TWI814835B - Resin composition, prepreg, laminate, metal foil clad laminate and printed circuit board - Google Patents

Resin composition, prepreg, laminate, metal foil clad laminate and printed circuit board Download PDF

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TWI814835B
TWI814835B TW108119378A TW108119378A TWI814835B TW I814835 B TWI814835 B TW I814835B TW 108119378 A TW108119378 A TW 108119378A TW 108119378 A TW108119378 A TW 108119378A TW I814835 B TWI814835 B TW I814835B
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resin composition
epoxy resin
silicone rubber
prepreg
metal foil
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TW202026355A (en
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唐軍旗
李志光
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大陸商廣東生益科技股份有限公司
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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
    • 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
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • 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
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Epoxy Resins (AREA)

Abstract

本發明涉及一種樹脂組合物及使用其製作的預浸料、層壓板、覆金屬箔層壓板以及印刷電路板。本發明的樹脂組合物包括環氧樹脂（A）、酚性固化劑（B）、有機矽橡膠（C）。本發明的樹脂組合物及使用其製得的預浸料、層壓板以及覆金屬箔層壓板具有良好的耐熱性及低模量、低熱膨脹係數的特性，可以抑制印刷電路板加工過程中焊盤開裂的現象。The present invention relates to a resin composition and prepregs, laminates, metal foil-clad laminates and printed circuit boards produced using the resin composition. The resin composition of the present invention includes epoxy resin (A), phenolic curing agent (B), and organic silicone rubber (C). The resin composition of the present invention and the prepregs, laminates and metal foil-clad laminates prepared by using the same have good heat resistance, low modulus and low thermal expansion coefficient, and can inhibit the soldering pads during the processing of printed circuit boards. cracking phenomenon.

Description

樹脂組合物、預浸料、層壓板、覆金屬箔層壓板和印刷電路板Resin composition, prepreg, laminate, metal foil clad laminate and printed circuit board

本發明涉及用於電子產品的封裝技術領域，尤其涉及一種印刷電路板用樹脂組合物及使用其製備的預浸料、層壓板、覆金屬箔層壓板和印刷電路板。The present invention relates to the field of packaging technology for electronic products, and in particular to a resin composition for printed circuit boards and prepregs, laminates, metal foil-clad laminates and printed circuit boards prepared using the resin composition.

隨著電腦、電子和資訊通訊設備的日益小型化、高性能化和多功能化，需要印刷電路板（PCB）滿足小型化、薄型化、高積體化和高可靠性的更高要求，與此相伴，對用於PCB的半導體封裝用層壓板也提出了具有更優異的耐濕性、耐熱性和可靠性等的要求。另外，隨著半導體封裝密度的提高，如何減少封裝過程中產生的翹曲以及PCB加工過程中焊接部位的開裂也逐漸成為迫切需要解決的問題。As computers, electronics and information communication equipment become increasingly miniaturized, high-performance and multi-functional, printed circuit boards (PCBs) are required to meet higher requirements for miniaturization, thinness, high integration and high reliability, and Along with this, there are also requirements for laminates for semiconductor packaging used in PCBs to have better moisture resistance, heat resistance, reliability, etc. In addition, as the density of semiconductor packaging increases, how to reduce warpage during the packaging process and cracking of the welding parts during PCB processing has gradually become an urgent problem that needs to be solved.

環氧樹脂具有優異的力學性能和工藝加工性，在製作印刷電路板用覆金屬箔層壓材料中是一種常用的基體樹脂。含有環氧樹脂的樹脂組合物具有優異的柔韌性、耐化學性、黏合性等，但是，其固化物通常存在吸水率高，耐濕熱性不足的問題，難以滿足高端基板的性能需求。Epoxy resin has excellent mechanical properties and processability, and is a commonly used matrix resin in the production of metal foil laminates for printed circuit boards. Resin compositions containing epoxy resin have excellent flexibility, chemical resistance, adhesion, etc. However, their cured products usually have problems such as high water absorption and insufficient heat and humidity resistance, making it difficult to meet the performance requirements of high-end substrates.

本發明的發明人出人意料地發現：通過向含有環氧樹脂和酚性固化劑的樹脂組合物中添加特定含量的有機矽橡膠，不僅可以獲得具有良好的耐熱性及低模量、低熱膨脹係數特性的預浸料、層壓板以及覆金屬箔層壓板，而且還可以抑制PCB加工過程中焊盤開裂的現象，從而完成了本發明。The inventor of the present invention unexpectedly discovered that by adding a specific content of organic silicone rubber to a resin composition containing an epoxy resin and a phenolic curing agent, not only good heat resistance, low modulus, and low thermal expansion coefficient characteristics can be obtained Prepregs, laminates and metal foil-clad laminates, and can also suppress pad cracking during PCB processing, thereby completing the present invention.

本發明的一個方面提供一種樹脂組合物，其包含：環氧樹脂（A）、酚性固化劑（B）和有機矽橡膠（C），以環氧樹脂（A）和酚性固化劑（B）的總重量為100重量份計，所述有機矽橡膠（C）的量為20~100重量份，優選為30~70重量份。One aspect of the present invention provides a resin composition, which includes: epoxy resin (A), phenolic curing agent (B) and organic silicone rubber (C), with epoxy resin (A) and phenolic curing agent (B) ) is 100 parts by weight, and the amount of the organic silicone rubber (C) is 20 to 100 parts by weight, preferably 30 to 70 parts by weight.

在某些實施方案中，有機矽橡膠（C）為含乙烯基的聚矽氧烷與含矽氫的聚矽氧烷通過加成聚合得到的聚合物。In certain embodiments, the organic silicone rubber (C) is a polymer obtained by addition polymerization of vinyl-containing polysiloxane and silicon-hydrogen-containing polysiloxane.

在某些實施方案中，有機矽橡膠（C）表面包覆有由矽氧烷鍵交聯形成的聚甲基倍半矽氧烷。In certain embodiments, the surface of the organosilicone rubber (C) is coated with polymethylsilsesquioxane formed by cross-linking of siloxane bonds.

在某些實施方案中，有機矽橡膠（C）的D50粒徑為1~20 µm。In some embodiments, the D50 particle size of the organic silicone rubber (C) is 1~20 µm.

在某些實施方案中，酚性固化劑（B）為酚醛樹脂。In certain embodiments, phenolic curing agent (B) is a phenolic resin.

在某些實施方案中，環氧樹脂（A）和酚性固化劑（B）中的至少一種含有芳烷基或雙環戊二烯結構。In certain embodiments, at least one of the epoxy resin (A) and the phenolic curing agent (B) contains an aralkyl or dicyclopentadiene structure.

在某些實施方案中，所述樹脂組合物還包含無機填料(D)。In certain embodiments, the resin composition further includes an inorganic filler (D).

在某些實施方案中，以環氧樹脂（A）和酚性固化劑（B）的總重量為100重量份計，所述無機填料（D）的量為5~100重量份，優選為10~70重量份，進一步優選為15~60重量份。In certain embodiments, based on the total weight of epoxy resin (A) and phenolic curing agent (B) being 100 parts by weight, the amount of inorganic filler (D) is 5 to 100 parts by weight, preferably 10 ~70 parts by weight, more preferably 15~60 parts by weight.

本發明的另一方面提供一種預浸料，其包括基材及通過浸漬或塗覆而附著於基材上的上述樹脂組合物。Another aspect of the present invention provides a prepreg, which includes a base material and the above-mentioned resin composition attached to the base material by impregnation or coating.

本發明的另一方面提供一種層壓板，其包括至少一張上述預浸料。Another aspect of the invention provides a laminate comprising at least one sheet of the prepreg as described above.

本發明的另一方面提供一種覆金屬箔層壓板，其包括至少一張上述預浸料及覆於預浸料一側或兩側的金屬箔。Another aspect of the present invention provides a metal foil-clad laminate, which includes at least one piece of the above-mentioned prepreg and a metal foil covering one or both sides of the prepreg.

本發明的另一方面提供一種印刷電路板，其包括至少一張上述預浸料。Another aspect of the present invention provides a printed circuit board, which includes at least one piece of the above-mentioned prepreg.

本發明的樹脂組合物及使用其製得的預浸料、層壓板和覆金屬箔層壓板具有良好的耐熱性及低模量、低熱膨脹係數的特性，可以抑制PCB加工過程中焊盤開裂的現象。The resin composition of the present invention and the prepregs, laminates and metal foil-clad laminates prepared using the same have good heat resistance, low modulus and low thermal expansion coefficient, and can inhibit the occurrence of pad cracking during PCB processing. phenomenon.

為了更好地說明本發明，對本發明的某些具體實施方式進行詳細的說明，但本發明的實施方式不限定於這些，在申請專利範圍的範圍內可進行不同的變化。In order to better illustrate the present invention, some specific embodiments of the present invention are described in detail, but the embodiments of the present invention are not limited to these, and different changes can be made within the scope of the patent application.

本發明的樹脂組合物含有：環氧樹脂（A）、酚性固化劑（B）、有機矽橡膠（C）。The resin composition of the present invention contains: epoxy resin (A), phenolic curing agent (B), and organic silicone rubber (C).

對環氧樹脂（A）沒有特別的限制，只要其是每個分子含有至少兩個環氧基的化合物即可。環氧樹脂的實例可以包括：雙酚A型環氧樹脂、雙酚E型環氧樹脂、雙酚F型環氧樹脂、四甲基雙酚F型環氧樹脂、雙酚M型環氧樹脂、雙酚P型環氧樹脂、雙酚S型環氧樹脂、線性酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、雙酚A酚醛型環氧樹脂、溴化雙酚A型環氧樹脂、溴化酚醛型環氧樹脂、三官能酚型環氧樹脂、四官能酚型環氧樹脂、萘型環氧樹脂、萘酚酚醛環氧樹脂、苯氧基型環氧樹脂、聯苯型環氧樹脂、雙環戊二烯型環氧樹脂、雙環戊二烯酚醛型環氧樹脂、芳烷基型環氧樹脂、芳烷基酚醛型環氧樹脂、芳烷基萘酚酚醛型環氧樹脂、異氰酸酯改性環氧、脂環族環氧樹脂、多元醇型環氧樹脂、含磷環氧樹脂、含矽環氧樹脂、含氮環氧樹脂、含溴環氧樹脂、縮水甘油胺、縮水甘油酯、或通過丁二烯之類的雙鍵環氧化獲得的化合物。上述環氧樹脂可以根據需要單獨或結合使用。The epoxy resin (A) is not particularly limited as long as it is a compound containing at least two epoxy groups per molecule. Examples of the epoxy resin may include: bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, bisphenol M type epoxy resin , bisphenol P epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, brominated bisphenol A epoxy resin , Brominated phenolic epoxy resin, trifunctional phenolic epoxy resin, tetrafunctional phenolic epoxy resin, naphthalene epoxy resin, naphthol novolac epoxy resin, phenoxy epoxy resin, biphenyl ring Oxygen resin, dicyclopentadiene epoxy resin, dicyclopentadiene phenolic epoxy resin, aralkyl epoxy resin, aralkyl phenolic epoxy resin, aralkyl naphthol phenolic epoxy resin, Isocyanate modified epoxy, alicyclic epoxy resin, polyol epoxy resin, phosphorus-containing epoxy resin, silicon-containing epoxy resin, nitrogen-containing epoxy resin, bromine-containing epoxy resin, glycidylamine, glycidyl esters, or compounds obtained by epoxidation of double bonds such as butadiene. The above epoxy resins can be used alone or in combination as needed.

對酚性固化劑（B）沒有特別的限制，其可以選自分子結構中含有至少兩個苯酚基的有機化合物，例如酚醛樹脂，包括苯酚酚醛樹脂、甲酚酚醛樹脂、萘酚酚醛樹脂等。公知的用於環氧樹脂組合物的酚性固化劑都可以選擇，而且可以是一種或者至少兩種的混合物。There is no particular limitation on the phenolic curing agent (B), which can be selected from organic compounds containing at least two phenol groups in the molecular structure, such as phenolic resins, including phenol novolac resin, cresol novolac resin, naphthol novolac resin, etc. Well-known phenolic curing agents used in epoxy resin compositions can be selected, and can be one type or a mixture of at least two types.

儘管其詳細機理（在本發明的特殊樹脂組合物體系中）有待進一步研究，但是發明人發現：當環氧樹脂和酚性固化劑中的至少一種含有芳烷基或雙環戊二烯基時，可使本發明的樹脂組合物具有更高的耐熱性及更低的熱膨脹係數。含有芳烷基的環氧樹脂可以選自芳烷基型環氧樹脂、芳烷基酚醛型環氧樹脂等。含有雙環戊二烯基的環氧樹脂可以選自雙環戊二烯型環氧樹脂、雙環戊二烯酚醛型環氧樹脂等。含有芳烷基的酚性固化劑可以選自芳烷基型酚醛樹脂等。含有雙環戊二烯基的酚性固化劑可以選自雙環戊二烯型酚醛樹脂等。Although its detailed mechanism (in the special resin composition system of the present invention) needs further study, the inventor found that when at least one of the epoxy resin and the phenolic curing agent contains an aralkyl group or a dicyclopentadienyl group, The resin composition of the present invention can have higher heat resistance and lower thermal expansion coefficient. The epoxy resin containing an aralkyl group can be selected from aralkyl type epoxy resin, aralkyl phenolic type epoxy resin, etc. The epoxy resin containing dicyclopentadienyl group can be selected from dicyclopentadiene-type epoxy resin, dicyclopentadiene-type epoxy resin, etc. The phenolic curing agent containing an aralkyl group can be selected from aralkyl type phenolic resin, etc. The phenolic curing agent containing dicyclopentadienyl group can be selected from dicyclopentadiene-type phenolic resin and the like.

對環氧樹脂和酚性固化劑的用量沒有特別限制，只要能使層壓板和覆金屬箔層壓板在一定的固化條件下充分固化即可。There are no special restrictions on the amounts of epoxy resin and phenolic curing agent, as long as the laminate and metal foil-clad laminate can be fully cured under certain curing conditions.

可用於本發明的有機矽橡膠（C）沒有特別的限制，其可以選自分子主鏈由矽原子和氧原子交替構成鍵，矽原子上通常連有兩個有機基團的高分子聚合物。The organic silicone rubber (C) that can be used in the present invention is not particularly limited. It can be selected from high molecular polymers whose main chain of molecules is alternately composed of silicon atoms and oxygen atoms, and the silicon atoms are usually connected with two organic groups.

可用於本發明的有機矽橡膠（C）的用量沒有特別的限制，有機矽橡膠（C）在樹脂組合物中的用量以環氧樹脂（A）和酚性固化劑（B）的總重量為100重量份計，可以為20~100重量份，優選為30~70重量份。若有機矽橡膠的用量過多，則存在分散性問題，影響樹脂組合物、預浸料、層壓板及覆金屬箔層壓板的耐熱性、力學性能等。若有機矽橡膠的用量過少，則樹脂組合物、預浸料、層壓板及覆金屬箔層壓板不具備低模量和低熱膨脹係數特性。The amount of organic silicone rubber (C) that can be used in the present invention is not particularly limited. The amount of organic silicone rubber (C) used in the resin composition is based on the total weight of epoxy resin (A) and phenolic curing agent (B). It can be 20 to 100 parts by weight based on 100 parts by weight, preferably 30 to 70 parts by weight. If the amount of silicone rubber is too much, there will be dispersion problems, which will affect the heat resistance and mechanical properties of resin compositions, prepregs, laminates and metal foil-clad laminates. If the amount of silicone rubber is too small, the resin composition, prepreg, laminate and metal foil-clad laminate will not have low modulus and low thermal expansion coefficient properties.

可用於本發明的有機矽橡膠（C）為含乙烯基的聚矽氧烷與含矽氫的聚矽氧烷通過加成聚合得到的聚合物。The organic silicone rubber (C) that can be used in the present invention is a polymer obtained by addition polymerization of vinyl-containing polysiloxane and silicon-hydrogen-containing polysiloxane.

可用於本發明的有機矽橡膠（C）表面包覆有由矽氧烷鍵交聯形成的聚甲基倍半矽氧烷。包覆有聚甲基倍半矽氧烷可以降低有機矽橡膠（C）的凝聚性，提高有機矽橡膠（C）在樹脂組合物中的分散性。The surface of the organic silicone rubber (C) that can be used in the present invention is coated with polymethylsilsesquioxane formed by cross-linking of siloxane bonds. Coating with polymethylsilsesquioxane can reduce the cohesion of the organic silicone rubber (C) and improve the dispersion of the organic silicone rubber (C) in the resin composition.

可用於本發明的有機矽橡膠（C）的平均粒徑（D50）可以為1~20 µm。若有機矽橡膠（C）的D50低於1 µm，則為亞微米級有機填料，由於比表面積大，有機矽橡膠之間的凝聚力增加，在樹脂組合物中極易團聚。若有機矽橡膠（C）的D50高於20 µm，會導致有機矽橡膠（C）與環氧樹脂和酚性固化劑的結合力不強而容易脫落，從而影響樹脂組合物、預浸料、層壓板及覆金屬箔層壓板的耐熱性、力學性能等。The average particle size (D50) of the organic silicone rubber (C) that can be used in the present invention can be 1~20 µm. If the D50 of the silicone rubber (C) is less than 1 µm, it is a sub-micron organic filler. Due to the large specific surface area, the cohesion between the silicone rubbers increases and it is easy to agglomerate in the resin composition. If the D50 of the silicone rubber (C) is higher than 20 µm, the bonding force between the silicone rubber (C) and the epoxy resin and phenolic curing agent will not be strong and will easily fall off, thus affecting the resin composition, prepreg, Heat resistance and mechanical properties of laminates and metal foil-clad laminates.

符合上述所述的有機矽橡膠（C），作為市售品，可以列舉，信越有機矽公司製，商品名KMP-597、KMP-598、KMP-600、KMP-601、KMP-605等。Examples of commercially available silicone rubbers (C) that meet the above requirements include those manufactured by Shin-Etsu Silicone Co., Ltd. and have trade names of KMP-597, KMP-598, KMP-600, KMP-601, KMP-605, and the like.

本發明所述的樹脂組合物還包含無機填料(D)。當無機填料（D）用於本發明的樹脂組合物時，可以提高樹脂組合物和層壓板的耐熱性，同時可以提高層壓板和覆金屬箔層壓板的尺寸穩定性和降低熱膨脹係數，也能降低成本。The resin composition according to the present invention further contains an inorganic filler (D). When the inorganic filler (D) is used in the resin composition of the present invention, the heat resistance of the resin composition and the laminate can be improved, while the dimensional stability of the laminate and the metal foil-clad laminate can be improved and the thermal expansion coefficient can be reduced. cut costs.

對無機填料（D）的種類並沒有限定，可以選自結晶型二氧化矽、熔融二氧化矽、無定形二氧化矽、球形二氧化矽、空心二氧化矽、氫氧化鋁、氫氧化鎂、勃姆石、氧化鉬、鉬酸鋅、二氧化鈦、氧化鋅、氮化硼、氮化鋁、碳化矽、氧化鋁、複合矽微粉、玻璃粉、短玻璃纖維或空心玻璃等中的一種或者多種。為了使樹脂組合物具有更高的耐熱性、耐濕熱性和尺寸穩定性，優選結晶型二氧化矽、熔融二氧化矽、無定形二氧化矽、球形二氧化矽、空心二氧化矽、氫氧化鋁、氫氧化鎂、勃姆石、氮化硼、氮化鋁、碳化矽、氧化鋁、複合矽微粉、玻璃粉、短玻璃纖維或空心玻璃中的一種或者多種，進一步優選球形二氧化矽。The type of inorganic filler (D) is not limited and can be selected from crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, aluminum hydroxide, magnesium hydroxide, One or more of boehmite, molybdenum oxide, zinc molybdate, titanium dioxide, zinc oxide, boron nitride, aluminum nitride, silicon carbide, alumina, composite silicon powder, glass powder, short glass fiber or hollow glass. In order to provide the resin composition with higher heat resistance, moisture-heat resistance and dimensional stability, crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, hydroxide silica are preferred. One or more of aluminum, magnesium hydroxide, boehmite, boron nitride, aluminum nitride, silicon carbide, alumina, composite silicon powder, glass powder, short glass fiber or hollow glass, more preferably spherical silicon dioxide.

以環氧樹脂（A）和酚性固化劑（B）的總重量為100重量份計，所述無機填料（D）的量可以為5~100重量份，優選為10~70重量份，進一步優選為15~60重量份。Based on the total weight of the epoxy resin (A) and the phenolic curing agent (B) being 100 parts by weight, the amount of the inorganic filler (D) can be 5 to 100 parts by weight, preferably 10 to 70 parts by weight, further Preferably it is 15~60 parts by weight.

為了提高無機填料（D）與樹脂組合物的相容性，可以加入偶聯劑進行表面處理。對偶聯劑沒有限定，一般選自矽烷偶聯劑。對矽烷偶聯劑的種類沒有限定，可以列舉環氧基矽烷偶聯劑、氨基矽烷偶聯劑、乙烯基矽烷偶聯劑、苯乙烯基矽烷偶聯劑、異丁烯基矽烷偶聯劑、丙烯基矽烷偶聯劑、脲基矽烷偶聯劑、巰基矽烷偶聯劑、氯丙基矽烷偶聯劑、硫化基矽烷偶聯劑、異氰酸鹽基矽烷偶聯劑等。In order to improve the compatibility between the inorganic filler (D) and the resin composition, a coupling agent can be added for surface treatment. The coupling agent is not limited and is generally selected from silane coupling agents. The type of silane coupling agent is not limited, and examples thereof include epoxy silane coupling agent, aminosilane coupling agent, vinyl silane coupling agent, styryl silane coupling agent, isobutenyl silane coupling agent, acryl silane coupling agent, etc. Silane coupling agent, ureido silane coupling agent, mercapto silane coupling agent, chloropropyl silane coupling agent, sulfide silane coupling agent, isocyanate silane coupling agent, etc.

為了提高無機填料（D）在樹脂組合物中的分散性，可以加入濕潤分散劑。作為濕潤分散劑，只要是在塗料用途等中被使用的分散穩定劑，就沒有特別限定。作為濕潤分散劑的具體例，例如可列舉出，BYK公司製，商品名Disperbyk-110、Disperbyk-111、Disperbyk-180、Disperbyk-161、BYK-W996、BYK-W9010、BYK-W903等混潤分散劑。In order to improve the dispersibility of the inorganic filler (D) in the resin composition, a moist dispersing agent may be added. The wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for coating applications and the like. Specific examples of the wetting and dispersing agent include, for example, BYK Corporation, trade names Disperbyk-110, Disperbyk-111, Disperbyk-180, Disperbyk-161, BYK-W996, BYK-W9010, BYK-W903, etc. agent.

為了使樹脂組合物完全固化，本發明的樹脂組合物還可以根據需要加入促進劑（E）。促進劑（E）選自可以促進環氧樹脂與酚性固化劑的固化促進劑，其具體包括銅、鋅、鈷、鎳、錳之類的金屬的有機鹽、咪唑及其衍生物、叔胺等，可以是一種或者兩種以上複合使用。In order to completely cure the resin composition, an accelerator (E) may be added to the resin composition of the present invention as needed. The accelerator (E) is selected from curing accelerators that can promote epoxy resin and phenolic curing agents, which specifically include organic salts of metals such as copper, zinc, cobalt, nickel, and manganese, imidazole and its derivatives, and tertiary amines. etc., can be used in combination of one type or two or more types.

另外，為了使樹脂組合物具有較好的加工性和使用性能，還可以根據需要向樹脂組合物加入各種添加劑，例如阻燃劑、熱穩定劑、光穩定劑、抗氧化劑、潤滑劑等。In addition, in order to make the resin composition have better processability and usability, various additives can be added to the resin composition as needed, such as flame retardants, heat stabilizers, light stabilizers, antioxidants, lubricants, etc.

本發明的樹脂組合物可以通過本領域常規的方法製備，例如溶解、混合、預聚、預反應、攪拌所述環氧樹脂（A）、酚性固化劑（B）、有機矽橡膠（C）等來製備。The resin composition of the present invention can be prepared by conventional methods in this field, such as dissolving, mixing, prepolymerizing, prereacting, and stirring the epoxy resin (A), phenolic curing agent (B), and organic silicone rubber (C) Wait to prepare.

溶解樹脂需要使用有機溶劑，只要使各種樹脂能完全溶解、且混合時不發生分離即可，可以列舉：甲醇、乙醇、丁醇等醇類，乙基溶纖劑、丁基溶纖劑、乙二醇-甲醚、二乙二醇乙醚、二乙二醇丁醚等醚類，丙酮、丁酮、甲基乙基甲酮、甲基異丁基甲酮、環己酮等酮類，甲苯、二甲苯、均三甲苯等芳香族烴類，乙氧基乙基乙酸酯、醋酸乙酯等酯類，N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮等含氮類溶劑。上述溶劑可以單獨使用，也可以根據需要將兩種或者兩種以上混合使用。Organic solvents are required to dissolve resins, as long as the various resins can be completely dissolved and do not separate during mixing. Examples include: methanol, ethanol, butanol and other alcohols, ethyl cellosolve, butyl cellosolve, ethylene glycol - Ethers such as methyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, toluene, xylene, Aromatic hydrocarbons such as mesitylene, esters such as ethoxyethyl acetate and ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl Nitrogen-containing solvents such as base-2-pyrrolidone. The above-mentioned solvents can be used alone, or two or more types can be mixed and used as needed.

本發明的預浸料是由半固化狀態的本發明的樹脂組合物和基材形成。具體而言，預浸料是通過以下過程形成，即，清漆狀態的樹脂組合物浸潤基材，經過加熱使溶劑揮發並轉變為半固化狀態。The prepreg of the present invention is formed from the resin composition of the present invention in a semi-cured state and a base material. Specifically, prepregs are formed by a process in which a resin composition in a varnish state is infiltrated into a base material, and then heated to volatilize the solvent and transform it into a semi-cured state.

本發明所述的基材沒有特別的限制，其可以選自已知的用於製作各種印刷電路板材料的基材。具體為無機纖維(例如E玻璃、D玻璃、L玻璃、M玻璃、S玻璃、T玻璃、NE玻璃、Q玻璃、石英等玻璃纖維)、有機纖維(例如聚醯亞胺、聚醯胺、聚酯、聚苯醚、液晶聚合物等)。基材的形式通常是紡織物、無紡布、粗紗、短纖維、纖維紙等。在上述基材中，本發明所述的基材優選玻璃纖維布。本發明的層壓板包括至少一張上述的預浸料。The base material of the present invention is not particularly limited, and it can be selected from known base materials used for making various printed circuit board materials. Specifically, they are inorganic fibers (such as E glass, D glass, L glass, M glass, S glass, T glass, NE glass, Q glass, quartz and other glass fibers), organic fibers (such as polyimide, polyamide, polyamide, etc.) ester, polyphenylene ether, liquid crystal polymer, etc.). The form of substrate is usually woven fabric, non-woven fabric, roving, short fiber, fiber paper, etc. Among the above-mentioned base materials, the base material of the present invention is preferably glass fiber cloth. The laminate of the present invention includes at least one prepreg as described above.

本發明的覆金屬箔層壓板包括至少一張上述的預浸料及覆於預浸料一側或兩側的金屬箔。例如可通過使1～20片預浸料重疊，並用在其單面或兩面配置了銅及鋁等金屬箔的構成層壓成形，從而製造覆金屬箔層壓板。The metal foil-clad laminate of the present invention includes at least one piece of the above-mentioned prepreg and a metal foil covering one or both sides of the prepreg. For example, a metal foil-clad laminate can be manufactured by stacking 1 to 20 prepregs and laminating them in a configuration in which metal foils such as copper and aluminum are arranged on one or both sides.

本發明還提供了一種印刷電路板，所述印刷電路板包括至少一張如上所述的預浸料。本發明的印刷電路板的製備方法沒有特別的限制，可以通過公知的方法來製備。The present invention also provides a printed circuit board, which includes at least one piece of prepreg as described above. The preparation method of the printed circuit board of the present invention is not particularly limited and can be prepared by known methods.

以下，利用實施例和比較例，對本發明進行更詳細的說明。Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples.

＜樹脂組合物原料＞＜Resin composition raw materials＞

環氧樹脂（A1）：聯苯基芳烷基型酚醛環氧樹脂（NC-3000H，由日本化藥株式會社提供）Epoxy resin (A1): biphenylaralkyl type phenolic epoxy resin (NC-3000H, provided by Nippon Kayaku Co., Ltd.)

環氧樹脂（A2）：苯基芳烷基型酚醛環氧樹脂（NC-2000，由日本化藥株式會社提供）Epoxy resin (A2): phenylaralkyl type phenolic epoxy resin (NC-2000, provided by Nippon Kayaku Co., Ltd.)

環氧樹脂（A3）：雙環戊二烯酚醛環氧樹脂（HP-7200H，由DIC株式會社提供）Epoxy resin (A3): Dicyclopentadiene phenolic epoxy resin (HP-7200H, provided by DIC Co., Ltd.)

環氧樹脂（A4）：雙酚A型環氧樹脂（EPICLON® 1055，由DIC株式會社提供）Epoxy resin (A4): Bisphenol A type epoxy resin (EPICLON® 1055, provided by DIC Co., Ltd.)

酚性固化劑（B1）：聯苯基芳烷基型酚醛樹脂（MEHC-7851H，由明和化成株式會社提供）Phenolic curing agent (B1): biphenylaralkyl phenolic resin (MEHC-7851H, provided by Meiwa Kasei Co., Ltd.)

酚性固化劑（B2）：苯基芳烷基型酚醛樹脂（MEHC-7800H，由明和化成株式會社提供）Phenolic curing agent (B2): phenyl aralkyl phenolic resin (MEHC-7800H, provided by Meiwa Kasei Co., Ltd.)

酚性固化劑（B3）：線性酚醛樹脂（HF-4M，由明和化成株式會社提供）Phenolic curing agent (B3): Novolac phenolic resin (HF-4M, provided by Meiwa Kasei Co., Ltd.)

有機矽橡膠（C1）：KMP-600，D50：5 µm，表面包覆有由矽氧烷鍵交聯形成的聚甲基倍半矽氧烷（信越有機矽公司製）Silicone rubber (C1): KMP-600, D50: 5 µm, surface coated with polymethylsesesquioxane formed by cross-linking siloxane bonds (manufactured by Shin-Etsu Silicone Co., Ltd.)

有機矽橡膠（C2）：KMP-601，D50：12 µm，表面包覆有由矽氧烷鍵交聯形成的聚甲基倍半矽氧烷（信越有機矽公司製）Silicone rubber (C2): KMP-601, D50: 12 µm, surface coated with polymethylsesesquioxane cross-linked by siloxane bonds (manufactured by Shin-Etsu Silicone Co., Ltd.)

有機矽橡膠（C3）：KMP-602，D50：30 µm，表面包覆有由矽氧烷鍵交聯形成的聚甲基倍半矽氧烷（信越有機矽公司製）Silicone rubber (C3): KMP-602, D50: 30 µm, surface coated with polymethylsesesquioxane cross-linked by siloxane bonds (manufactured by Shin-Etsu Silicone Co., Ltd.)

有機矽橡膠（C4）：KMP-597，D50：5 µm，表面沒有包覆有由矽氧烷鍵交聯形成的聚甲基倍半矽氧烷（信越有機矽公司製）Silicone rubber (C4): KMP-597, D50: 5 µm, the surface is not coated with polymethylsesesquioxane formed by cross-linking of siloxane bonds (manufactured by Shin-Etsu Silicone Co., Ltd.)

無機填料（D1）：球形二氧化矽（Admatechs公司製“SC2050-MB”，D50：0.5 µm）Inorganic filler (D1): Spherical silica ("SC2050-MB" manufactured by Admatechs, D50: 0.5 µm)

無機填料（D2）：球形氧化鋁（Admatechs公司製“AO-502”，D50：0.7 µm）Inorganic filler (D2): Spherical alumina ("AO-502" manufactured by Admatechs, D50: 0.7 µm)

無機填料（D3）：勃姆石（壹石通公司製“BG-601”，D50：0.5 µm）Inorganic filler (D3): Boehmite ("BG-601" manufactured by Ishitong Co., Ltd., D50: 0.5 µm)

促進劑（E）： 2-乙基-4-甲基咪唑（四國化成公司製“2E4MI”）Accelerator (E): 2-ethyl-4-methylimidazole ("2E4MI" manufactured by Shikoku Chemicals Co., Ltd.)

織布基材：玻璃纖維布（日東紡公司製1078玻璃纖維布，單重47g/m2 ）Fabric base material: glass fiber cloth (1078 glass fiber cloth manufactured by Nittobo Co., Ltd., unit weight 47g/m 2 )

本發明實施例、比較例中各組分均以固形物計算。Each component in the examples and comparative examples of the present invention is calculated as solid matter.

（預浸料）(prepreg)

將環氧樹脂、酚性固化劑、有機矽橡膠、無機填料以及促進劑按照表1和2所示的質量份配合，用丙二醇甲醚和丁酮溶解和稀釋，製備出清漆狀態的樹脂組合物。Mix the epoxy resin, phenolic curing agent, organic silicone rubber, inorganic filler and accelerator according to the mass parts shown in Tables 1 and 2, dissolve and dilute with propylene glycol methyl ether and butanone, and prepare a resin composition in a varnish state. .

然後清漆狀態的樹脂組合物浸潤日東紡製1078玻璃纖維布，並將其在150~170ºC的鼓風烘箱中加熱乾燥5~7分鐘，使清漆狀態的樹脂組合物轉變為半固化狀態的樹脂組合物，厚度控制在90 µm，由此製造出預浸料。Then the resin composition in the varnish state is infiltrated into Nittobo 1078 glass fiber cloth, and heated and dried in a blast oven at 150~170ºC for 5~7 minutes, so that the resin composition in the varnish state is transformed into a semi-cured resin combination. Material, the thickness is controlled at 90 µm, and the prepreg is manufactured.

（覆金屬箔層壓板）(metal foil clad laminate)

分別將2張、9張的上述預浸料疊合，並在其各自兩側壓覆18 μm厚度的電解銅箔，在壓機中進行2小時固化，固化壓力為45 kg/cm2 ，固化溫度為190℃。Stack 2 and 9 sheets of the above-mentioned prepregs respectively, and cover them with electrolytic copper foil with a thickness of 18 μm on both sides, and cure them in a press for 2 hours. The curing pressure is 45 kg/cm 2 and cured. The temperature is 190℃.

（層壓板）(Laminate)

覆金屬箔層壓板將金屬箔蝕刻後，獲得厚度約為0.18 mm、0.81 mm的層壓板。Metal foil clad laminate After etching the metal foil, a laminate with a thickness of approximately 0.18 mm and 0.81 mm is obtained.

針對本發明使用所述樹脂組合物製備的層壓板以及覆金屬箔層壓板，檢測其耐熱性（Tg，T300）、模量以及平面方向熱膨脹係數（CTE），其測試結果如下述實施例進一步給予詳加說明與描述。For the laminates and metal foil-clad laminates prepared using the resin composition of the present invention, their heat resistance (Tg, T300), modulus and plane direction thermal expansion coefficient (CTE) were tested. The test results are further given in the following examples. Explain and describe in detail.

表1至2中物性資料的測試方法如下：The test methods for the physical property data in Tables 1 to 2 are as follows:

玻璃化轉變溫度（Tg）：將在實施例和比較例中製備的覆銅箔層壓板試樣蝕刻掉銅箔，取長為60 mm、寬為8~12 mm、厚為0.81 mm的層壓板作為樣品，使用動態機械熱分析儀（DMA）進行測量，升溫速率10℃/min，結果取tanδ的轉變峰溫度，單位為ºC。Glass transition temperature (Tg): Etch away the copper foil from the copper-clad laminate samples prepared in the examples and comparative examples, and take a laminate with a length of 60 mm, a width of 8~12 mm, and a thickness of 0.81 mm. As a sample, a dynamic mechanical thermal analyzer (DMA) was used for measurement with a heating rate of 10°C/min. The result was taken as the transition peak temperature of tan δ in ºC.

T300帶銅：取長為6.5 mm、寬為6.5 mm、厚為0.846 mm的覆金屬箔層壓板作為樣品，樣品在105ºC烘箱中烘2小時後在乾燥器中冷卻至室溫。使用熱分析機械法（TMA）進行測量，升溫速率10ºC/min，從室溫升溫至300ºC，並在300ºC保持恆溫，分層時間即為從恆溫拐點到分層的時間，單位為min，對於在300ºC以下開始分層的樣品，記錄開始分層時的溫度，單位為ºC。T300 with copper: Take a metal foil-clad laminate with a length of 6.5 mm, a width of 6.5 mm, and a thickness of 0.846 mm as a sample. The sample is baked in a 105ºC oven for 2 hours and then cooled to room temperature in a desiccator. The thermal analysis mechanical method (TMA) is used for measurement. The heating rate is 10ºC/min, from room temperature to 300ºC, and maintained at a constant temperature at 300ºC. The stratification time is the time from the constant temperature inflection point to stratification, and the unit is min. For For samples that begin to stratify below 300ºC, record the temperature when stratification begins, in ºC.

XY向熱膨脹係數：將在實施例和比較例中製備的覆銅箔層壓板試樣蝕刻掉銅箔，取長為60 mm、寬為4 mm、厚為0.18 mm的層壓板作為樣品，玻纖經紗方向為X向，玻纖緯紗方向為Y向，樣品在105ºC烘箱中烘1小時後在乾燥器中冷卻至室溫。使用熱分析機械法（TMA）進行測量，升溫速率10ºC/min，從室溫升溫至300 ºC，測定從50℃到130℃下的平面方向熱膨脹係數，單位為ppm/ºC。XY thermal expansion coefficient: Etch away the copper foil from the copper-clad laminate samples prepared in the Examples and Comparative Examples, and take a laminate with a length of 60 mm, a width of 4 mm, and a thickness of 0.18 mm as a sample. The warp direction is the X direction, and the glass fiber weft direction is the Y direction. The sample is dried in a 105ºC oven for 1 hour and then cooled to room temperature in a desiccator. The thermal analysis mechanical method (TMA) is used to measure, with a heating rate of 10ºC/min, from room temperature to 300ºC, and the thermal expansion coefficient in the plane direction from 50℃ to 130℃, the unit is ppm/ºC.

剝離強度：取長為50 mm、寬為50 mm的覆金屬箔層壓板作為樣品，在樣品上用貼膠帶或其他辦法利用蝕刻製備金屬箔寬度為3.0 mm的試樣條。使用抗剝儀或其他等效儀器以50mm/min的速度在垂直方向施加壓力，使金屬箔剝離層壓板，可得到覆金屬箔層壓板的剝離強度，單位為N/mm。Peel strength: Take a metal foil-clad laminate with a length of 50 mm and a width of 50 mm as a sample. Use tape or other methods to prepare a metal foil sample strip with a width of 3.0 mm by etching on the sample. Use an anti-peel meter or other equivalent instrument to apply pressure in the vertical direction at a speed of 50mm/min to peel the metal foil from the laminate. The peel strength of the metal foil-clad laminate can be obtained in N/mm.

彎曲模量：將在實施例和比較例中製備的覆銅箔層壓板試樣蝕刻掉銅箔，取長為76.2 mm、寬為25.4 mm、厚為0.81 mm的層壓板作為樣品，採用材料試驗機進行測量，跨距為25.4 mm，試驗速度0.76mm/min，單位為GPa。Flexural modulus: The copper foil was etched away from the copper-clad laminate samples prepared in the examples and comparative examples, and a laminate with a length of 76.2 mm, a width of 25.4 mm, and a thickness of 0.81 mm was taken as a sample, and a material test was performed The measurement is carried out using a machine, the span is 25.4 mm, the test speed is 0.76mm/min, and the unit is GPa.

掃描電子顯微鏡（SEM）：觀察焊盤是否存在開裂，採用掃描電子顯微鏡進行觀察。樣品製作：由上下各兩張樹脂組合物製備的預浸料與高Tg FR-4板材（生益科技S1000-2M）加工成具備via-in-pad（焊盤下過孔）焊盤結構的四層PCB樣品，並將LTCC陶瓷器件貼裝在四層PCB上，PCB樣品經過-40℃(30min)—125℃(30min)的TCT 1000h測試後，用SEM觀察焊盤位置的形貌（每個樣品一式三份），若觀察到有裂紋出現，則為焊盤開裂，“0/3”表示每個樣品測量3次，0次出現裂紋。Scanning electron microscope (SEM): Observe whether there is cracking in the pad, use a scanning electron microscope to observe. Sample production: The prepreg prepared from the upper and lower resin compositions and the high Tg FR-4 plate (Shengyi Technology S1000-2M) are processed into a via-in-pad pad structure. Four-layer PCB sample, and the LTCC ceramic device was mounted on the four-layer PCB. After the PCB sample was tested at TCT 1000h at -40°C (30min)-125°C (30min), the morphology of the pad position was observed with SEM (each time Each sample is tested in triplicate). If cracks are observed, it means the pad is cracked. "0/3" means that each sample is measured 3 times and cracks appear 0 times.

表1（實施例） 序號 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 環氧樹脂A1 25 25     25 50       25 25 25 25 25 25 25 25 25   環氧樹脂A2     25       50                         環氧樹脂A3       25       50                       環氧樹脂A4 25 25 25 25 25       50 25 25 25 25 25 25 25 25 25 50 酚性固化劑B1 25 25 25 25   25 25 25 25 50     25 25 25   25 25   酚性固化劑B2         25           50                 酚性固化劑B3 25 25 25 25 25 25 25 25 25     50 25 25 25 25 25 25 50 有機矽橡膠C1 60   60 60 60 60 60 60 60 60 60 60 20 100 60 60     60 有機矽橡膠C2   60                                   有機矽橡膠C3                                 60     有機矽橡膠C4                                   60   無機填料D1 60 60 60 60 60 60 60 60 60 60     60 60 100 5 60 60 60 無機填料D2                     60                 無機填料D3                       60               促進劑E 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Tg（ºC） 175 175 175 175 175 180 180 185 170 180 185 170 175 175 175 175 165 175 155 T300帶銅(min) ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 50 30 ＞60 20 X向熱膨脹係數(ppm/ºC) 10 10 10 10 10 10 10 10 10 10 10 10 12 7 9 11 12 11 14 Y向熱膨脹係數(ppm/ºC) 10 10 10 10 10 10 10 10 10 10 10 10 12 7 9 11 12 11 14 剝離強度(N/mm) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.8 1.0 1.0 彎曲模量(GPa) 12 12 12 12 12 12 12 12 12 12 12 12 14 8 14 10 12 11 12 焊盤開裂 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 1/3 1/3 Table 1 (Example) serial number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Epoxy resin A1 25 25 25 50 25 25 25 25 25 25 25 25 25 Epoxy resin A2 25 50 Epoxy resin A3 25 50 Epoxy resin A4 25 25 25 25 25 50 25 25 25 25 25 25 25 25 25 50 Phenolic curing agent B1 25 25 25 25 25 25 25 25 50 25 25 25 25 25 Phenolic curing agent B2 25 50 Phenolic curing agent B3 25 25 25 25 25 25 25 25 25 50 25 25 25 25 25 25 50 Silicone rubber C1 60 60 60 60 60 60 60 60 60 60 60 20 100 60 60 60 Silicone rubber C2 60 Silicone rubber C3 60 Silicone rubber C4 60 Inorganic filler D1 60 60 60 60 60 60 60 60 60 60 60 60 100 5 60 60 60 Inorganic filler D2 60 Inorganic filler D3 60 Accelerator E 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Tg（ºC） 175 175 175 175 175 180 180 185 170 180 185 170 175 175 175 175 165 175 155 T300 with copper (min) >60 >60 >60 >60 >60 >60 >60 >60 >60 >60 >60 >60 >60 >60 >60 50 30 >60 20 X-direction thermal expansion coefficient (ppm/ºC) 10 10 10 10 10 10 10 10 10 10 10 10 12 7 9 11 12 11 14 Y-direction thermal expansion coefficient (ppm/ºC) 10 10 10 10 10 10 10 10 10 10 10 10 12 7 9 11 12 11 14 Peel strength(N/mm) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.8 1.0 1.0 Flexural modulus (GPa) 12 12 12 12 12 12 12 12 12 12 12 12 14 8 14 10 12 11 12 Cracked pad 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 0/3 1/3 1/3

表2（比較例） 序號 1 2 3 環氧樹脂A1 25 25 25 環氧樹脂A4 25 25 25 酚性固化劑B1 25 25 25 酚性固化劑B3 25 25 25 有機矽橡膠C1 15 120   無機填料D1 60 60 60 促進劑E 0.5 0.5 0.5 Tg（ºC） 175 140 175 T300帶銅（min） ＞60 10 ＞60 X向熱膨脹係數（ppm/ºC） 15 18 20 Y向熱膨脹係數（ppm/ºC） 15 18 20 剝離強度（N/mm） 1.0 0.5 1.0 彎曲模量（GPa） 15 8 17 焊盤開裂 3/3 3/3 3/3 Table 2 (Comparative Example) serial number 1 2 3 Epoxy resin A1 25 25 25 Epoxy resin A4 25 25 25 Phenolic curing agent B1 25 25 25 Phenolic curing agent B3 25 25 25 Silicone rubber C1 15 120 Inorganic filler D1 60 60 60 Accelerator E 0.5 0.5 0.5 Tg（ºC） 175 140 175 T300 with copper (min) >60 10 >60 X-direction thermal expansion coefficient (ppm/ºC) 15 18 20 Y-direction thermal expansion coefficient (ppm/ºC) 15 18 20 Peel strength (N/mm) 1.0 0.5 1.0 Flexural modulus (GPa) 15 8 17 Cracked pad 3/3 3/3 3/3

有機矽橡膠的用量過低時（比較例1），對模量和熱膨脹係數的降低作用不大，焊盤均開裂；有機矽橡膠的用量過高時（比較例2），有機矽橡膠團聚，導致性能劣化，如Tg下降，T300升高等，不滿足PCB加工要求；不含有機矽橡膠（比較例3），熱膨脹係數和模量均沒有下降，表明有機矽橡膠具備降低熱膨脹係數和模量的功能。When the dosage of organic silicone rubber is too low (Comparative Example 1), it has little effect on reducing the modulus and thermal expansion coefficient, and the pads are all cracked; when the dosage of organic silicone rubber is too high (Comparative Example 2), the organic silicone rubber agglomerates, Resulting in performance degradation, such as Tg decrease, T300 increase, etc., which does not meet PCB processing requirements; it does not contain organic silicone rubber (Comparative Example 3), and the thermal expansion coefficient and modulus did not decrease, indicating that organic silicone rubber has the ability to reduce the thermal expansion coefficient and modulus. Function.

而使用根據本發明的含有環氧樹脂（A）、酚性固化劑（B）、有機矽橡膠（C）、無機填料（D）的樹脂組合物，以環氧樹脂（A）和酚性固化劑（B）的總重量為100重量份計，有機矽橡膠（C）的量為20~100重量份，製備出的預浸料具備高耐熱性及低模量和熱膨脹係數的特性，可以抑制PCB加工過程中焊盤開裂的現象。實施例17使用粒徑大的有機矽橡膠C3，有機矽橡膠與樹脂結合力不強，導致T300和剝離強度有所降低，熱膨脹係數有所上升，所以優選有機矽橡膠的D50粒徑為1~20 µm；實施例18使用表面沒有包覆有由矽氧烷交聯形成的聚甲基倍半矽氧烷的有機矽橡膠C4，導致有機矽橡膠在樹脂組合物中分散不均，由於應力分布不均，引起熱膨脹係數上升，彎曲模量下降，對焊盤開裂有影響；實施例19環氧樹脂和酚性固化劑中均不含有芳烷基或雙環戊二烯結構，提高Tg、T300和降低熱膨脹係數的效果不如環氧樹脂或酚性固化劑中至少一種含有芳烷基或雙環戊二烯結構的實施例，對改善焊盤開裂有影響，所以優選環氧樹脂或酚性固化劑中至少一種含有芳烷基或雙環戊二烯結構。The resin composition containing epoxy resin (A), phenolic curing agent (B), organic silicone rubber (C), and inorganic filler (D) according to the present invention is used to cure the epoxy resin (A) and phenolic curing agent. The total weight of agent (B) is 100 parts by weight, and the amount of silicone rubber (C) is 20 to 100 parts by weight. The prepared prepreg has the characteristics of high heat resistance, low modulus and thermal expansion coefficient, and can inhibit The phenomenon of solder pad cracking during PCB processing. Example 17 uses organic silicone rubber C3 with a large particle size. The binding force between the organic silicone rubber and the resin is not strong, resulting in a decrease in T300 and peel strength, and an increase in the thermal expansion coefficient. Therefore, the D50 particle size of the organic silicone rubber is preferably 1~ 20 µm; Example 18 uses silicone rubber C4 whose surface is not coated with polymethylsilsesquioxane formed by siloxane cross-linking, resulting in uneven dispersion of the silicone rubber in the resin composition due to stress distribution. Uneven, causing the thermal expansion coefficient to increase and the flexural modulus to decrease, which has an impact on pad cracking; neither the epoxy resin nor the phenolic curing agent in Example 19 contains aralkyl or dicyclopentadiene structures, which increases Tg, T300 and The effect of reducing the thermal expansion coefficient is not as good as that of the embodiments in which at least one of the epoxy resin or phenolic curing agents contains an aralkyl or dicyclopentadiene structure, and has an impact on improving solder pad cracking, so epoxy resin or phenolic curing agents are preferred. At least one contains an aralkyl or dicyclopentadiene structure.

以上實施例，並非對本發明的組合物的含量作任何限制，凡是依據本發明的技術實質或組合物的重量份或含量對以上實施例所作的任何細微修改、等同變化與修飾，均仍屬於本發明技術方案的範圍內。The above examples do not place any restrictions on the content of the composition of the present invention. Any slight modifications, equivalent changes and modifications made to the above examples based on the technical essence of the present invention or the weight part or content of the composition still belong to the present invention. within the scope of the technical solution of the invention.

申請人聲明，本發明通過上述實施例來說明本發明的詳細組成，但本發明並不局限於上述詳細組成，即不意味著本發明必須依賴上述詳細組成才能實施。所屬技術領域的技術人員應該明瞭，對本發明的任何改進、對本發明產品各原料的等效替換及輔助成分的添加、具體方式的選擇等，均落在本發明的保護範圍和公開範圍之內。The applicant declares that the present invention illustrates the detailed composition of the present invention through the above embodiments, but the present invention is not limited to the above detailed composition, that is, it does not mean that the present invention must rely on the above detailed composition to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacement of raw materials of the product of the present invention, addition of auxiliary ingredients, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims (8)

一種樹脂組合物，其特徵在於，所述樹脂組合物由環氧樹脂(A)、酚性固化劑(B)和有機矽橡膠(C)和任選的其他組分組成；其中，所述其他組分為選自無機填料(D)、促進劑(E)和添加劑中的至少一種，其中所述添加劑選自阻燃劑、熱穩定劑、光穩定劑、抗氧化劑和潤滑劑中的一種或多種；其中所述酚性固化劑(B)為酚醛樹脂；其中所述環氧樹脂(A)和酚性固化劑(B)中的至少一種含有芳烷基結構，或者所述環氧樹脂(A)含有雙環戊二烯結構；其中，所述有機矽橡膠(C)為含乙烯基的聚矽氧烷與含矽氫的聚矽氧烷通過加成聚合得到的聚合物；並且其中，以環氧樹脂(A)和酚性固化劑(B)的總重量為100重量份計，所述有機矽橡膠(C)的量為30~70重量份，所述有機矽橡膠(C)表面包覆有由矽氧烷鍵交聯形成的聚甲基倍半矽氧烷。 A resin composition, characterized in that the resin composition is composed of epoxy resin (A), phenolic curing agent (B), organic silicone rubber (C) and optional other components; wherein, the other The component is at least one selected from the group consisting of inorganic filler (D), accelerator (E) and additives, wherein the additives are selected from one group consisting of flame retardants, heat stabilizers, light stabilizers, antioxidants and lubricants, or A variety of; wherein the phenolic curing agent (B) is a phenolic resin; wherein at least one of the epoxy resin (A) and the phenolic curing agent (B) contains an aralkyl structure, or the epoxy resin ( A) contains a dicyclopentadiene structure; wherein, the organic silicone rubber (C) is a polymer obtained by addition polymerization of vinyl-containing polysiloxane and silicon-hydrogen-containing polysiloxane; and wherein, The total weight of the epoxy resin (A) and the phenolic curing agent (B) is 100 parts by weight, the amount of the organic silicone rubber (C) is 30 to 70 parts by weight, and the surface of the organic silicone rubber (C) is coated with Coated with polymethylsesquioxane formed by cross-linking of siloxane bonds. 根據請求項1所述的樹脂組合物，其中所述有機矽橡膠(C)的D50粒徑為1~20μm。 The resin composition according to claim 1, wherein the D50 particle size of the organic silicone rubber (C) is 1 to 20 μm. 根據請求項1所述的樹脂組合物，其中所述樹脂組合物包含無機填料(D)。 The resin composition according to claim 1, wherein the resin composition contains an inorganic filler (D). 根據請求項3所述的樹脂組合物，其中以環氧樹脂(A)和酚性固化劑(B)的總重量為100重量份計，所述無機填料(D)的量為5~100重量份。 The resin composition according to claim 3, wherein the amount of the inorganic filler (D) is 5 to 100 parts by weight based on the total weight of the epoxy resin (A) and the phenolic curing agent (B) being 100 parts by weight. share. 一種預浸料，其特徵在於，所述預浸料包括基材及通過浸漬或塗覆而附著於基材上的如請求項1~4中任一項所述的樹脂組合物。 A prepreg, characterized in that the prepreg includes a base material and a resin composition as described in any one of claims 1 to 4 attached to the base material by impregnation or coating. 一種層壓板，其特徵在於，所述層壓板包括至少一張如請求項5所述的預浸料。 A laminate, characterized in that the laminate includes at least one piece of the prepreg according to claim 5. 一種覆金屬箔層壓板，其特徵在於，所述覆金屬箔層壓板包括至少一張如請求項5所述的預浸料及覆於預浸料一側或兩側的金屬箔。 A metal foil-clad laminate, characterized in that the metal foil-clad laminate includes at least one prepreg as described in claim 5 and a metal foil covering one or both sides of the prepreg. 一種印刷電路板，其特徵在於，所述印刷電路板包括至少一張根據請求項5所述的預浸料。 A printed circuit board, characterized in that the printed circuit board includes at least one piece of prepreg according to claim 5.
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