大，會帶來介電性能之明顯下降。 The end-functionalized polyphenylene ether resin is 100 parts by weight, and the amount of the co-crosslinking agent added is 5 to 50 parts by weight, for example, 7 parts by weight, 10 parts by weight, 13 parts by weight, 16 parts by weight, and 19 parts by weight. Parts, 22 parts by weight, 25 parts by weight, 28 parts by weight, 31 parts by weight, 35 parts by weight, 38 parts by weight Parts, 41 parts by weight, 44 parts by weight, or 47 parts by weight. The main purpose of the introduction of the co-crosslinking agent is to further improve the heat resistance of the cured product of polyphenylene ether, because the maleimide resin can be different from the end-functionalized polyphenylene ether resin and olefin resin. The saturated double bond undergoes a curing cross-linking reaction to form a cross-linked network structure composed of the three. The system has better heat stability; the addition of maleimide imide resin is too small to improve the crosslinking density and heat resistance. The purpose is that if the amount is too large, the crosslinking density of the system can be effectively improved, but because of the polarity of the maleimide structure, the dielectric properties will be significantly reduced.
本發明中，所述含磷聚苯醚樹脂組合物亦包含引發劑。所述引發劑之半衰期溫度t1/2不小於100℃，係過氧化物自由基引發劑，選自過氧化二異丙苯、過氧化苯甲酸叔丁酯、2,5-二(2-乙基己醯過氧)-2,5-二甲基己烷、二-(叔丁基過氧異丙基)苯、過氧化(2,4-二氯苯甲醯)、2,5-二甲基-2,5-雙(叔丁基過氧)己烷、過氧化-2-乙基己基碳酸叔丁酯、2,5-二甲基-2,5-雙(叔丁基過氧)-3-已炔、4,4-二(叔丁基過氧化)戊酸丁酯、1,1-雙(叔丁基過氧化)-3,3,5-三甲基環已烷、3,3,5,7,7-五甲基-1,2,4-三氧雜環庚烷、二叔丁基過氧化物或叔丁基過氧化異丙苯中任一種或至少兩種之混合物，較佳係過氧化二異丙苯，因該化合物具有較高之半衰期溫度及反應起始溫度，因此在無須固化時，在半固化過程中，不會過度地引發固化反應，亦不會降低聚苯醚樹脂之儲存穩定性。 In the present invention, the phosphorus-containing polyphenylene ether resin composition also includes an initiator. The half-life temperature t1 / 2 of the initiator is not less than 100 ° C and is a peroxide radical initiator selected from the group consisting of dicumyl peroxide, tert-butyl peroxide benzoate, and 2,5-bis (2-ethyl Hexamethylene peroxo) -2,5-dimethylhexane, di- (tert-butylperoxyisopropyl) benzene, peroxo (2,4-dichlorobenzidine), 2,5-di Methyl-2,5-bis (t-butylperoxy) hexane, 2-ethylhexyl peroxyt-butyl carbonate, 2,5-dimethyl-2,5-bis (t-butylperoxy) ) -3-hexyne, 4,4-bis (t-butylperoxy) butyl valerate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, Any one or at least two of 3,3,5,7,7-pentamethyl-1,2,4-trioxane, di-tert-butyl peroxide or t-butyl cumene peroxide The mixture is preferably dicumyl peroxide. Because the compound has a high half-life temperature and a reaction initiation temperature, when it is not required to be cured, the curing reaction will not be excessively initiated during the semi-curing process. Will reduce the storage stability of polyphenylene ether resin.
本發明聚苯醚樹脂組合物中之引發劑，目的在於提高交聯固化效果。雖然端基官能化聚苯醚樹脂與交聯劑亦可在加熱高溫條件下進行固化，惟層壓板應用時，工藝條件難以滿足高溫要求，使其加工難度增加，此外，其亦不利於工藝效率，增加生產成本，因此加入引發劑更加有利。 以端基官能化聚苯醚樹脂係100重量份計，所述引發劑之添加量係0.5~7重量份，例如1.3重量份、1.6重量份、1.9重量份、2.2重量份、2.5重量份、3.1重量份、3.5重量份、3.9重量份、4.3重量份、4.7重量份、5重量份、5.4重量份、5.8重量份、6.2重量份或6.6重量份。 The purpose of the initiator in the polyphenylene ether resin composition of the present invention is to improve the crosslinking curing effect. Although the end-functionalized polyphenylene ether resin and cross-linking agent can also be cured under high temperature and heating conditions, when the laminate is applied, the process conditions are difficult to meet the high temperature requirements, making it more difficult to process, and it is not conducive to process efficiency. , Increase production costs, so adding initiator is more advantageous. Based on 100 parts by weight of the terminal functionalized polyphenylene ether resin, the amount of the initiator added is 0.5 to 7 parts by weight, such as 1.3 parts by weight, 1.6 parts by weight, 1.9 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 3.1 parts by weight, 3.5 parts by weight, 3.9 parts by weight, 4.3 parts by weight, 4.7 parts by weight, 5 parts by weight, 5.4 parts by weight, 5.8 parts by weight, 6.2 parts by weight or 6.6 parts by weight.
本發明中，所述含磷聚苯醚樹脂組合物亦包含矽烷偶聯劑，以端基官能化聚苯醚樹脂係100重量份計，所述矽烷偶聯劑添加量為0.1~10重量份，例如0.5重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份、5重量份、5.5重量份、6重量份、6.5重量份、7重量份、7.5重量份、8重量份、8.5重量份、9重量份或9.5重量份。 In the present invention, the phosphorus-containing polyphenylene ether resin composition also includes a silane coupling agent. Based on 100 parts by weight of the terminal-functionalized polyphenylene ether resin system, the silane coupling agent is added in an amount of 0.1 to 10 parts by weight. For example, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, or 9.5 parts by weight.
對偶聯劑之種類並無特別限定。偶聯劑可進一步降低樹脂固化物之表面張力，使其黏度得到進一步之降低，提高樹脂組合物之流動性。特別係在添加填料之情形時，偶聯劑之加入可有效地提高樹脂與填料之間的結合力，消除此兩者之間的介面，進一步降低固化物之吸水率。所述偶聯劑可以係矽烷類、矽烷預聚體、鈦酸酯類，矽烷偶聯劑亦可以係環氧基矽烷偶聯劑、氨基矽烷偶聯劑、苯氨基矽烷偶聯劑、乙烯基矽烷偶聯劑、異氰酸酯基矽烷偶聯劑、丙烯基矽烷偶聯劑、異丁烯基矽烷偶聯劑、苯乙烯基矽烷偶聯劑、脲基矽烷偶聯劑、氯丙基矽烷偶聯劑、硫基矽烷偶聯劑或硫化基矽烷偶聯劑等。 The type of the coupling agent is not particularly limited. The coupling agent can further reduce the surface tension of the cured resin, further reduce its viscosity, and improve the fluidity of the resin composition. Especially when adding a filler, the addition of a coupling agent can effectively improve the binding force between the resin and the filler, eliminate the interface between the two, and further reduce the water absorption of the cured product. The coupling agent may be a silane, a silane prepolymer, or a titanate. The silane coupling agent may also be an epoxy silane coupling agent, an amino silane coupling agent, a phenylamino silane coupling agent, or a vinyl group. Silane coupling agent, isocyanate-based silane coupling agent, acrylic silane coupling agent, isobutylene silane coupling agent, styryl silane coupling agent, urea-based silane coupling agent, chloropropylsilane coupling agent, sulfur Based silane coupling agent or sulfurized silane coupling agent.
本發明中，所述含磷聚苯醚樹脂組合物亦包含填料，所述填料係有機或無機填料，無機填料選自結晶型二氧化矽、熔融二氧化矽、球形二氧化矽、空心二氧化矽、玻璃粉、氮化鋁、氮化硼、碳化矽、氫氧化 鋁、二氧化鈦、鈦酸鍶、鈦酸鋇、氧化鋁、硫酸鋇、滑石粉、矽酸鈣、碳酸鈣或雲母中任一種或至少兩種之混合物；有機填料選自聚四氟乙烯粉末、聚苯硫醚或聚醚碸粉末中任一種或至少兩種之混合物。 In the present invention, the phosphorus-containing polyphenylene ether resin composition also includes a filler. The filler is an organic or inorganic filler. The inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, and hollow dioxide. Silicon, glass frit, aluminum nitride, boron nitride, silicon carbide, hydroxide Aluminium, titanium dioxide, strontium titanate, barium titanate, alumina, barium sulfate, talc, calcium silicate, calcium carbonate, or a mixture of at least two of mica; the organic filler is selected from polytetrafluoroethylene powder, poly Either phenylene sulfide or polyether sulfonium powder or a mixture of at least two of them.
此外，無機填料之形狀、粒徑等亦無特別限定，一般粒徑係0.01-50μm，較佳係0.01-20μm，更佳係0.01-10μm，此種粒徑範圍之無機填料在樹脂液中更易分散。 In addition, the shape and particle size of the inorganic filler are also not particularly limited. Generally, the particle size is 0.01-50 μm, preferably 0.01-20 μm, and more preferably 0.01-10 μm. The inorganic filler in this particle size range is easier in the resin solution. dispersion.
以端基官能化聚苯醚樹脂係100重量份計，所述填料之添加量係10~300重量份，例如30重量份、60重量份、90重量份、120重量份、150重量份、180重量份、210重量份、240重量份或270重量份。 Based on 100 parts by weight of the terminal functionalized polyphenylene ether resin, the filler is added in an amount of 10 to 300 parts by weight, such as 30 parts by weight, 60 parts by weight, 90 parts by weight, 120 parts by weight, 150 parts by weight, 180 parts by weight Parts by weight, 210 parts by weight, 240 parts by weight, or 270 parts by weight.
本發明所述之“包含”，係指其除所述組份外，亦可包含其他組份，此些其他組份賦予所述含磷聚苯醚樹脂組合物不同之特性。除此之外，本發明所述之“包含”，亦可替換為封閉式之“為”或“由……組成”。 The “comprising” in the present invention means that it may contain other components in addition to the components, and these other components impart different characteristics to the phosphorus-containing polyphenylene ether resin composition. In addition, the "comprising" described in the present invention can also be replaced with a closed "is" or "consisting of".
例如，所述含磷聚苯醚樹脂組合物亦可含有各種添加劑，作為具體例，可列舉抗氧劑、熱穩定劑、抗靜電劑、紫外線吸收劑、顏料、著色劑或潤滑劑等。此些各種添加劑可單獨使用，亦可兩種或兩種以上混合使用。 For example, the phosphorus-containing polyphenylene ether resin composition may also contain various additives. Specific examples include antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, and lubricants. These various additives may be used alone or in combination of two or more.
進一步，本發明提供一種使用上述含磷聚苯醚樹脂組合物製作之預浸料，包含基材及通過含浸乾燥後附著於基材上之如上所述之含磷聚苯醚樹脂組合物。 Furthermore, the present invention provides a prepreg made using the above-mentioned phosphorus-containing polyphenylene ether resin composition, comprising a substrate and the phosphorus-containing polyphenylene ether resin composition as described above, which is adhered to the substrate after being impregnated and dried.
製作時，首先將端基官能化聚苯醚樹脂、含磷組合物、任選交聯劑、任選共交聯劑、任選引發劑、任選偶聯劑以及任選填料溶解至一 種或多種有機溶劑中，製得均一之膠液。對有機溶劑並無特別限定，只要可溶解以上組分，且不影響其反應性；適合之溶劑包含：酮類如甲乙酮、丙酮等，醚類如丙二醇單甲醚、二丁醚等，酯類如乙酸乙酯，芳香類如甲苯、二甲苯等，鹵代烴類如三氯乙烷等。每種溶劑可單獨使用，亦可組合使用。膠液中樹脂固體物質之濃度可根據膠液浸漬到基材之種類及工藝做適當改變，例如其合適之濃度係30~80%。藉由上述製得之膠液浸漬到基材，接著，對其進行加熱烘乾以除去有機溶劑並部分固化基材內之樹脂組合物，從而得到預浸料。 When making, firstly dissolve the terminal functionalized polyphenylene ether resin, phosphorus-containing composition, optional cross-linking agent, optional co-cross-linking agent, optional initiator, optional coupling agent and optional filler to In one or more organic solvents, a uniform glue solution is prepared. There is no particular limitation on the organic solvent, as long as it can dissolve the above components without affecting its reactivity; suitable solvents include: ketones such as methyl ethyl ketone, acetone, etc., ethers such as propylene glycol monomethyl ether, dibutyl ether, and the like Such as ethyl acetate, aromatics such as toluene and xylene, and halogenated hydrocarbons such as trichloroethane. Each solvent can be used alone or in combination. The concentration of the resin solid matter in the glue solution can be appropriately changed according to the type and process of the glue solution immersed in the substrate, for example, its appropriate concentration is 30 ~ 80%. The glue solution prepared above is impregnated into the substrate, and then heated and dried to remove the organic solvent and partially cure the resin composition in the substrate to obtain a prepreg.
所述基材係有機纖維、碳纖維或玻璃纖維製得之紡織物或無紡織物；對於玻璃纖維製得之紡織物或無紡織物，其主要成分中包含重量比50~80%之SiO2、重量比0~30%之CaO、重量比0~20%之Al2O3、重量比5~25%之B2O3、及重量比0~5%之MgO。所述增強材料較佳係編製纖維布，可選為E-Glass，T-Glass，NE-Glass，L-Glass，Q-Glass。 The base material is a woven or non-woven fabric made of organic fibers, carbon fibers, or glass fibers. For woven or non-woven fabrics made of glass fibers, the main component contains 50 to 80% by weight of SiO2 and weight. CaO ratio of 0 to 30%, Al2O3 ratio of 0 to 20% by weight, B2O3 ratio of 5 to 25% by weight, and MgO of 0 to 5% by weight. The reinforcing material is preferably a knitted fabric, and can be selected from E-Glass, T-Glass, NE-Glass, L-Glass, and Q-Glass.
用來浸漬上述基材之樹脂含量，較佳係使預浸料中之樹脂含量係30品質%或更高。由於基材之介電常數往往高於樹脂組合物，為降低由此些預浸料製得之層壓板之介電常數，樹脂組合物成分在預浸料中之含量較佳係高於上述含量。例如使用樹脂組分含量係40%之預浸料製得之層壓板，其介電常數係3.5，而使用樹脂含量係50%或更高之預浸料製得之層壓板，其介電常數係3.2或更低。此外，上述之預浸料係在條件為80~170℃下烘烤2~15分鐘，惟並不以此為限。 The resin content used to impregnate the above substrate is preferably such that the resin content in the prepreg is 30% by mass or more. Since the dielectric constant of the substrate is often higher than that of the resin composition, in order to reduce the dielectric constant of laminates made from these prepregs, the content of the resin composition components in the prepreg is preferably higher than the above content . For example, the dielectric constant of a laminate made of a prepreg with a resin content of 40% is 3.5, and the dielectric constant of a laminate made of a prepreg with a resin content of 50% or more Department 3.2 or lower. In addition, the above-mentioned prepreg is baked under the conditions of 80-170 ° C for 2-15 minutes, but it is not limited thereto.
此外，本發明亦提供一種層壓板，其包含至少一張疊合之如上所述之預浸料。 In addition, the present invention also provides a laminate comprising at least one laminated prepreg as described above.
此外，本發明亦提供一種使用上述含磷聚苯醚樹脂組合物製作之覆銅箔層壓板，包含數張疊合之預浸料及壓覆於疊合後預浸料之一面或兩面之銅箔。 In addition, the present invention also provides a copper-clad laminate made of the above-mentioned phosphorus-containing polyphenylene ether resin composition, comprising a plurality of laminated prepregs and a copper foil laminated on one or both sides of the laminated prepreg. .
具體而言，其係藉由堆疊一張或多張本發明之預浸料，在其一面或兩面附上銅箔等，接著進行熱壓而製得，在層壓板表面之銅箔上進行蝕刻形成所需線路圖而得到印刷電路板。此外，亦可藉由以下方式及步驟製備多層印刷電路板：使用印刷電路板作為內層印刷電路板，對其上方之銅箔進行表面處理，按照需求以一定順序將本發明之預浸料及上述進行過表面處理之印刷電路板堆疊進行熱壓，熱壓條件可根據本發明之聚苯醚樹脂組合物之組成比例而定，對此並無特別限定。熱壓條件較佳係150~250℃之溫度範圍及1.0MPa~10.0MPa之壓力範圍下熱壓一段時間。以此方法及步驟獲得之層壓板及印刷電路板具有良好之高頻特性如介電性能等，同時亦具有良好之工藝加工性、耐熱性及耐濕性。 Specifically, it is prepared by stacking one or more prepregs of the present invention, attaching copper foil or the like to one or both sides thereof, and then performing hot pressing to etch the copper foil on the surface of the laminate. A desired circuit pattern is formed to obtain a printed circuit board. In addition, the multilayer printed circuit board can also be prepared by the following methods and steps: using the printed circuit board as the inner layer printed circuit board, surface-treating the copper foil thereon, and applying the prepreg of the present invention and the above in a certain order according to requirements. The surface-treated printed circuit board stack is hot-pressed, and the hot-pressing conditions can be determined according to the composition ratio of the polyphenylene ether resin composition of the present invention, and there is no particular limitation on this. The hot-pressing conditions are preferably hot-pressing for a period of time in a temperature range of 150 to 250 ° C and a pressure range of 1.0 MPa to 10.0 MPa. The laminates and printed circuit boards obtained by this method and steps have good high-frequency characteristics such as dielectric properties, and also have good processability, heat resistance and humidity resistance.
此外，為了進一步提高材料於高頻高速領域之應用，在本發明中之覆銅箔層壓板生產中，所使用之銅箔，可選擇電解銅箔或壓延銅箔，其表面粗糙度小於5微米，可改善及提高層壓板材料在高頻高速印刷電路板使用之訊號損失。同時，為提高銅箔接觸預浸料一面之結合力，上述所用之銅箔亦可使用矽烷偶聯劑進行化學處理，所用之偶聯劑係環氧基矽烷偶聯劑、乙烯基矽烷偶聯劑或丙烯酸酯基矽烷偶聯劑中之一種或多種之混合物，目的係提高銅箔與基材之結合力，防止在印刷電路板使用過程中產生掉新、掉焊盤等風險。 In addition, in order to further improve the application of the material in the high-frequency and high-speed field, the copper foil used in the production of the copper-clad laminate in the present invention can be selected from electrolytic copper foil or rolled copper foil, and its surface roughness is less than 5 microns. , Can improve and increase the signal loss of laminate materials used in high-frequency high-speed printed circuit boards. At the same time, in order to improve the binding force of the side where the copper foil contacts the prepreg, the copper foil used above can also be chemically treated with a silane coupling agent. The coupling agent used is an epoxy silane coupling agent, a vinyl silane coupling Agent or a mixture of one or more of acrylate-based silane coupling agents, the purpose of which is to improve the bonding force between the copper foil and the substrate, and prevent the risk of new or missing pads during the use of the printed circuit board.
本發明亦提供一種印刷電路板，其包含至少一張疊合之如上 所述之預浸料。 The present invention also provides a printed circuit board, which includes at least one piece superimposed above. Said prepreg.
與習知技術相較，本發明具有如下功效：本發明之聚苯醚樹脂組合物，係低分子量之官能化聚苯醚樹脂組合物，具有良好之工藝加工性，保持了聚苯醚樹脂良好之介電特性及耐熱性，再添加特定結構含磷阻燃劑成分，既保持了原有聚苯醚樹脂體系之耐熱性、介電性能、低吸水性，同時實現無鹵阻燃，阻燃達到UL 94V-0級別。 Compared with the conventional technology, the present invention has the following effects: The polyphenylene ether resin composition of the present invention is a low molecular weight functionalized polyphenylene ether resin composition, which has good processability and maintains good polyphenylene ether resin. Dielectric properties and heat resistance, and the addition of a specific structure phosphorus-containing flame retardant component, which maintains the heat resistance, dielectric properties, and low water absorption of the original polyphenylene ether resin system, while achieving halogen-free flame retardant and flame retardant Reached UL 94V-0 level.
下面結合附圖並通過具體實施方式來進一步說明本發明的技術手段。 The technical means of the present invention will be further described below with reference to the drawings and specific embodiments.
合成例1：DOPO衍生物之製備Synthesis Example 1: Preparation of DOPO derivatives
朝配有加料漏斗、熱電偶、機械攪拌器及氮流之四頸反應器中加入叔丁醇鉀230g，溶劑無水DMSO1.5L。在室溫下攪拌該混合物，直至其變成均勻溶液。將溶液冷卻至10℃，以10小份加入DOPO 42.3g，以保持反應溫度低於30℃。在1小時內將加料漏斗中之二氯乙烷92g緩慢加入至上述溶液中。加熱至50度反應1小時。冷卻至10℃反應並加入3L水。過濾漿料，並用水、丙酮合乙酸乙酯洗滌濕濾餅，得到532g粗濕物質，使該物質在MeCN/乙醇/水5320ml中回流，並緩慢冷卻至5℃。藉由漏斗過濾白色固體，並於80℃真空烘箱中乾燥8~10小時，得到乾燥之白色粉末260g，即為式(1)之DOPO衍生物1，其中R1係-CH2-CH2-。 To a four-necked reactor equipped with an addition funnel, a thermocouple, a mechanical stirrer, and a nitrogen stream, 230 g of potassium tert-butoxide and 1.5 L of anhydrous DMSO as a solvent were added. The mixture was stirred at room temperature until it became a homogeneous solution. The solution was cooled to 10 ° C and 42.3 g of DOPO was added in 10 small portions to keep the reaction temperature below 30 ° C. 92 g of dichloroethane in the addition funnel was slowly added to the solution over 1 hour. Heat to 50 degrees for 1 hour. The reaction was cooled to 10 ° C and 3 L of water was added. The slurry was filtered, and the wet cake was washed with water and acetone and ethyl acetate to obtain 532 g of a crude wet material, which was refluxed in 5320 ml of MeCN / ethanol / water, and slowly cooled to 5 ° C. The white solid was filtered through a funnel and dried in a vacuum oven at 80 ° C. for 8-10 hours to obtain 260 g of a dry white powder, which is the DOPO derivative 1 of formula (1), wherein R1 is -CH2-CH2-.
合成例2Synthesis Example 2
合成方法參照合成例1，將其中之二氯甲烷替換成二氯對二甲苯，得 到式(1)之DOPO衍生物2，其中R1係苯基。 For the synthesis method, refer to Synthesis Example 1. Replace the dichloromethane with dichloroparaxylene to obtain To DOPO derivative 2 of formula (1), wherein R1 is phenyl.
混合例1：含磷阻燃組合物之製備(P15.4%)Mixing Example 1: Preparation of a phosphorus-containing flame retardant composition (P15.4%)
將35重量份之次磷酸鹽化合物、100重量份之合成例1的DOPO衍生物以及18重量份之聚磷腈化合物混合，得到含磷組合物；所述次磷酸鹽化合物係：
所述聚磷腈化合物具有如下結構：
混合例2：含磷組合物之製備(P16%)Mixing Example 2: Preparation of a phosphorus-containing composition (P16%)
將50重量份之次磷酸鹽化合物、100重量份之合成例1的DOPO衍生物以及25重量份之聚磷腈化合物混合，得到含磷組合物；所述次磷酸鹽化合物係：
所述聚磷腈化合物具有如下結構：
混合例3：含磷組合物之製備(P13.8%)Mixing Example 3: Preparation of a phosphorus-containing composition (P13.8%)
將10重量份之次磷酸鹽化合物、100重量份之合成例1的DOPO衍生物以及25重量份之聚磷腈化合物混合，得到含磷組合物；所述次磷酸鹽化合物係：
所述聚磷腈化合物具有如下結構：
其中q係3；其中R係苯氧基。 Where q is 3; where R is phenoxy.
混合例4含磷組合物之製備(P15%)Preparation of Mixing Example 4 Phosphorous Composition (P15%)
將30重量份之次磷酸鹽化合物、100重量份之合成例2的DOPO衍生物以及40重量份之聚磷腈化合物混合，得到含磷組合物；所述次磷酸鹽化合物係：
所述聚磷腈化合物具有如下結構兩者之混合物：
其中q係3；其中R係苯氧基。 Where q is 3; where R is phenoxy.
實施例1Example 1
將100g甲基丙烯酸酸甲酯改性之聚苯醚SA9000與作為溶劑之甲苯混合，溶解完全得到端基官能化聚苯醚樹脂溶液，接著加入45g苯乙烯-丁二烯共聚物R100作為交聯劑，加入2g過氧化二異丙苯作為引發劑，45g混合例1之含磷組合物作為阻燃劑，0.8g環氧基矽烷偶聯劑及80g二氧化矽(SC-2050SQ)作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。 100 g of methyl methacrylate-modified polyphenylene ether SA9000 was mixed with toluene as a solvent to completely dissolve a terminally functionalized polyphenylene ether resin solution, and then 45 g of styrene-butadiene copolymer R100 was added as a cross-linking agent. Agent, adding 2 g of dicumyl peroxide as an initiator, 45 g of the phosphorus-containing composition of Mixing Example 1 as a flame retardant, 0.8 g of an epoxy silane coupling agent, and 80 g of silicon dioxide (SC-2050SQ) as a filler, The above mixture is mixed in toluene, and stirred to dissolve to obtain a uniform resin composition, that is, a glue solution.
將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度係35μm的銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得到雙面覆銅之層壓板。 The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. A copper foil with a thickness of 35 μm was attached to both sides of the eight sheets of prepreg prepared above, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
實施例2Example 2
將100g甲基丙烯酸酸甲酯基改性之聚苯醚SA9000與作為溶劑之甲苯混合，溶解完全得到端基官能化聚苯醚樹脂溶液，接著加入20g聚丁二烯聚物B-1000作為交聯劑，加入2.0g過氧化二異丙苯作為引發劑，30g混合例2之含磷組合物作為阻燃劑，0.8g乙烯基矽烷偶聯劑及80g二氧化矽(SC-2050SQ)作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。 100 g of methyl methacrylate-modified polyphenylene ether SA9000 was mixed with toluene as a solvent, and the terminally functionalized polyphenylene ether resin solution was completely dissolved, and then 20 g of polybutadiene polymer B-1000 was added as a solvent. Adding agent, adding 2.0 g of dicumyl peroxide as an initiator, 30 g of the phosphorus-containing composition of Mixing Example 2 as a flame retardant, 0.8 g of a vinyl silane coupling agent, and 80 g of silicon dioxide (SC-2050SQ) as a filler , The above mixture is mixed in toluene, and stirred to dissolve to obtain a uniform resin composition, that is, a glue solution.
將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度係35μm之銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得 到雙面覆銅之層壓板。 The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. On the two sides of the 8 prepregs prepared above, copper foils with a thickness of 35 μm were attached to both sides, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes. To double-sided copper-clad laminates.
實施例3Example 3
將100g甲基丙烯酸酸甲酯基改性之聚苯醚SA9000與作為溶劑之甲苯100g混合，溶解完全得到端基官能化聚苯醚樹脂溶液，接著加入30g苯乙烯-丁二烯共聚物R100作為交聯劑，15g雙馬來醯亞胺樹脂作為共固化劑，再加入3.0g過氧化二異丙苯作為引發劑，35g混合例2之含磷組合物作為阻燃劑，2g乙烯基基矽烷偶聯劑及150g二氧化矽作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。 100 g of methyl methacrylate-modified polyphenylene ether SA9000 was mixed with 100 g of toluene as a solvent, and dissolved to obtain a terminally functionalized polyphenylene ether resin solution, followed by adding 30 g of styrene-butadiene copolymer R100 as Cross-linking agent, 15 g of bismaleimide resin as co-curing agent, 3.0 g of dicumyl peroxide as initiator, 35 g of phosphorus-containing composition of mixing example 2 as flame retardant, 2 g of vinyl silane The coupling agent and 150 g of silicon dioxide are used as fillers. The above mixture is mixed in toluene and stirred to dissolve to obtain a uniform resin composition, that is, a glue solution.
將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度係35μm的銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得到雙面覆銅之層壓板。 The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. A copper foil with a thickness of 35 μm was attached to both sides of the eight sheets of prepreg prepared above, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
實施例4Example 4
將100g苯乙烯基聚苯醚OPE-2000與作為溶劑之甲苯100g混合，溶解完全得到端基官能化聚苯醚樹脂溶液，接著加入35g聚丁二烯聚合物B-2000作為交聯劑，加入2.5g過氧化二異丙苯作為引發劑，50g混合例3之含磷組合物作為阻燃劑，150g乙烯基處理之二氧化矽作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。 100 g of styrene-based polyphenylene ether OPE-2000 was mixed with 100 g of toluene as a solvent, and dissolved to obtain a terminally functionalized polyphenylene ether resin solution. Then 35 g of polybutadiene polymer B-2000 was added as a cross-linking agent. 2.5 g of dicumyl peroxide as an initiator, 50 g of the phosphorus-containing composition of Mixing Example 3 as a flame retardant, and 150 g of vinyl-treated silicon dioxide as a filler. The above mixture was mixed in toluene and stirred to dissolve to obtain uniformity. Resin composition, namely glue.
將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度係35μm之銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得到雙面覆銅之層壓板。 The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. A copper foil with a thickness of 35 μm was attached to both sides of the eight sheets of prepreg prepared above, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
實施例5Example 5
將100g苯乙烯基封端的聚苯醚樹脂OPE-2000與作為溶劑之甲苯100g混合溶解完全得到端基官能化聚苯醚樹脂溶液，接著加入20g苯乙烯-丁二烯共聚物R100作為交聯劑，10g雙馬來醯亞胺樹脂作為共固化劑，再加入3.0g過氧化二異丙苯作為引發劑，45g混合例2之含磷組合物作為阻燃劑，200g乙烯基基矽烷偶聯劑及150g二氧化矽作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。 100g of styrene-terminated polyphenylene ether resin OPE-2000 and 100g of toluene as a solvent were mixed and dissolved to obtain a terminally functionalized polyphenylene ether resin solution, and then 20g of styrene-butadiene copolymer R100 was added as a crosslinking agent. 10 g of bismaleimide imide resin as a co-curing agent, 3.0 g of dicumyl peroxide as an initiator, 45 g of the phosphorus-containing composition of Mixing Example 2 as a flame retardant, and 200 g of a vinyl silane coupling agent And 150 g of silicon dioxide as a filler, the above mixture was mixed in toluene, and stirred to dissolve to obtain a uniform resin composition, that is, a glue solution.
將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度係35μm之銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得到雙面覆銅之層壓板。 The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. A copper foil with a thickness of 35 μm was attached to both sides of the eight sheets of prepreg prepared above, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
實施例6Example 6
將100g甲基丙烯酸酸甲酯基改性之聚苯醚SA9000及作為溶劑之甲苯100g混合溶解完全得到端基官能化聚苯醚樹脂溶液，接著加入75g苯乙烯-丁二烯共聚物R100作為交聯劑，45g雙馬來醯亞胺樹脂作為共固化劑，再加入3.0g過氧化二異丙苯作為引發劑，35g混合例4之含磷組合物作為阻燃劑，200g乙烯基基矽烷處理之二氧化矽SC-2300SVJ作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度係35μm之銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得到雙面覆銅之層壓板。 100 g of methyl methacrylate-modified polyphenylene ether SA9000 and 100 g of toluene as a solvent were mixed and dissolved to obtain a terminally functionalized polyphenylene ether resin solution, and then 75 g of a styrene-butadiene copolymer R100 was added as a solvent. Additive, 45 g of bismaleimide resin as co-curing agent, and then add 3.0 g of dicumyl peroxide as an initiator, 35 g of the phosphorus-containing composition of Mixing Example 4 as a flame retardant, and 200 g of vinyl silane treatment Silicon dioxide SC-2300SVJ is used as a filler, and the above mixture is mixed in toluene and stirred to dissolve to obtain a uniform resin composition, that is, a glue solution. The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. A copper foil with a thickness of 35 μm was attached to both sides of the eight sheets of prepreg prepared above, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
實施例7Example 7
將100g甲基丙烯酸酸甲酯基改性之聚苯醚SA9000與作為溶劑之甲苯100g混合，溶解完全得到端基官能化聚苯醚樹脂溶液，接著加入30馬來酸酐接枝改性聚丁二烯聚合物Ricon156MA17作為交聯劑，25g馬來醯亞胺樹脂作為共交聯劑，加入2.5g過氧化二異丙苯作為引發劑，35g混合例3之含磷組合物作為阻燃劑，300g乙烯基基矽烷處理之二氧化矽SC-2300SVJ作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。 100 g of methyl methacrylate-modified polyphenylene ether SA9000 was mixed with 100 g of toluene as a solvent, and dissolved to obtain a terminally functionalized polyphenylene ether resin solution, followed by 30 maleic anhydride graft-modified polybutadiene. The olefin polymer Ricon156MA17 was used as a cross-linking agent, 25 g of maleimide resin was used as a co-cross-linking agent, 2.5 g of dicumyl peroxide was added as an initiator, and 35 g of the phosphorus-containing composition of Mixing Example 3 was used as a flame retardant. Vinyl silane-treated silicon dioxide SC-2300SVJ was used as a filler. The above mixture was mixed in toluene and stirred to dissolve to obtain a uniform resin composition, that is, a glue solution.
將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度為35μm之銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得到雙面覆銅之層壓板。 The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. A copper foil with a thickness of 35 μm was attached to both sides of the eight sheets of prepreg prepared above, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
比較例1 Comparative Example 1
將100g甲基丙烯酸酸甲酯基改性之聚苯醚SA9000與作為溶劑之甲苯混合，溶解完全得到端基官能化聚苯醚樹脂溶液，然後加入45g苯乙烯-丁二烯共聚物R100作為交聯劑，加入2g過氧化二異丙苯作為引發劑，54gDOPO衍生物XP-7866作為阻燃劑，0.8g環氧基矽烷偶聯劑及80g二氧化矽作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。 100 g of methyl methacrylate-modified polyphenylene ether SA9000 was mixed with toluene as a solvent, and the terminally functionalized polyphenylene ether resin solution was completely dissolved, and then 45 g of styrene-butadiene copolymer R100 was added as a solvent. Add 2 g of dicumyl peroxide as an initiator, 54 g of DOPO derivative XP-7866 as a flame retardant, 0.8 g of epoxy silane coupling agent and 80 g of silicon dioxide as a filler. Mix the above mixture in toluene , And stir to dissolve to obtain a uniform resin composition, that is, a glue solution.
將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度係35μm的銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得到雙面覆銅之層壓板。 The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. A copper foil with a thickness of 35 μm was attached to both sides of the eight sheets of prepreg prepared above, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
比較例2 Comparative Example 2
將100g甲基丙烯酸酸甲酯基改性之聚苯醚SA9000與作為溶劑之甲苯混合，溶解完全得到端基官能化聚苯醚樹脂溶液，接著加入45g苯乙烯-丁二烯共聚物R100作為交聯劑，加入2g過氧化二異丙苯作為引發劑，100g聚磷腈SPB-100作為阻燃劑，0.8g環氧基矽烷偶聯劑及80g二氧化矽作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。 100 g of methyl methacrylate-modified polyphenylene ether SA9000 was mixed with toluene as a solvent, and the terminally functionalized polyphenylene ether resin solution was completely dissolved, and then 45 g of styrene-butadiene copolymer R100 was added as a solvent. Adding agent, adding 2 g of dicumyl peroxide as an initiator, 100 g of polyphosphazene SPB-100 as a flame retardant, 0.8 g of epoxy silane coupling agent and 80 g of silicon dioxide as a filler, put the above mixture in toluene Mix and stir to dissolve to obtain a uniform resin composition, that is, a glue solution.
將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度係35μm之銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得到雙面覆銅之層壓板。 The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. A copper foil with a thickness of 35 μm was attached to both sides of the eight sheets of prepreg prepared above, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
比較例3 Comparative Example 3
將100g甲基丙烯酸酸甲酯基改性之聚苯醚SA9000與作為溶劑之甲苯混合，溶解完全得到端基官能化聚苯醚樹脂溶液，接著加入45g苯乙烯-丁二烯共聚物R100作為交聯劑，加入2g過氧化二異丙苯作為引發劑，45g乙基-雙(四溴苯鄰二甲醯亞胺)BT-93W，0.8g環氧基矽烷偶聯劑及80g二氧化矽作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。 100 g of methyl methacrylate-modified polyphenylene ether SA9000 was mixed with toluene as a solvent, and the terminally functionalized polyphenylene ether resin solution was completely dissolved, and then 45 g of styrene-butadiene copolymer R100 was added as a solvent. Adding agent, adding 2 g of dicumyl peroxide as an initiator, 45 g of ethyl-bis (tetrabromophthalimide) BT-93W, 0.8 g of epoxy silane coupling agent and 80 g of silicon dioxide as As a filler, the above mixture is mixed in toluene, and stirred to dissolve to obtain a uniform resin composition, that is, a glue solution.
將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度係35μm之銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得到雙面覆銅之層壓板。 The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. A copper foil with a thickness of 35 μm was attached to both sides of the eight sheets of prepreg prepared above, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
比較例4 Comparative Example 4
將100g甲基丙烯酸酸甲酯基改性之聚苯醚SA9000與作為溶劑之甲苯 100g混合，溶解完全得到端基官能化聚苯醚樹脂溶液，10g雙馬來醯亞胺樹脂作為共固化劑，再加入3.0g過氧化二異丙苯作為引發劑，25g混合例2之含磷組合物作為阻燃劑，2g乙烯基基矽烷偶聯劑及150g二氧化矽作為填料，將上述混合物在甲苯中混合，並攪拌溶解得到均一之樹脂組合物，即膠液。 100 g of methyl methacrylate-modified polyphenylene ether SA9000 and toluene as a solvent 100g mixed, dissolved completely to obtain a terminal functionalized polyphenylene ether resin solution, 10g of bismaleimide resin as a co-curing agent, and then added 3.0g of dicumyl peroxide as an initiator, and 25g of phosphorus contained in mixing example 2 The composition is used as a flame retardant, 2 g of a vinyl silane coupling agent, and 150 g of silicon dioxide as a filler. The above mixture is mixed in toluene and stirred to dissolve to obtain a uniform resin composition, that is, a glue solution.
將上述製備得到之膠液浸滲E-玻纖布，在155℃下加熱乾燥3~10min，將溶劑揮發完全，得到預浸料。在重疊以上製備得到之8張預浸料兩面各附上厚度係35μm之銅箔，在200℃之溫度及3.0MPa之壓力下熱壓90分鐘，得到雙面覆銅之層壓板。 The E-glass fiber cloth impregnated with the glue solution prepared above is heated and dried at 155 ° C for 3 to 10 minutes, and the solvent is completely evaporated to obtain a prepreg. A copper foil with a thickness of 35 μm was attached to both sides of the eight sheets of prepreg prepared above, and hot-pressed at a temperature of 200 ° C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
對實施例及比較例進行性能測試，結果如表1及表2所示：
從以上測試結果可得知，實施例1~7種採用之含磷阻燃劑組合物，可在較少之添加量下，達到良好之V-0阻燃劑級別，當其搭配官能化之聚苯醚樹脂、烯烴樹脂以及雙馬來醯亞胺樹脂組成之熱固性組合物固化後可得到具有優異耐熱性、介電性能同時又滿足UL 94V-0之阻燃要求。 It can be known from the above test results that the phosphorus-containing flame retardant compositions used in Examples 1 to 7 can reach a good V-0 flame retardant level with a relatively small amount of addition. After curing, the thermosetting composition composed of polyphenylene ether resin, olefin resin and bismaleimide resin can have excellent heat resistance and dielectric properties while meeting the flame retardance requirements of UL 94V-0.
對比例1中，單獨使用DOPO衍生物作為阻燃劑時，即使添加量增加，其阻燃效果亦不充分；而單獨使用聚磷腈化合物作為阻燃劑，即使添加量很大亦無法滿足UL 94V-0之阻燃要求，且由於增塑性帶來固化產物之玻璃化轉變溫度急劇下降，耐熱性極差；對比例4中，使用單一之雙馬來醯亞胺作為交聯劑時，固化產物之耐熱性及阻燃性較好，惟會導致介電性能之惡化；對比例3使用了含溴之阻燃劑，可達到良好之耐熱性及阻燃性能，惟無法滿足無鹵環保技術需求。 In Comparative Example 1, when a DOPO derivative was used alone as a flame retardant, even if the amount added was increased, the flame retardant effect was not sufficient; and when a polyphosphazene compound was used alone as a flame retardant, even if the amount was large, it could not satisfy the UL The flame retardant requirements of 94V-0, and the glass transition temperature of the cured product due to plasticization drastically decreased, and the heat resistance was extremely poor; in Comparative Example 4, when a single bismaleimide was used as the crosslinking agent, it was cured. The product has good heat resistance and flame retardancy, but will cause deterioration of dielectric properties. Comparative Example 3 uses a bromine-containing flame retardant, which can achieve good heat resistance and flame retardancy, but cannot meet halogen-free environmental protection technology. demand.
申請人聲明，本發明藉由上述實施例來說明本發明之詳細方法，但本發明並不侷限於上述詳細方法，即不代表本發明必須依賴上述詳細方法才能實施。所屬技術領域之技術人員應明瞭，對本發明之任何改良，對本發明產品各原料之等效替換及輔助成分之添加、具體方式之選擇等，均落於本發明之保護範圍及公開範圍內。 The applicant states that the present invention describes the detailed method of the present invention by using the foregoing embodiments, but the present invention is not limited to the detailed method, that is, it does not mean that the present invention must rely on the detailed method to be implemented. Those skilled in the art should know that any improvement to the present invention, equivalent replacement of each raw material of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.
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