TWI753194B - Resin composition, prepreg for printed circuit, and metal-clad laminate - Google Patents
Resin composition, prepreg for printed circuit, and metal-clad laminate Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
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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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
本發明提供樹脂組合物、印刷電路用預浸片及覆金屬層壓板。所述樹脂組合物包含：樹脂；和填料，其中所述樹脂是矽芳炔樹脂。通過使用樹脂組合物，製得的覆金屬層壓板可以至少具有低介電損耗因數、高耐熱性、低熱膨脹係數、無鹵無磷阻燃等特性中的一個。The present invention provides a resin composition, a prepreg for a printed circuit, and a metal-clad laminate. The resin composition comprises: a resin; and a filler, wherein the resin is a silicon aryne resin. By using the resin composition, the prepared metal-clad laminate can have at least one of low dielectric loss factor, high heat resistance, low thermal expansion coefficient, halogen-free and phosphorus-free flame retardancy and the like.
Description
本發明涉及印刷電路板技術領域。具體地，本發明涉及一種樹脂組合物、印刷電路用預浸片及覆金屬層壓板。The present invention relates to the technical field of printed circuit boards. Specifically, the present invention relates to a 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他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 kind of plate-like material made by dipping electronic glass fiber cloth or other reinforcing materials with resin solution, covering one or both sides with metal foil and hot pressing. It is called metal-clad laminate, abbreviated as It is metal clad laminate or metal clad laminate, such as copper clad laminate or copper clad laminate (Copper Clad Laminate, CCL). Metal clad laminates such as copper clad laminates are the base laminates for the manufacture of printed circuit boards (PCBs), which are one of the important components in the electronics industry. Almost every electronic device, ranging from electronic watches and calculators to computers, communication electronic equipment, and military weapon systems, as long as there are electronic components such as integrated circuits, for the electrical interconnection between them, printed boards are used. . The metal clad laminate is mainly responsible for the three functions of conduction, insulation and support on the entire printed circuit board.
隨著電子設備向小型化、多功能化、高性能化及高可靠性方面的迅速發展，要求印刷電路板朝著高精度、高密度、高性能、微孔化和薄型化方向的發展越來越快。而CCL在很大程度上決定了PCB的性能。With the rapid development of electronic equipment in terms of miniaturization, multi-function, high performance and high reliability, printed circuit boards are required to develop in the direction of high precision, high density, high performance, microvia and thinning. sooner. And CCL largely determines the performance of the PCB.
印刷電路板高精度、高密度、高性能、微孔化、薄型化和多層化的發展趨勢要求覆銅板具有更高的熱性能和力學性能。如電子產品中越來越多的應用到多層板，為保證多層電路板性能穩定可靠，這就需要層壓有具有低介電損耗因數、高耐熱性、低熱膨脹係數、無鹵無磷阻燃等特性。The development trend of printed circuit boards with high precision, high density, high performance, microporation, thinning and multi-layering requires copper clad laminates to have higher thermal and mechanical properties. For example, more and more electronic products are applied to multi-layer boards. In order to ensure the stable and reliable performance of multi-layer circuit boards, it is necessary to laminate with low dielectric loss factor, high heat resistance, low thermal expansion coefficient, halogen-free and phosphorus-free flame retardant, etc. characteristic.
本發明的一個目的在於提供一種樹脂組合物、通過用增強材料如玻璃纖維布（簡稱玻纖布）浸潤所述樹脂組合物得到的印刷電路用預浸片以及包含所述印刷電路用預浸片的覆金屬層壓板，使得覆金屬層壓板至少具有低介電損耗因數、高耐熱性、低熱膨脹係數、無鹵無磷阻燃等特性中的一個。An object of the present invention is to provide a resin composition, a prepreg for printed circuits obtained by impregnating the resin composition with a reinforcing material such as glass fiber cloth (glass cloth for short), and a prepreg for printed circuits comprising the same The metal-clad laminate has at least one of the characteristics of low dielectric loss factor, high heat resistance, low thermal expansion coefficient, halogen-free and phosphorus-free flame retardancy.
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片的絕緣板和包含所述印刷電路用預浸片、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低介電損耗因數、高耐熱性、低熱膨脹係數、無鹵無磷阻燃等特性中的一個。Another object of the present invention is to provide an insulating board including the printed circuit prepreg and a printed circuit board including the printed circuit prepreg, the insulating board, or the metal-clad laminate, wherein the The insulating board or metal-clad laminate has one of the characteristics of low dielectric loss factor, high heat resistance, low thermal expansion coefficient, halogen-free and phosphorus-free flame retardancy and the like.
因此，在一個方面，本發明提供一種樹脂組合物，所述樹脂組合物包含： 樹脂；和 填料， 其中所述樹脂是矽芳炔樹脂，並且所述矽芳炔樹脂與所述填料的重量比為（30～95）:（5～70）。Accordingly, in one aspect, the present invention provides a resin composition comprising: a resin; and a filler, wherein the resin is a silaryne resin, and the weight ratio of the silylene resin to the filler is It is (30～95):(5～70).
根據本發明的一個實施方案，所述矽芳炔樹脂由下式表示：
根據本發明的另一個實施方案，所述填料包括無機填料和有機填料。According to another embodiment of the present invention, the fillers include inorganic fillers and organic fillers.
根據本發明的另一個實施方案，所述無機填料選自：二氧化矽、勃姆石、氧化鋁、滑石、雲母、高嶺土、氫氧化鋁、氫氧化鎂、硼酸鋅、錫酸鋅、鉬酸鋅、氧化鋅、氧化鈦、氮化硼、碳酸鈣、硫酸鋇、鈦酸鋇、硼酸鋁、鈦酸鉀、E玻璃粉、S玻璃粉、D玻璃粉、NE玻璃粉、空心微粉或勃姆石中的任意一種或者至少兩種的混合物。According to another embodiment of the present invention, the inorganic filler is selected from the group consisting of: silica, boehmite, alumina, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, molybdic acid Zinc, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, barium titanate, aluminum borate, potassium titanate, E glass powder, S glass powder, D glass powder, NE glass powder, hollow micropowder or boehm Any one of the stones or a mixture of at least two of them.
根據本發明的另一個實施方案，所述有機填料選自：聚四氟乙烯粉末、聚醯亞胺粉末、聚醚碸粉末或橡膠微粒中的任意一種或至少兩種的組合。According to another embodiment of the present invention, the organic filler is selected from any one or a combination of at least two of polytetrafluoroethylene powder, polyimide powder, polyether dust powder or rubber particles.
根據本發明的另一個實施方案，所述填料的平均粒徑在0.005 μm至20 μm的範圍內。優選地，所述填料的平均粒徑在0.01 μm的至10 μm的範圍內。According to another embodiment of the present invention, the average particle size of the filler is in the range of 0.005 μm to 20 μm. Preferably, the average particle size of the filler is in the range of 0.01 μm to 10 μm.
根據本發明的另一個實施方案，所述樹脂組合物還包含促進劑，其中所述促進劑與所述矽芳炔樹脂的重量比為（0.01～5）：100。According to another embodiment of the present invention, the resin composition further comprises an accelerator, wherein the weight ratio of the accelerator to the silyl aryne resin is (0.01-5):100.
根據本發明的另一個實施方案，所述促進劑選自：過氧化物、乙醯丙酮的金屬鹽、環烷酸的金屬鹽、五氧化釩、胺、季銨鹽、咪唑、三苯基膦或其任何兩種或更多種的混合物。According to another embodiment of the present invention, the accelerator is selected from the group consisting of peroxides, metal salts of acetylacetone, metal salts of naphthenic acids, vanadium pentoxide, amines, quaternary ammonium salts, imidazole, triphenylphosphine or a mixture of any two or more thereof.
根據本發明的另一個實施方案，所述樹脂組合物還包含分散劑、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、潤滑劑或其任何兩種或更多種的混合物。According to another embodiment of the present invention, the resin composition further comprises a dispersant, an antifoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant or any two thereof a mixture of one or more.
根據本發明的另一個實施方案，所述樹脂組合物還包含溶劑。According to another embodiment of the present invention, the resin composition further comprises a solvent.
優選地，所述溶劑選自甲苯、二甲苯、環己烷、四氫呋喃、丁酮或其任何兩種或更多種的混合物。Preferably, the solvent is selected from toluene, xylene, cyclohexane, tetrahydrofuran, butanone, or a mixture of any two or more thereof.
在另一個方面，本發明提供一種印刷電路用預浸片，所述印刷電路用預浸片包括增強材料及通過浸潤乾燥後附著在其上的如上面中任何一項所述的樹脂組合物。In another aspect, the present invention provides a prepreg for a printed circuit, the prepreg for a printed circuit comprising a reinforcing material and the resin composition as described in any one of the above adhered thereon after drying by infiltration.
在再一個方面，本發明提供一種絕緣板，所述絕緣板含有至少一張如上面所述的印刷電路用預浸片。In yet another aspect, the present invention provides an insulating board containing at least one prepreg for a printed circuit as described above.
在又一個方面，本發明提供一種覆金屬層壓板，所述覆金屬層壓板包括至少一張如上面所述的印刷電路用預浸片和金屬箔。In yet another aspect, the present invention provides a metal-clad laminate, the metal-clad laminate comprising at least one prepreg for a printed circuit as described above and a metal foil.
在再一個方面，本發明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片，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 provides a printed circuit board, the printed circuit board comprising: at least one prepreg for printed circuit as described above, or at least one insulating board as described above, or at least one Sheet metal clad laminates as described above.
根據本發明，可以提供一種樹脂組合物、通過用增強材料浸潤所述樹脂組合物得到的印刷電路用預浸片及包含所述印刷電路用預浸片的覆金屬層壓板或絕緣板，以及包含所述印刷電路用預浸片、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低介電損耗因數、高耐熱性、低熱膨脹係數、無鹵無磷阻燃等特性中的一個。According to the present invention, there can be provided a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a reinforcing material, and a metal-clad laminate or an insulating board comprising the prepreg for a printed circuit, and a The prepreg for printed circuit, the insulating board or the printed circuit board of the metal-clad laminate can at least have low dielectric loss factor, high heat resistance, low thermal expansion coefficient, halogen-free and no One of the characteristics of phosphorus flame retardant.
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，本領域具有通常知識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 technical solutions in the examples of the present invention will be clearly and completely described below 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 in the present invention, all other embodiments and/or all other examples obtained by persons with ordinary knowledge in the art without creative efforts shall fall within the protection scope of the present invention.
在下面的描述中，層和膜可以互換地使用。樹脂組合物在下文中有時也稱作膠黏劑。In the description below, layers and films are used interchangeably. The resin composition is also sometimes referred to as an adhesive hereinafter.
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 characteristics are meant to be within the error range of measurement, eg, within ±10%, or within ±5%, or within ±1% of the stated numerical 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片不同的特性。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”。In the present invention, "comprising", "including" or "containing" means that it may have other components in addition to the above-mentioned components, and these other components impart different properties to the prepreg. In addition, "comprising", "including" or "containing" described in the present invention may also include "consisting essentially of", and may be replaced by "is" 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, the amounts, ratios, etc. are by weight unless otherwise specified.
對於本發明而言，術語“無鹵無磷阻燃”表示本發明的組合物不含有有意添加的含鹵素阻燃劑或含磷阻燃劑。For the purposes of the present invention, the term "halogen-free and phosphorus-free flame retardant" means that the compositions of the present invention do not contain intentionally added halogen-containing flame retardants or phosphorus-containing flame retardants.
在本發明的組合物中，優選鹵素元素的含量不超過1重量%，更優選不超過0.1重量%，再更優選不超過0.01重量%，並且進一步優選不超過0.001重量%，或者為0。In the composition of the present invention, the content of the halogen element is preferably not more than 1% by weight, more preferably not more than 0.1% by weight, still more preferably not more than 0.01% by weight, and further preferably not more than 0.001% by weight, or 0.
在本發明的組合物中，優選磷元素的含量不超過1重量%，更優選不超過0.1重量%，再更優選不超過0.01重量%，並且進一步優選不超過0.001重量%，或者為0。In the composition of the present invention, the content of phosphorus element is preferably not more than 1% by weight, more preferably not more than 0.1% by weight, still more preferably not more than 0.01% by weight, and still more preferably not more than 0.001% by weight, or 0.
在本發明中，包含溶劑的樹脂組合物也可以稱為樹脂膠液。In the present invention, the resin composition containing the solvent may also be referred to as a resin glue.
如上所述，本發明可以提供一種樹脂組合物，所述樹脂組合物包含： 樹脂；和 填料， 其中所述樹脂是矽芳炔樹脂，並且所述矽芳炔樹脂與所述填料的重量比為（30～95）：（5～70）。As described above, the present invention can provide a resin composition comprising: a resin; and a filler, wherein the resin is a silyl aryne resin, and the weight ratio of the silyl aryne resin to the filler is (30-95): (5-70).
矽芳炔樹脂Silicon Arylene Resin
矽芳炔樹脂可以是分子主鏈含有矽元素、苯環和炔烴結構的樹脂。Silicon aryl acetylene resins can be resins whose molecular backbone contains silicon elements, benzene rings and alkyne structures.
矽芳炔樹脂可以由下式表示：
優選地，矽芳炔樹脂可以由下式表示
在上述式中，在苯環上的兩個炔基可以處於鄰位、間位或對位。矽芳炔樹脂可以二乙炔基苯與二氯矽烷聚合得到。例如，可以通過二乙炔基苯與二氯矽烷通過格氏反應聚合得到。In the above formula, the two alkynyl groups on the benzene ring may be in ortho, meta or para positions. Silicon aryl alkyne resins can be obtained by the polymerization of diethynyl benzene and dichlorosilane. For example, it can be obtained by polymerizing diethynylbenzene and dichlorosilane by Grignard reaction.
二乙炔基苯的實例可以包括1,2-二乙炔基苯、1,3-二乙炔基苯和1,4-二乙炔基苯。Examples of diethynylbenzene may include 1,2-diethynylbenzene, 1,3-diethynylbenzene, and 1,4-diethynylbenzene.
二氯矽烷的實例可以包括R’R”SiCl2 ，或R1 R2 SiCl2 ，其中R’、R”、R1 和R2 各自獨立地是選自由以下各項組成的組中的基團：氫、C1-6 烷基或C3-6 環烷基。Examples of dichlorosilanes may include R'R"SiCl 2 , or R 1 R 2 SiCl 2 , wherein R', R", R 1 and R 2 are each independently a group selected from the group consisting of : hydrogen, C 1-6 alkyl or C 3-6 cycloalkyl.
二氯矽烷的具體實例可以包括甲基二氯矽烷和二氯二甲基矽烷。Specific examples of the dichlorosilane may include methyldichlorosilane and dichlorodimethylsilane.
C1-6 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、叔丁基、各種戊基和各種己基。C3-6 環烷基的實例可以包括環丙基、環丁基、環戊基和環己基。Examples of C1-6 alkyl groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, various pentyl groups, and various hexyl groups. Examples of C 3-6 cycloalkyl groups may include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
矽芳炔樹脂的數均分子量可以為約250至10000，優選500至2000。低分子量的矽芳炔樹脂在溶劑中更易溶解。但是，過低分子量的矽芳炔樹脂的反應時間太久，不利於樹脂體系的固化加工。The number average molecular weight of the silyl aryne resin may be about 250 to 10,000, preferably 500 to 2,000. Low molecular weight siloxane resins are more soluble in solvents. However, the reaction time of too low molecular weight silicon aryne resin is too long, which is not conducive to the curing process of the resin system.
填料filler
填料可以包括無機填料和有機填料。Fillers may include inorganic fillers and organic fillers.
無機填料可以選自：二氧化矽、勃姆石、氧化鋁、滑石、雲母、高嶺土、氫氧化鋁、氫氧化鎂、硼酸鋅、錫酸鋅、鉬酸鋅、氧化鋅、氧化鈦、氮化硼、碳酸鈣、硫酸鋇、鈦酸鋇、硼酸鋁、鈦酸鉀、E玻璃粉、S玻璃粉、D玻璃粉、NE玻璃粉、空心微粉或勃姆石中的任意一種或者至少兩種的混合物。The inorganic filler may be selected from: silica, boehmite, alumina, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc molybdate, zinc oxide, titanium oxide, nitride Any one or at least two of boron, calcium carbonate, barium sulfate, barium titanate, aluminum borate, potassium titanate, E glass powder, S glass powder, D glass powder, NE glass powder, hollow micropowder or boehmite mixture.
有機填料可以選自：聚四氟乙烯粉末、聚醯亞胺粉末、聚醚碸粉末或橡膠微粒中的任意一種或至少兩種的組合。The organic filler can be selected from: any one or a combination of at least two of polytetrafluoroethylene powder, polyimide powder, polyether dust powder or rubber particles.
填料的平均粒徑在0.005 μm至20 μm的範圍內。優選地，填料的平均粒徑在0.01 μm至10 μm的範圍內。The average particle size of the filler is in the range of 0.005 μm to 20 μm. Preferably, the average particle size of the filler is in the range of 0.01 μm to 10 μm.
矽芳炔樹脂與填料的重量比可以為約（30～95）：（5～70），優選約（30～90）：（10～70），進一步優選約（30～85）：（15～70）。The weight ratio of the silicon aryne resin to the filler can be about (30-95): (5-70), preferably about (30-90): (10-70), more preferably about (30-85): (15- 70).
促進劑accelerator
任選地，樹脂組合物還包含促進劑。促進劑用於促進矽芳炔樹脂的固化反應。Optionally, the resin composition further includes an accelerator. Accelerators are used to promote the curing reaction of silicon aryne resins.
促進劑可以選自：過氧化物、乙醯丙酮的金屬鹽、環烷酸的金屬鹽、五氧化釩、胺、季銨鹽、咪唑、三苯基膦或其任何兩種或更多種的混合物。The accelerator may be selected from the group consisting of peroxides, metal salts of acetylacetone, metal salts of naphthenic acids, vanadium pentoxide, amines, quaternary ammonium salts, imidazoles, triphenylphosphine or any two or more thereof. mixture.
優選地，在需要控制組合物的磷含量的情況下，促進劑可以選自：過氧化物、乙醯丙酮的金屬鹽、環烷酸的金屬鹽、五氧化釩、胺、季銨鹽、咪唑或其任何兩種或更多種的混合物，以得到無磷的樹脂組合物。Preferably, where it is desired to control the phosphorus content of the composition, the accelerator may be selected from the group consisting of peroxides, metal salts of acetylacetone, metal salts of naphthenic acids, vanadium pentoxide, amines, quaternary ammonium salts, imidazoles or a mixture of any two or more thereof to obtain a phosphorus-free resin composition.
過氧化物的實例可以包括：過氧化二枯基、叔丁基過氧化枯基、過氧化二叔丁基、過氧化異丙基碳酸叔丁酯、2,5-二甲基-2,5-二叔丁基枯基過氧基己炔-3、2,5-二甲基2,5-二叔丁基過氧化己烷、過氧化對孟烷、1,1-雙（叔戊基過氧）環己烷、過氧化氫二異丙基苯、過氧化苯甲醯或過氧化苯甲醯衍生物。胺的實例可以包括苯胺。Examples of peroxides may include: dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5 -Di-tert-butylcumylperoxyhexyn-3, 2,5-dimethyl 2,5-di-tert-butylperoxyhexane, p-menan peroxide, 1,1-bis(tert-amyl Peroxy) cyclohexane, dicumyl hydroperoxide, benzyl peroxide or benzyl peroxide derivatives. Examples of amines may include aniline.
乙醯丙酮的金屬鹽和環烷酸的金屬鹽中的金屬可以獨立為鹼金屬、鹼土金屬或過渡金屬。例如，鉀、鈣、鈉、鎂、鋁、鋅、鐵、鈷等。The metals in the metal salts of acetylacetone and naphthenic acids may independently be alkali metals, alkaline earth metals or transition metals. For example, potassium, calcium, sodium, magnesium, aluminum, zinc, iron, cobalt, and the like.
促進劑與矽芳炔樹脂的重量比可以為約（0.01～5）：100，優選為約（0.05～2.5）：100。以矽芳炔樹脂為100質量份計，促進劑的用量為約0.01～5質量份，例如0.05質量份、0.08質量份、0.15質量份、0.25質量份、0.35質量份、0.45質量份、0.55質量份、0.65質量份、0.75質量份、0.85質量份、0.95質量份，1.0質量份、1.2質量份、1.5質量份、2.0質量份、2.5質量份、3.0質量份、3.5質量份、4.0質量份、或4.5質量份，或它們任何兩個值之間的範圍或數值，優選約0.05～2.5質量份。The weight ratio of accelerator to silicon aryne resin may be about (0.01-5):100, preferably about (0.05-2.5):100. Based on 100 parts by mass of the silicon aryne resin, the amount of the accelerator used is about 0.01 to 5 parts by mass, such as 0.05 parts by mass, 0.08 parts by mass, 0.15 parts by mass, 0.25 parts by mass, 0.35 parts by mass, 0.45 parts by mass, 0.55 parts by mass parts, 0.65 parts by mass, 0.75 parts by mass, 0.85 parts by mass, 0.95 parts by mass, 1.0 parts by mass, 1.2 parts by mass, 1.5 parts by mass, 2.0 parts by mass, 2.5 parts by mass, 3.0 parts by mass, 3.5 parts by mass, 4.0 parts by mass, or 4.5 parts by mass, or a range or numerical value between any two of them, preferably about 0.05 to 2.5 parts by mass.
為了更好地將填料分散在樹脂組合物中，本發明的樹脂組合物中還可以加入偶聯劑。偶聯劑可以防止填料團聚，改善樹脂和填料之間的結合力，減小添加填料而導致的缺陷，減小吸水率，而且偶聯劑還可以改善樹脂組合物的表面張力，進一步提高樹脂組合物的流動性，增強浸潤效果。偶聯劑可以為矽烷偶聯劑，優選環氧基矽烷偶聯劑、氨基矽烷偶聯劑、苯胺基矽烷偶聯劑、乙烯基矽烷聯劑、異氨酸酯基矽烷偶聯劑、丙烯基矽烷偶聯劑、異丁烯矽烷偶聯劑、苯乙烯矽烷偶聯劑、陰離子矽烷偶聯劑或脲基矽烷偶聯劑等中的任意一種或者至少兩種的混合物。作為具體例，可列舉出，γ-氨丙基三乙氧基矽烷、N-β-(氨乙基)-γ-氨丙基三甲氧基矽烷等氨基矽烷偶聯劑、γ-縮水甘油醚氧丙基三甲氧基矽烷等環氧基矽烷偶聯劑、γ-甲基丙烯醯氧丙基三甲氧基矽烷等乙烯基矽烷偶聯劑、N-β-(N-乙烯基苯偶醯基氨乙基)-γ-氨丙基三甲氧基矽烷鹽酸鹽等陰離子矽烷偶聯劑。In order to better disperse the filler in the resin composition, a coupling agent may also be added to the resin composition of the present invention. Coupling agent can prevent filler agglomeration, improve the bonding force between resin and filler, reduce defects caused by adding filler, reduce water absorption, and coupling agent can also improve the surface tension of resin composition, further improve resin composition The fluidity of the material increases the wetting effect. The coupling agent can be a silane coupling agent, preferably epoxy silane coupling agent, amino silane coupling agent, anilino silane coupling agent, vinyl silane coupling agent, isoamidate silane coupling agent, acryl Any one of silane coupling agent, isobutylene silane coupling agent, styrene silane coupling agent, anionic silane coupling agent or ureido silane coupling agent, etc., or a mixture of at least two of them. Specific examples include aminosilane coupling agents such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-glycidyl ether. Epoxy silane coupling agents such as oxypropyltrimethoxysilane, vinyl silane coupling agents such as γ-methacryloyloxypropyltrimethoxysilane, N-β-(N-vinylbenzyl Anionic silane coupling agents such as aminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride.
偶聯劑的用量並無特別地限定，優選地，以樹脂組合物總重為100質量份計，偶聯劑的用量為約0～5質量份，更優選約0.005～4質量份，進一步優選約0.05～3質量份。偶聯劑的用量例如為0.5質量份、1質量份、1.5質量份、2質量份、2.5質量份、3質量份、3.5質量份、4質量份或4.5質量份，或它們任何兩個值之間的範圍或數值。The amount of the coupling agent is not particularly limited, preferably, based on the total weight of the resin composition as 100 parts by mass, the amount of the coupling agent is about 0 to 5 parts by mass, more preferably about 0.005 to 4 parts by mass, even more preferably About 0.05 to 3 parts by mass. The amount of coupling agent used is, for example, 0.5 parts by mass, 1 part by mass, 1.5 parts by mass, 2 parts by mass, 2.5 parts by mass, 3 parts by mass, 3.5 parts by mass, 4 parts by mass, or 4.5 parts by mass, or any two of them. range or value between.
另外，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兩種混合使用。In addition, the resin composition may further contain various auxiliary agents. Specific examples of auxiliary agents include filler dispersants, antifoaming agents, antioxidants, thermal stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and the like. These adjuvants may be used alone or in combination of any two or more.
本發明的樹脂組合物可以通過公知的方法如配合、攪拌、混合矽芳炔樹脂、填料、以及任選的促進劑、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、潤滑劑或其任何兩種或更多種的混合物來製備。The resin composition of the present invention can be prepared by known methods such as compounding, stirring, and mixing the silaryl alkyne resin, filler, and optional accelerator, dispersant, defoamer, antioxidant, heat stabilizer, antistatic agent, UV absorbers, pigments, colorants, lubricants, or a mixture of any two or more thereof.
根據本發明的樹脂組合物還可以包含溶劑。The resin composition according to the present invention may further contain a solvent.
作為本發明中的溶劑，沒有特別限定。作為具體例，可以舉出甲苯、二甲苯、環己烷、四氫呋喃、丁酮或其任何兩種或更多種的混合物。上述溶劑可以單獨使用一種，也可以兩種或者兩種以上混合使用。溶劑的使用量本領域技術人員可以根據自己的經驗來選擇，使得到的樹脂膠液達到適於使用的黏度即可。It does not specifically limit as a solvent in this invention. Specific examples include toluene, xylene, cyclohexane, tetrahydrofuran, butanone, or a mixture of any two or more thereof. One of the above-mentioned solvents may be used alone, or two or more of them may be used in combination. The amount of solvent used can be selected by those skilled in the art according to their own experience, so that the obtained resin glue can reach a viscosity suitable for use.
根據本發明的樹脂組合物可以是無鹵樹脂組合物或無鹵無磷樹脂組合物。The resin composition according to the present invention may be a halogen-free resin composition or a halogen-free and phosphorus-free resin composition.
在本發明的樹脂組合物中包含的樹脂是矽芳炔樹脂，是指本發明的樹脂組合物除了含有矽芳炔樹脂之外，不含有其他樹脂。但是，如上所述，本發明的樹脂組合物可以含有除樹脂和填料之外的其他組分。The resin contained in the resin composition of the present invention is a silyl aryne resin, which means that the resin composition of the present invention does not contain other resins except the silyl aryne resin. However, as described above, the resin composition of the present invention may contain other components than the resin and filler.
增強材料Reinforcing material
所述增強材料可以為無機或有機材料。The reinforcing material may be an inorganic or organic material.
無機增強材料的實例可以包括玻璃纖維、碳纖維、硼纖維、金屬等的機織織物或無紡布或紙。玻璃纖維布或無紡布的實例可以包括E-glass、Q型布、NE布、D型布、S型布、高矽氧布等。有機增強材料的實例可以包括有機纖維如聚酯、聚胺、聚丙烯酸、聚醯亞胺、芳綸、聚四氟乙烯、間規聚苯乙烯等製造的織布或無紡布或紙。然而增強材料不限於此，其他的可用於樹脂增強的增強材料同樣可以在本發明中使用。優選地，增強材料為玻纖布。Examples of inorganic reinforcing materials may include woven or non-woven fabrics or paper of glass fibers, carbon fibers, boron fibers, metals, and the like. Examples of the glass fiber cloth or non-woven fabric may include E-glass, Q-type cloth, NE cloth, D-type cloth, S-type cloth, high silica cloth, and the like. Examples of the organic reinforcing material may include woven or non-woven fabrics or paper made of organic fibers such as polyester, polyamine, polyacrylic acid, polyimide, aramid, polytetrafluoroethylene, syndiotactic polystyrene, and the like. However, the reinforcing material is not limited to this, and other reinforcing materials that can be used for resin reinforcement can also be used in the present invention. Preferably, the reinforcing material is glass fiber cloth.
通過機械攪拌、乳化或球磨分散，將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如玻璃纖維布，經烘乾得預浸片。將該預浸片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 resin composition is prepared into a resin glue solution, and then a reinforcing material such as glass fiber cloth is infiltrated with the resin glue solution, and a prepreg sheet is obtained by drying. A metal clad laminate can be prepared by hot pressing the prepreg and metal foil such as copper foil or aluminum foil in a vacuum press.
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50～90℃，進一步優選約55～85℃。In order to reduce the viscosity of the resin glue, it can be soaked under heating. Heating is performed so that the temperature of the resin glue solution is lower than the boiling point of the solvent used, and the temperature of the resin glue solution during infiltration is preferably about 50-90°C, more preferably about 55-85°C.
在另一方面，本發明還可以提供一種印刷電路用預浸片，所述印刷電路用預浸片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 comprising a reinforcing material and the resin composition according to any one of the above adhered thereon after being soaked and dried .
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片。In yet another aspect, the present invention can also provide an insulating board or a metal-clad laminate comprising at least one prepreg for a printed circuit as described above.
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片，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 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，可以提供一種樹脂組合物、通過用增強材料浸潤所述樹脂組合物得到的印刷電路用預浸片及包含所述印刷電路用預浸片的覆金屬層壓板或絕緣板，以及包含所述印刷電路用預浸片、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低介電損耗因數、高耐熱性、低熱膨脹係數、無鹵無磷阻燃等特性中的一個。According to the present invention, there can be provided a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a reinforcing material, and a metal-clad laminate or an insulating board comprising the prepreg for a printed circuit, and a The prepreg for printed circuit, the insulating board or the printed circuit board of the metal-clad laminate can at least have low dielectric loss factor, high heat resistance, low thermal expansion coefficient, halogen-free and no One of the characteristics of phosphorus flame retardant.
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 are further described below through specific embodiments. However, these examples are intended to illustrate the present invention and should not be construed to limit the present invention.
實施例中所用的材料如下：The materials used in the examples are as follows:
矽芳炔樹脂：製備過程如下。Silicon aryne resin: The preparation process is as follows.
在充滿氮氣的反應釜中加入3.5份鎂粉（化學純，上海國藥集團化學試劑有限公司），和40份四氫呋喃（THF）溶劑，在室溫下攪拌並滴加13.5份溴乙烷（化學純，上海國藥集團化學試劑有限公司）和40份THF的混合溶液，滴加完成後於50℃保溫1h。然後在冰水冷浴條件下，滴加7.5份1,3-二乙炔基苯（山東膠州市精細化工有限公司）和40份THF溶劑的混合物，滴加完畢後，於65℃保溫1h。然後再次冷卻，在冰水冷浴條件下滴加5.5份二氯二甲基矽烷（化學純，浙江新安化工集團有限公司，蒸餾後使用）和40 mL THF的混合物，滴加完畢後分別於40℃和70℃保溫1h。反應完成後，蒸除反應物中的THF，並與冰水冷浴條件下滴加7.2份冰醋酸和50份甲苯溶劑的混合物，充分攪拌後再滴加140份2.0%稀鹽酸水溶液，充分攪拌後分離出上層有機相。將有機相充分水洗至中性，然後乾燥，過濾，並蒸除甲苯，得到矽苯炔樹脂（即，實施例和比較例中所用的矽芳炔樹脂）。Add 3.5 parts of magnesium powder (chemically pure, Shanghai Sinopharm Chemical Reagent Co., Ltd.), and 40 parts of tetrahydrofuran (THF) solvent to a nitrogen-filled reactor, stir at room temperature and add 13.5 parts of bromoethane (chemically pure) , Shanghai Sinopharm Group Chemical Reagent Co., Ltd.) and a mixed solution of 40 parts of THF, and kept at 50 °C for 1 h after the dropwise addition. Then, under the condition of ice-water cooling bath, a mixture of 7.5 parts of 1,3-diethynylbenzene (Shandong Jiaozhou Fine Chemical Co., Ltd.) and 40 parts of THF solvent was added dropwise. Then it was cooled again, and a mixture of 5.5 parts of dichlorodimethylsilane (chemically pure, Zhejiang Xin'an Chemical Group Co., Ltd., used after distillation) and 40 mL of THF was added dropwise in an ice-water cooling bath. Incubate at 70°C for 1h. After the reaction was completed, the THF in the reactant was distilled off, and the mixture of 7.2 parts of glacial acetic acid and 50 parts of toluene solvent was added dropwise under the condition of ice-water cooling bath, and then 140 parts of 2.0% dilute hydrochloric acid aqueous solution was added dropwise after full stirring. The upper organic phase was separated. The organic phase was thoroughly washed with water until neutral, then dried, filtered, and toluene was distilled off to obtain a silyl acetylene resin (ie, the silyl aryl acetylene resin used in the Examples and Comparative Examples).
玻纖布：型號為2116的E型玻纖布，日東紡Glass fiber cloth: E-type glass fiber cloth model 2116, Nittobo
銅箔：35 μm （1Oz）RTF銅箔，蘇州福田金屬有限公司Copper foil: 35 μm (1Oz) RTF copper foil, Suzhou Futian Metal Co., Ltd.
D50：表示平均粒徑，是指將粒子的總體積作為100%而求出基於粒徑的累積度數分布曲線時，剛好相當於體積為50%的點的粒徑，其使用雷射衍射散射法的粒度分布測定。D50: Indicates the average particle size, which is the particle size at the point where the volume is 50% when the cumulative power distribution curve based on the particle size is obtained by taking the total volume of the particles as 100%, using the laser diffraction scattering method particle size distribution determination.
實施例1Example 1
將100份矽芳炔樹脂（數均分子量1200）在230份甲苯中充分溶解，然後加入230份熔融二氧化矽（D50=3.0 μm，江蘇聯瑞新材料股份有限公司），混合均勻，得到樹脂膠液。取平整光潔，型號為2116的E型玻璃纖維布均勻浸漬上述膠液，在鼓風烘箱中於170℃烘烤5min製得預浸片，將6張上述預浸片重疊，上下覆35 mm銅箔，於真空熱壓機中在3MPa壓力和220℃溫度下壓製90min得到覆銅層壓板。Fully dissolve 100 parts of silicon aryl acetylene resin (number average molecular weight 1200) in 230 parts of toluene, then add 230 parts of fused silica (D50=3.0 μm, Jiangsu Lianrui New Materials Co., Ltd.), and mix evenly to obtain resin glue. Take a flat and clean E-type glass fiber cloth with a model of 2116 and evenly impregnate the above glue solution, bake it in a blast oven at 170 ° C for 5 minutes to obtain a prepreg sheet, overlap 6 of the above prepreg sheets, and cover the top and bottom with 35 mm copper The foil was pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 min to obtain a copper clad laminate.
實施例2Example 2
將200份矽芳炔樹脂（數均分子量1200）在400份甲苯中充分溶解，然後加入15份鈦酸鋇（BT-300，D50約0.5 μm，山東國瓷功能材料股份有限公司）和2份氣相二氧化矽（AEROSIL 300，粒徑小於100 nm，美國贏創德固賽），混合均勻，得到樹脂膠液。取平整光潔，型號為2116的E型玻璃纖維布均勻浸漬上述膠液，在鼓風烘箱中於170℃烘烤5min製得預浸片，將6張上述預浸片重疊，上下覆35 mm銅箔，於真空熱壓機中在3MPa壓力和220℃溫度下壓製90min得到覆銅層壓板。Dissolve 200 parts of silicon aryne resin (number average molecular weight 1200) in 400 parts of toluene, then add 15 parts of barium titanate (BT-300, D50 about 0.5 μm, Shandong Guoci Functional Materials Co., Ltd.) and 2 parts Fumed silica (AEROSIL 300, particle size less than 100 nm, Evonik Degussa, USA), mixed uniformly to obtain resin glue. Take a flat and clean E-type glass fiber cloth with a model of 2116 and evenly impregnate the above glue solution, bake it in a blast oven at 170 ° C for 5 minutes to obtain a prepreg sheet, overlap 6 of the above prepreg sheets, and cover the top and bottom with 35 mm copper The foil was pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 min to obtain a copper clad laminate.
實施例3Example 3
將100份矽芳炔樹脂（數均分子量1200）在230份甲苯中充分溶解，然後加入230份熔融二氧化矽（D50=3.0 μm，江蘇聯瑞新材料股份有限公司）混合均勻，然後加入0.5份乙醯丙酮鈷和0.7份三苯基膦的乙醇溶液，混合均勻，得到樹脂膠液。取平整光潔，型號為2116的E型玻璃纖維布均勻浸漬上述膠液，在鼓風烘箱中於170℃烘烤5min製得預浸片，將6張上述預浸片重疊，上下覆35 mm銅箔，於真空熱壓機中在3MPa壓力和200℃溫度下壓製90min得到覆銅層壓板。Fully dissolve 100 parts of silicon aryl alkyne resin (number average molecular weight 1200) in 230 parts of toluene, then add 230 parts of fused silica (D50=3.0 μm, Jiangsu Lianrui New Materials Co., Ltd.) and mix evenly, then add 0.5 Parts of cobalt acetylacetonate and 0.7 parts of triphenylphosphine in ethanol are mixed uniformly to obtain resin glue. Take a flat and clean E-type glass fiber cloth with a model of 2116 and evenly impregnate the above glue solution, bake it in a blast oven at 170 ° C for 5 minutes to obtain a prepreg sheet, overlap 6 of the above prepreg sheets, and cover the top and bottom with 35 mm copper The foil was pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 200° C. for 90 min to obtain a copper clad laminate.
實施例4Example 4
將100份矽芳炔樹脂（數均分子量1200）和2份矽烷偶聯劑（KBM-1003，信越化學工業株式會社）在230份甲苯中充分溶解，然後加入230份熔融二氧化矽（D50=3.0 μm，江蘇聯瑞新材料股份有限公司）混合均勻，然後加入0.5份乙醯丙酮鈷和0.7份三苯基膦的乙醇溶液，混合均勻，得到樹脂膠液。取平整光潔，型號為2116的E型玻璃纖維布均勻浸漬上述膠液，在鼓風烘箱中於170℃烘烤5min製得預浸片，將6張上述預浸片重疊，上下覆35 mm銅箔，於真空熱壓機中在3MPa壓力和220℃溫度下壓製90min得到覆銅層壓板。100 parts of silyl aryne resin (number average molecular weight 1200) and 2 parts of silane coupling agent (KBM-1003, Shin-Etsu Chemical Co., Ltd.) were fully dissolved in 230 parts of toluene, and then 230 parts of fused silica (D50= 3.0 μm, Jiangsu Lianrui New Materials Co., Ltd.) and mix evenly, then add 0.5 parts of cobalt acetylacetonate and 0.7 parts of triphenylphosphine in ethanol, and mix well to obtain a resin glue. Take a flat and clean E-type glass fiber cloth with a model of 2116 and evenly impregnate the above glue solution, bake it in a blast oven at 170 ° C for 5 minutes to obtain a prepreg sheet, overlap 6 of the above prepreg sheets, and cover the top and bottom with 35 mm copper The foil was pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 min to obtain a copper clad laminate.
實施例5Example 5
將100份矽芳炔樹脂（數均分子量1200）在200份甲苯中充分溶解，然後加入100份聚四氟乙烯粉（M-112，D50=20 μm，日本大金工業株式會社），混合均勻，得到樹脂膠液。取平整光潔，型號為2116的E型玻璃纖維布均勻浸漬上述膠液，在鼓風烘箱中於170℃烘烤5min製得預浸片，將6張上述預浸片重疊，上下覆35 mm銅箔，於真空熱壓機中在3MPa壓力和220℃溫度下壓製90min得到覆銅層壓板。Fully dissolve 100 parts of silicene resin (number average molecular weight 1200) in 200 parts of toluene, then add 100 parts of polytetrafluoroethylene powder (M-112, D50=20 μm, Japan Daikin Industry Co., Ltd.), mix well , to obtain resin glue. Take a flat and clean E-type glass fiber cloth with a model of 2116 and evenly impregnate the above glue solution, bake it in a blast oven at 170 ° C for 5 minutes to obtain a prepreg sheet, overlap 6 of the above prepreg sheets, and cover the top and bottom with 35 mm copper The foil was pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 min to obtain a copper clad laminate.
實施例6Example 6
將100份矽芳炔樹脂（數均分子量1200）和2份矽烷偶聯劑（KBM-1003，信越化學工業株式會社）在200份甲苯中充分溶解，然後加入100份聚四氟乙烯粉（M-112，D50=20 μm，日本大金工業株式會社）混合均勻，然後加入0.5份乙醯丙酮鈷和0.7份三苯基膦的乙醇溶液，混合均勻，得到樹脂膠液。取平整光潔，型號為2116的E型玻璃纖維布均勻浸漬上述膠液，在鼓風烘箱中於170℃烘烤5min製得預浸片，將6張上述預浸片重疊，上下覆35 mm銅箔，於真空熱壓機中在3MPa壓力和220℃溫度下壓製90min得到覆銅層壓板。100 parts of silyl aryne resin (number average molecular weight 1200) and 2 parts of silane coupling agent (KBM-1003, Shin-Etsu Chemical Co., Ltd.) were fully dissolved in 200 parts of toluene, and then 100 parts of polytetrafluoroethylene powder (M -112, D50=20 μm, Japan Daikin Industry Co., Ltd.) and mix evenly, then add 0.5 part of cobalt acetylacetonate and 0.7 part of triphenylphosphine in ethanol solution, and mix well to obtain resin glue. Take a flat and clean E-type glass fiber cloth with a model of 2116 and evenly impregnate the above glue solution, bake it in a blast oven at 170 ° C for 5 minutes to obtain a prepreg sheet, overlap 6 of the above prepreg sheets, and cover the top and bottom with 35 mm copper The foil was pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 min to obtain a copper clad laminate.
比較例1：Comparative Example 1:
將3份雙氰胺（Dicy）溶解於210份二甲基甲醯胺（DMF）溶劑中，然後加入120份含溴雙酚A型環氧樹脂的丙酮溶液（美國陶氏化學，D.E.R.530A80，固含量80重量%）和0.1份2-乙基-4-甲基咪唑。將上述組合物在常溫充分攪拌，得到分散均勻的樹脂組合物。然後加入230份熔融二氧化矽（D50=3.0 μm，江蘇聯瑞新材料股份有限公司），混合均勻，得到樹脂膠液。取平整光潔，型號為2116的E型玻璃纖維布均勻浸漬上述膠液，在鼓風烘箱中於170℃烘烤5min製得預浸片，將6張上述預浸片重疊，上下覆35 mm銅箔，於真空熱壓機中在3MPa壓力和220℃溫度下壓制90min得到覆銅層壓板。Dissolve 3 parts of dicyandiamide (Dicy) in 210 parts of dimethylformamide (DMF) solvent, and then add 120 parts of acetone solution containing bromobisphenol A epoxy resin (Dow Chemical, DER530A80, solids content 80% by weight) and 0.1 part of 2-ethyl-4-methylimidazole. The above composition was sufficiently stirred at room temperature to obtain a uniformly dispersed resin composition. Then, 230 parts of fused silica (D50=3.0 μm, Jiangsu Lianrui New Materials Co., Ltd.) were added, and the mixture was uniformly mixed to obtain a resin glue. Take a flat and clean E-type glass fiber cloth with model 2116 and evenly impregnate the above glue, bake it in a blast oven at 170 ° C for 5 minutes to prepare a prepreg sheet, overlap 6 of the above prepreg sheets, and cover the top and bottom with 35 mm copper The foil was pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 min to obtain a copper clad laminate.
比較例2：Comparative Example 2:
將50份線性苯酚酚醛（韓國科隆，KPE-F2002）溶解於215份丁酮溶劑中，然後加入65份雙酚A型酚醛環氧樹脂的丁酮溶液（長春人造樹脂股份有限公司，BNE200A80，固含量80重量%）和0.1份2-乙基-4-甲基咪唑。將上述組合物在常溫充分攪拌，得到分散均勻的樹脂組合物。然後加入230份熔融二氧化矽（D50=3.0 μm，江蘇聯瑞新材料股份有限公司），混合均勻，得到樹脂膠液。取平整光潔，型號為2116的E型玻璃纖維布均勻浸漬上述膠液，在鼓風烘箱中於170℃烘烤5min製得預浸片，將6張上述預浸片重疊，上下覆35 mm銅箔，於真空熱壓機中在3MPa壓力和220℃溫度下壓製90min得到覆銅層壓板。Dissolve 50 parts of linear phenol novolac (Kolon, Korea, KPE-F2002) in 215 parts of methyl ethyl ketone solvent, and then add 65 parts of bisphenol A type novolac epoxy resin in butanone solution (Changchun Artificial Resin Co., Ltd., BNE200A80, solid content 80% by weight) and 0.1 part of 2-ethyl-4-methylimidazole. The above composition was sufficiently stirred at room temperature to obtain a uniformly dispersed resin composition. Then, 230 parts of fused silica (D50=3.0 μm, Jiangsu Lianrui New Materials Co., Ltd.) were added, and the mixture was uniformly mixed to obtain a resin glue solution. Take a flat and clean E-type glass fiber cloth with model 2116 and evenly impregnate the above glue, bake it in a blast oven at 170 ° C for 5 minutes to prepare a prepreg sheet, overlap 6 of the above prepreg sheets, and cover the top and bottom with 35 mm copper The foil was pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 min to obtain a copper clad laminate.
比較例3：Comparative Example 3:
將3份雙氰胺（Dicy）溶解於210份DMF溶劑中，然後加入120份含溴雙酚A型環氧樹脂的丙酮溶液（美國陶氏化學，D.E.R.530A80，固含量80重量%）和0.1份2-乙基-4-甲基咪唑。將上述組合物在常溫充分攪拌，得到分散均勻的樹脂組合物。然後加入200份聚四氟乙烯粉（M-112，D50=20 μm，日本大金工業株式會社），混合均勻，得到樹脂膠液。取平整光潔，型號為2116的E型玻璃纖維布均勻浸漬上述膠液，在鼓風烘箱中於170℃烘烤5min製得預浸片，將6張上述預浸片重疊，上下覆35 mm銅箔，於真空熱壓機中在3MPa壓力和220℃溫度下壓製90min得到覆銅層壓板。Dissolve 3 parts of dicyandiamide (Dicy) in 210 parts of DMF solvent, then add 120 parts of acetone solution containing bromobisphenol A epoxy resin (Dow Chemical, USA, DER530A80, solid content 80% by weight) and 0.1 parts of 2-ethyl-4-methylimidazole. The above composition was sufficiently stirred at room temperature to obtain a uniformly dispersed resin composition. Then, 200 parts of polytetrafluoroethylene powder (M-112, D50=20 μm, Daikin Industries, Ltd., Japan) were added, and the mixture was uniformly mixed to obtain a resin glue solution. Take a flat and clean E-type glass fiber cloth with model 2116 and evenly impregnate the above glue, bake it in a blast oven at 170 ° C for 5 minutes to prepare a prepreg sheet, overlap 6 of the above prepreg sheets, and cover the top and bottom with 35 mm copper The foil was pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 min to obtain a copper clad laminate.
比較例4：Comparative Example 4:
將100份矽芳炔樹脂（數均分子量1200）在200份甲苯中充分溶解，得到樹脂膠液。取平整光潔，型號為2116的E型玻璃纖維布均勻浸漬上述膠液，在鼓風烘箱中於170℃烘烤5min製得預浸片，將6張上述預浸片重疊，上下覆35 mm銅箔，於真空熱壓機中在3MPa壓力和220℃溫度下壓制90min得到覆銅層壓板。100 parts of silicon aryne resin (number average molecular weight 1200) was fully dissolved in 200 parts of toluene to obtain resin glue. Take a flat and clean E-type glass fiber cloth with a model of 2116 and evenly impregnate the above glue solution, bake it in a blast oven at 170 ° C for 5 minutes to obtain a prepreg sheet, overlap 6 of the above prepreg sheets, and cover the top and bottom with 35 mm copper The foil was pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 min to obtain a copper clad laminate.
將實施例1至6和比較例1～4的覆銅層壓板進行性能評價。評價結果總結在下面的表中。The copper-clad laminates of Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to performance evaluation. The evaluation results are summarized in the table below.
測試表中所述性能的方法如下：Here's how to test the performance described in the table:
1）玻璃化轉變溫度Tg：使用動態熱機械分析（DMA）測試，按照IPC-TM-6502.4.24所規定的DMA測試方法；1) Glass transition temperature Tg: use dynamic thermomechanical analysis (DMA) test, according to the DMA test method specified in IPC-TM-6502.4.24;
2）熱分解溫度（Td）：使用熱失重分析（TGA）測試，按照標準IPC-TM-650 2.4.24.6；2) Thermal decomposition temperature (Td): Tested using thermogravimetric analysis (TGA), in accordance with standard IPC-TM-650 2.4.24.6;
3）剝離強度（PS）：指在室溫下將每毫米銅箔剝離覆銅板所需的拉力；3) Peel strength (PS): refers to the tensile force required to peel off each millimeter of copper foil from the copper clad laminate at room temperature;
4）介電常數（Dk）和介電損耗因數（Df）：1GHz使用平板電容法測定，按照標準IPC-TM-650 2.4.24，而10GHz使用諧振腔法（SPDR）法測定，按照標準IPC-TM-650 2.5.5.5。4) Dielectric Constant (Dk) and Dielectric Dissipation Factor (Df): 1GHz is measured using the plate capacitance method, according to standard IPC-TM-650 2.4.24, while 10GHz is measured using the resonant cavity method (SPDR) method, according to standard IPC - TM-650 2.5.5.5.
5）阻燃性：按照UL94“50W （20 mm）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。5) Flame retardancy: According to UL94 "50W (20 mm) vertical burning test: V-0, V-1 and V-2" test method, V-0 is identified as flame retardant.
6）熱膨脹係數和50～260℃熱膨脹比例：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。6) Thermal expansion coefficient and thermal expansion ratio at 50-260°C: The test is tested by a static thermal analyzer (TMA), and the test is in accordance with the standard IPC-TM-650 2.4.24.
7）熱應力：將覆銅層壓板漂浮在熔融狀態的錫液表面，溫度288℃，以分層或氣泡的時間作為測試結果。7) Thermal stress: float the copper clad laminate on the molten tin surface at a temperature of 288°C, and take the time of delamination or bubbles as the test result.
由上述實施例和對比例測試結果可知，該實施例樣品均可以做到無鹵無磷阻燃，而且Tg、Td的測試結果都遠高於常規的印刷電路板用，板材的介電損耗因數結果說明其在高頻高速板材中將具有很好應用性能，其CTE和熱應力表現優異。另外，較高的填料含量會降低層壓板的銅箔附著力，提高樹脂含量，加入促進劑可以有一定程度的改善。It can be seen from the test results of the above examples and comparative examples that the samples of this example can be flame retardant without halogen and phosphorus, and the test results of Tg and Td are much higher than those of conventional printed circuit boards. The dielectric loss factor of the board is The results show that it will have good application performance in high frequency and high speed sheet, and its CTE and thermal stress performance are excellent. In addition, higher filler content will reduce the copper foil adhesion of the laminate and increase the resin content, which can be improved to a certain extent by adding accelerators.
如上，可以提供一種樹脂組合物、通過用玻纖布浸潤所述樹脂組合物得到的印刷電路用預浸片及包含所述印刷電路用預浸片的覆金屬層壓板或絕緣板，以及包含所述印刷電路用預浸片、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低介電損耗因數、高耐熱性、低熱膨脹係數、無鹵無磷阻燃等特性中的一個。As above, it is possible to provide a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a glass fiber cloth, and a metal-clad laminate or an insulating board comprising the prepreg for a printed circuit, and a prepreg comprising the The prepreg for printed circuit, the insulating board or the printed circuit board of the metal-clad laminate, so that the metal-clad laminate can at least have low dielectric loss factor, high heat resistance, low thermal expansion coefficient, halogen-free and phosphorus-free One of the characteristics of flame retardant.
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. Thus, provided that these modifications and variations of the present invention fall within the scope of the patent application of the present invention and the scope of equivalent technologies, the present invention is also intended to include these modifications and variations.
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| TW201731955A (en) * | 2016-03-10 | 2017-09-16 | Shengyi Technology Co Ltd | Halogen-free thermosetting resin composition, and prepreg and laminate for printed circuits using same |
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| CN104962085A (en) * | 2015-07-13 | 2015-10-07 | 华东理工大学 | Method for improving mechanical property of silicon-containing arylacetylene resin based composite material |
| CN105623506A (en) * | 2015-12-31 | 2016-06-01 | 中物功能材料研究院有限公司 | Ceramic-based composite coating and preparation method thereof |
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