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WO2019127388A1 - 树脂组合物、预浸料、层压板以及覆金属箔层压板 - Google Patents

树脂组合物、预浸料、层压板以及覆金属箔层压板 Download PDF

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Publication number
WO2019127388A1
WO2019127388A1 PCT/CN2017/119902 CN2017119902W WO2019127388A1 WO 2019127388 A1 WO2019127388 A1 WO 2019127388A1 CN 2017119902 W CN2017119902 W CN 2017119902W WO 2019127388 A1 WO2019127388 A1 WO 2019127388A1
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WO
WIPO (PCT)
Prior art keywords
resin
mass
molecular weight
resin composition
formula
Prior art date
Application number
PCT/CN2017/119902
Other languages
English (en)
French (fr)
Inventor
唐军旗
李志光
Original Assignee
广东生益科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to PCT/CN2017/119902 priority Critical patent/WO2019127388A1/zh
Priority to EP17936498.9A priority patent/EP3744788B1/en
Priority to JP2020515255A priority patent/JP6964764B2/ja
Priority to KR1020207012854A priority patent/KR102313621B1/ko
Publication of WO2019127388A1 publication Critical patent/WO2019127388A1/zh

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    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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    • H—ELECTRICITY
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Definitions

  • the present invention relates to the field of packaging materials for electronic products, and more particularly to a resin composition and a prepreg, a laminate, and a metal foil-clad laminate prepared using the same.
  • packaging density is increasing, such as POP package (package stack technology), MCP package (multi-chip package), and the requirements for thermal expansion coefficient (CTE) and rigidity of package substrates are increasing.
  • CTE thermal expansion coefficient
  • rigidity of package substrates are increasing.
  • BGA packages ball grid array packages
  • low XY CTE and high rigidity package substrates can exhibit warpage reduction.
  • the low thermal expansion coefficient and high rigidity of the package substrate are required. As the package density becomes higher and higher, the thermal expansion coefficient becomes lower and the rigidity becomes higher and higher. For a package form with a single package form, the effect of reducing warpage can be exhibited, but for a package form with a complicated package form, it is obviously not applicable due to its fixing property. At the same time, the thermal stress generated by the components such as the chip during the installation process cannot be alleviated, and the welded portion is liable to cause cracking and the circuit is ineffective.
  • the package substrate is easily hygroscopic under high temperature and high humidity.
  • evaporation of water causes voids between the resin and the resin, between the resin and the substrate, and between the resin and the metal foil, resulting in circuit failure.
  • the ever-increasing use of ambient temperature places higher demands on the heat resistance of the package substrate.
  • An object of the present invention is to provide a resin composition which uses a prepreg, a laminate, and a metal foil-clad laminate prepared by the resin composition to have a low XY coefficient of thermal expansion and modulus, and at the same time, has good heat resistance. And heat and humidity resistance.
  • the present invention adopts the following technical means:
  • One aspect of the present invention provides a resin composition
  • a resin composition comprising an epoxy resin (A), a cyanate resin (B), a bismaleimide resin (C), and having the formula (1), formula (2) a structure represented by the formula (3) and the formula (4), a high molecular weight resin (D) having a weight average molecular weight of 100,000 or more and 200,000 or less, and an inorganic filler (E).
  • k:l:m:n is a molar fraction, wherein k+l+m+n ⁇ 1, 0 ⁇ k ⁇ 0.30, 0.01 ⁇ l ⁇ 0.20, 0.10 ⁇ m ⁇ 0.60, 0 ⁇ n ⁇ 0.60;
  • R 1 is a hydrogen atom or an alkyl group of 1 to 8 carbon atoms; in the formula (3), R 2 and R 3 are each independently a hydrogen atom or an alkyl group of 1 to 8 carbon atoms;
  • R 4 is a hydrogen atom or an alkyl group of 1 to 8 carbon atoms, and R 5 is Ph(phenyl), -COO(CH 2 ) 2 Ph or -COOCH 2 Ph.
  • the R 1 is a hydrogen atom or a methyl group
  • the R 2 is a hydrogen atom or a methyl group
  • the R 3 is an alkyl group of 1 to 8 carbon atoms
  • the R 4 is a hydrogen atom or a base.
  • the content of the high molecular weight resin (D) is 100% by mass relative to the total content of the epoxy resin (A), the cyanate resin (B), and the bismaleimide resin (C). ⁇ 60% by mass.
  • the high molecular weight resin (D) has an epoxy value in the range of 0.10 eq/kg to 0.80 eq/kg; preferably, the high molecular weight resin (D) has an epoxy value of 0.35 eq/kg. Further, the high molecular weight resin (D) has an epoxy value in the range of 0.40 eq/kg to 0.65 eq/kg.
  • the content of the epoxy resin (A) is 100% by mass based on the total content of the epoxy resin (A), the cyanate resin (B), and the bismaleimide resin (C). 20 to 80% by mass, preferably 30 to 70% by mass, and more preferably 40 to 60% by mass.
  • the content of the cyanate resin (B) is 100% by mass based on the total content of the epoxy resin (A), the cyanate resin (B), and the bismaleimide (C). 15 to 70% by mass, preferably 20 to 60% by mass, and more preferably 20 to 50% by mass.
  • the content of the bismaleimide resin (C) is relative to the total content of the epoxy resin (A), the cyanate resin (B), and the bismaleimide resin (C). 100% by mass is 5 to 50% by mass, preferably 10 to 40% by mass.
  • the content of the inorganic filler (E) is 10% by mass based on 100% by mass of the total content of the epoxy resin (A), the cyanate resin (B), and the bismaleimide resin (C). ⁇ 300% by mass, preferably 30 to 270% by mass, and more preferably 50 to 250% by mass.
  • Another aspect of the present invention provides a prepreg comprising a substrate and the above resin composition attached to the substrate by dipping or coating.
  • Another aspect of the invention provides a laminate comprising at least one of the above prepregs.
  • Another aspect of the present invention provides a metal foil-clad laminate comprising at least one of the above prepreg and a metal foil coated on one or both sides of the prepreg.
  • the resin composition provided by the present invention has advantages of good heat resistance, heat and humidity resistance, and low coefficient of thermal expansion and modulus, and prepregs, laminates, and metal foil-clad laminates prepared using the resin composition. It has good heat resistance, heat and humidity resistance, and low coefficient of thermal expansion and modulus, which helps to reduce the warpage of the package carrier. It is suitable for packages with various package shapes.
  • the resin composition of the present invention contains an epoxy resin (A), a cyanate resin (B), a bismaleimide resin (C), a high molecular weight resin (D), and an inorganic filler (E), and optionally Promoter (F) and other additives.
  • A epoxy resin
  • B cyanate resin
  • C bismaleimide resin
  • D high molecular weight resin
  • E inorganic filler
  • F Promoter
  • the epoxy resin (A) is a matrix resin in the resin composition of the present invention, which is selected from an organic compound containing at least two epoxy groups in a molecular structure, and may be selected from a bisphenol A type epoxy resin and a bisphenol F type.
  • the epoxy resin of the present invention is further preferably a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol type.
  • Epoxy resin, naphthol novolac type epoxy resin, bismuth type epoxy resin, phenolphthalein type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, aralkyl phenolic type epoxy resin, in the molecule Any one or a mixture of at least two kinds of epoxy resins having an arylene ether structure, particularly preferably a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol novolac type epoxy resin, a fluorene type ring Any one or a mixture of at least two of an oxyresin, a phenolphthalein type epoxy resin, an aralkyl novolac type epoxy resin, and an epoxy resin having an arylene ether structure in its molecule.
  • the epoxy resin (A) has at least a biphenyl type epoxy resin having a structure represented by the formula (5)
  • the formula (5) The content of the biphenyl type epoxy resin of the structure shown is 0 to 80% by mass, preferably 0 to 60% by mass based on 100% by mass of the total epoxy resin content.
  • R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms, and x is 20 or less. Integer.
  • the content of the epoxy resin (A) in the resin composition may be 100% by mass based on the total content of the epoxy resin (A), the cyanate resin (B), and the bismaleimide resin (C). 20 to 80% by mass, preferably 30 to 70% by mass, more preferably 40 to 60% by mass, can ensure the resin composition has good processability, and the rigidity and heat resistance of the resin composition are not excessively reduced.
  • the cyanate resin (B) is a thermosetting resin component in the resin composition of the present invention, and is used in combination with the epoxy resin (A) to improve the adhesion of the resin composition, particularly adhesion to a metal foil and heat resistance. Sex and dielectric properties, etc.
  • the content of the cyanate resin (B) in the resin composition is limited, and optionally, the content of the cyanate resin (B) is relative to the epoxy resin (A), the cyanate resin (B), and the double
  • the total content of the maleimide resin (C) is from 100 to 70% by mass, preferably from 20 to 60% by mass, and more preferably from 20 to 50% by mass.
  • the content of the cyanate resin is more than 70% by mass, the water absorption of the laminate is improved due to the introduction of the polar group cyanate group, and the moist heat resistance is deteriorated, and the content of the cyanate resin is less than 15% by mass.
  • the dielectric properties of the laminate are lowered due to a decrease in the content of the triazine ring of the cyanate ester-based self-polymerization product, and the glass transition temperature is lowered.
  • the cyanate resin (B) may be selected from a cyanate monomer or a cyanate prepolymer having at least two cyanate groups in a molecular structure, preferably selected from the group consisting of bisphenol A type cyanate resins, bisphenol F.
  • Type cyanate resin bisphenol M type cyanate resin, bisphenol S type cyanate resin, bisphenol E type cyanate resin, bisphenol P type cyanate resin, novolac type cyanate resin, Naphthol type cyanate resin, naphthol novolac type cyanate resin, dicyclopentadiene type cyanate resin, aralkyl type cyanate resin, aralkyl novolac type cyanate resin, bisphenol A type Cyanate ester prepolymer, bisphenol F type cyanate prepolymer, bisphenol M type cyanate prepolymer, bisphenol S type cyanate prepolymer, bisphenol E type cyanate prepolymer , bisphenol P type cyanate prepolymer, novolac type cyanate prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, dicyclopentadiene type cyanate
  • the bismaleimide resin (C) mainly serves to further improve the mechanical properties, heat resistance, and planar thermal expansion coefficient of the laminate resin composition.
  • the maleimide compound of the present invention is not particularly limited and may be selected from compounds having at least one maleimide group in a molecular structure, preferably having at least two maleimide groups in a molecular structure.
  • a compound further preferably from N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N- (2,6-Dimethylphenyl)maleimide, bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidobenzene) Oxy)-phenyl)propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleamide) Aminophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide, biphenyl-containing horse Imidide
  • the content of the bismaleimide (C) may be 5 to 5% by mass based on the total content of the epoxy resin (A), the cyanate resin (B), and the bismaleimide resin (C). 50% by mass, preferably 10 to 40% by mass.
  • the high molecular weight resin (D) is an epoxy-modified acrylate-based resin which mainly functions as a low-elastic resin component in the resin composition of the present invention.
  • the high molecular weight resin (D) is a resin having a structure represented by the formula (1), the formula (2), the formula (3), and the formula (4), and having a weight average molecular weight of 100,000 or more and 200,000 or less.
  • R 1 is a hydrogen atom or an alkyl group of 1-8 carbon atoms
  • R 2 and R 3 are each independently a hydrogen atom or 1-8 carbon atoms
  • R 4 is a hydrogen atom or an alkyl group of 1 to 8 carbon atoms
  • R 5 is Ph(phenyl) or -COOCH 2 Ph or -COOCH 2 CH 2 Ph.
  • the R 1 is a hydrogen atom or a methyl group
  • the R 2 is a hydrogen atom or a methyl group
  • the R 3 is an alkyl group of 1 to 8 carbon atoms
  • the R 4 is a hydrogen atom or a base.
  • the structures of the formula (1), the formula (2), the formula (3) and the formula (4) are continuous or discontinuous.
  • the structure of the formula (1) of the high molecular weight resin (D) contains a cyano group, which can react with the cyanate resin (B) and the bismaleimide resin (C) under high temperature reaction, and the introduction of the cyano group can improve the resin combination. Heat resistance of materials, prepregs, laminates and metal foil laminates.
  • the structure of the formula (2) of the high molecular weight resin (D) contains an epoxy group, and the curing strength of the high molecular weight resin (D) and the resin composition can be improved, thereby improving the heat resistance and moist heat resistance of the resin composition.
  • the content of the epoxy group the content of the structure of the formula (2) in the high molecular weight resin (D) may be 0.01 to 0.20 (in terms of mole fraction), and the epoxy value of the high molecular weight resin (D) may be 0.10 eq/kg. In the range of 0.80 eq/kg, it is preferably in the range of 0.35 eq/kg to 0.70 eq/kg, and more preferably in the range of 0.40 eq/kg to 0.65 eq/kg.
  • the epoxy value is the number of equivalents of the epoxy group in 1 kg of the high molecular weight resin (D). If the epoxy value is less than 0.10 eq/kg, the compatibility of the high molecular weight resin (D) in the resin composition is lowered, and the heat resistance of the resin composition, the prepreg, the laminate, and the metal foil-clad laminate is The heat and humidity resistance will decrease. When the epoxy value is higher than 0.80 eq/kg, the high molecular weight resin (D) increases the crosslinking density of the resin composition, lowers the elasticity, and improves the modulus.
  • the high molecular weight resin (D) has the structure of the formula (2) and the formula (3) containing an ester group
  • the structure of the formula (4) may contain an ester group, and the ester group is highly hygroscopic, but the ester group of the formula (2) and the epoxidized glycidol
  • the ester group in the structure of the formula (4) contains a benzene ring structure, both of which can improve the bonding strength of the resin composition, and the cured product of the resin composition still has good heat and humidity resistance in the case of moisture absorption, thereby The heat and humidity resistance of the resin composition, the prepreg, the laminate, and the metal foil-clad laminate can be improved.
  • the high molecular weight resin (D) has a weight average molecular weight of 100,000 or more and 200,000 or less.
  • the weight average molecular weight of the high molecular weight resin (D) is 100,000 or less, the heat resistance of the high molecular weight resin (D) is deteriorated, and the prepreg is sticky, affecting storage and subsequent processing, and it is difficult to achieve low elasticity and Good resistance to heat and humidity.
  • the weight average molecular weight of the high molecular weight resin (D) is 200,000 or more, the viscosity of the varnish liquid (the stage A state) of the resin composition is too large, which affects the dispersion uniformity of the inorganic filler (E) in the resin composition and the substrate.
  • the wettability, while the high molecular weight resin (D) differs greatly from the melt flowability of the other components of the resin composition, and the high molecular weight resin (D) resin layer is present in the laminate (after curing).
  • the content of the high molecular weight resin (D) is 5 to 60% by mass based on 100% by mass of the total content of the epoxy resin (A), the cyanate resin (B), and the bismaleimide resin (C). If the content of the high molecular weight resin (D) is less than 5% by mass, the high molecular weight resin (D) cannot form an effective or large continuous phase in the resin composition, and does not function to lower the modulus, if the high molecular weight resin When the content of the (D) is more than 60% by mass, the high molecular weight resin (D) is not uniformly dispersed in the resin composition, and the viscosity of the resin composition in the varnish state is too high, so that it is difficult to effectively wet the substrate.
  • the weight average molecular weight of the high molecular weight resin (D) is less than 100,000 and the content is more than 60% by mass, since the high molecular weight resin (D) itself has low melt fluidity, it does not affect uniform dispersion of the inorganic filler;
  • the weight average molecular weight of the high molecular weight resin (D) is more than 200,000 and the content is less than 5% by mass, since the high fluidity of the high molecular weight resin (D) itself is high, the uniform dispersion of the inorganic filler is still affected.
  • the inorganic filler (E) is contained in the resin composition, and the heat resistance and moist heat resistance of the resin composition and the laminate can be improved, and the dimensional stability and the thermal expansion coefficient of the laminate and the metal foil-clad laminate can be improved.
  • the type of the inorganic filler (E) is not limited, and may be selected from crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, aluminum hydroxide, magnesium hydroxide, and borax.
  • crystalline silica fused silica
  • amorphous silica amorphous silica
  • spherical silica hollow silica
  • aluminum hydroxide magnesium hydroxide
  • borax borax.
  • molybdenum, molybdenum oxide, zinc molybdate, titanium dioxide, zinc oxide, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, composite silicon micropowder, glass powder, short glass fiber or hollow glass crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, aluminum hydroxide, magnesium hydroxide, and borax.
  • crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, hydrogen are preferred.
  • the content of the inorganic filler (E) is 10% by mass based on 100% by mass of the total content of the epoxy resin (A), the cyanate resin (B), and the bismaleimide resin (C). ⁇ 300% by mass, preferably 30 to 270% by mass, and more preferably 50 to 250% by mass.
  • a coupling agent may be added for surface treatment.
  • the coupling agent is not limited, and is generally selected from a silane coupling agent, and the type of the silane coupling agent is not limited, and examples thereof include an epoxy silane coupling agent, an aminosilane coupling agent, a vinyl silane coupling agent, and a styryl group.
  • Silane coupling agent isobutylene silane coupling agent, propylene silane coupling agent, ureido silane coupling agent, mercapto silane coupling agent, chloropropyl silane coupling agent, sulfurized silane coupling agent, isocyanic acid a salt-based silane coupling agent or the like.
  • the resin composition further needs to be added with a promoter (F) selected from a curing accelerator capable of promoting curing of a cyanate resin or an epoxy resin, which is specifically
  • a promoter (F) selected from a curing accelerator capable of promoting curing of a cyanate resin or an epoxy resin, which is specifically
  • An organic salt of a metal such as copper, zinc, cobalt, nickel or manganese, an imidazole and a derivative thereof, a tertiary amine or the like may be used alone or in combination of two or more.
  • the resin composition needs to be added with various additives, and may be a flame retardant, a heat stabilizer, a light stabilizer, an antioxidant, a lubricant, or the like.
  • the resin composition of the present invention can dissolve, mix, prepolymerize, pre-react, and agitate the epoxy resin (A), cyanate resin (B), bismaleimide resin (C), and high molecular weight resin. (D), etc. to prepare. It is necessary to use an organic solvent to dissolve the resin, as long as the various resins can be completely dissolved and the separation does not occur, and examples thereof include methanol, ethanol, ethylene glycol, acetone, methyl ethyl ketone, methyl ethyl ketone, and cyclohexane.
  • One or more solvents can be used.
  • the prepreg of the present invention is formed of a resin composition of the present invention and a substrate in a semi-cured state. Specifically, the prepreg is formed by a process in which a resin composition in a varnish state wets a substrate, and the solvent is volatilized by heating to be converted into a semi-cured state.
  • the substrate of the present invention is not particularly limited, and is usually a woven fabric, a nonwoven fabric, a roving, a short fiber, a fiber paper, etc.
  • the material may be an inorganic fiber (for example, E glass, D glass, L glass, M glass, S glass, Glass fibers such as T glass, NE glass, and quartz, or organic fibers (for example, polyimide, polyamide, polyester, polyphenylene ether, liquid crystal polymer, etc.) are preferably glass fiber cloth.
  • the laminate of the present invention comprises at least one of the above prepregs.
  • the metal foil-clad laminate of the present invention comprises at least one of the above prepreg and a metal foil coated on one or both sides of the prepreg.
  • a metal foil-clad laminate can be produced by laminating 1 to 20 prepregs and laminating a metal foil such as copper or aluminum on one or both sides thereof.
  • Epoxy resin (A1) biphenyl aralkyl type epoxy resin ("NC-3000-H” manufactured by Nippon Kayaku Co., Ltd., structure shown by formula (5))
  • Epoxy resin (A2) naphthalene-based epoxy resin ("HP-6000” manufactured by DIC Corporation, structure shown in formula (6))
  • R 10 in the formula (6) is a hydrogen atom, a methyl group or an ethyl group.
  • Epoxy resin (A3) bisphenol A type epoxy resin ("828US” manufactured by Mitsubishi Chemical Corporation)
  • Cyanate resin (B1) bisphenol A type cyanate resin ("BA-3000S” manufactured by Lonza Co., Ltd.)
  • Cyanate resin (B2) phenolic cyanate resin ("PT-30S” manufactured by Lonza Co., Ltd.)
  • Bismaleimide resin (C1) bis(3-ethyl-5-methyl-4-bismaleimidophenyl)methane ("TY-2002” manufactured by Tianyi Chemical Co., Ltd.)
  • Bismaleimide resin (C2) diphenylmethane type bismaleimide resin (made by Huading Polymer Synthetic Resin Co., Ltd.)
  • High molecular weight resin (D1) epoxy-modified acrylate resin ("PMS-22-1" manufactured by Nagase ChemteX Co., Ltd., weight average molecular weight 100,000, epoxy value 0.63 eq/kg)
  • High molecular weight resin (D2) epoxy-modified acrylate resin ("PMS-22-1 modified MW1" manufactured by Nagase ChemteX Co., Ltd., weight average molecular weight 200,000, epoxy value 0.63 eq/kg)
  • High molecular weight resin (D3) epoxy-modified acrylate resin ("PMS-22-4" manufactured by Nagase ChemteX Co., Ltd., weight average molecular weight 100,000, epoxy value 0.63 eq/kg)
  • High molecular weight resin (D4) epoxy modified acrylate resin ("PMS-22-4 modified MW1" manufactured by Nagase ChemteX Co., Ltd., weight average molecular weight 200,000, epoxy value 0.63 eq/kg)
  • High molecular weight resin (D5) epoxy-modified acrylate resin ("PMS-19-5 modified MW1" manufactured by Nagase ChemteX Co., Ltd., weight average molecular weight 100,000, epoxy value 0.40 eq/kg)
  • High molecular weight resin (D6) epoxy modified acrylate resin ("PMS-22-5" manufactured by Nagase ChemteX Co., Ltd., weight average molecular weight 100,000, epoxy value 0.21 eq/kg)
  • (D1) to (D6) have a structure represented by the formula (1), the formula (2), the formula (3), and the formula (4), k + l + m + n ⁇ 1, 0 ⁇ k ⁇ 0.30, 0.01 ⁇ l ⁇ 0.20, 0.10 ⁇ m ⁇ 0.60, 00 ⁇ n ⁇ 0.60.
  • High molecular weight resin (D7) epoxy-modified acrylate resin ("PMS-22-5 modified EP1" manufactured by Nagase ChemteX Co., Ltd., weight average molecular weight 100,000, epoxy value 0.09 eq/kg), wherein (D7) has The structure represented by the formula (1), the formula (2), the formula (3), and the formula (4), but the epoxy value is less than 0.10 eq/kg.
  • High molecular weight resin (D8) epoxy-modified acrylate resin ("PMS-19-5" manufactured by Nagase ChemteX Co., Ltd., weight average molecular weight: 700,000, epoxy value: 0.40 eq/kg), wherein (D8) has the formula (1) A structure represented by the formula (2), the formula (3), and the formula (4), but having a weight average molecular weight of more than 200,000.
  • Organometallic salt promoter zinc octoate (manufactured by leading chemical company, model "BICATZ”)
  • Imidazole accelerator 2-ethyl-4-methylimidazole ("2E4MI” manufactured by Shikoku Chemicals Co., Ltd.)
  • glass fiber cloth (2116 glass fiber cloth made by Nitto Spin Co., Ltd., single weight 104g/m 2 , thickness 92 ⁇ m)
  • each component was calculated as a solid matter.
  • the resin component of the varnish state was prepared by mixing and diluting with dimethylformamide and methyl ethyl ketone in the mass ratio shown in Example 2 or Table 2 (Comparative Example).
  • the resin composition in the varnish state was infiltrated with Nippon Spinning 2116 glass fiber cloth, and it was heat-dried in a blast oven at 165 ° C for 7 minutes to convert the resin composition in a varnish state into a resin composition in a semi-cured state.
  • the thickness was controlled to be 130 to 140 ⁇ m, thereby producing a prepreg.
  • the laminate prepared by using the resin composition of the present invention and the metal foil-clad laminate were tested for heat resistance (Tg, T300), moist heat resistance, and plane direction thermal expansion coefficient (CTE), and the test results were as follows. Further details and descriptions will be given.
  • Glass transition temperature (Tg) A laminate having a length of 60 mm, a width of 8 to 12 mm, and a thickness of 1.0 mm was used as a sample, and was measured using a dynamic mechanical thermal analyzer (DMA) at a heating rate of 10 ° C/min. The peak temperature of tan ⁇ , in °C.
  • DMA dynamic mechanical thermal analyzer
  • T300 with copper A metal foil laminate having a length of 6.5 mm, a width of 6.5 mm, and a thickness of 1.1 mm was taken as a sample, and the sample was baked in an oven at 105 ° C for 2 hours and then cooled to room temperature in a desiccator. The measurement was carried out using a thermal analysis mechanical method (TMA) at a heating rate of 10 ° C/min, from room temperature to 300 ° C, and at 300 ° C for 10 min. The delamination time was the time from the constant temperature inflection point to the delamination, in min. For samples starting to stratify below 300 °C, record the temperature at which delamination begins, in °C.
  • TMA thermal analysis mechanical method
  • XY-direction thermal expansion coefficient a laminate with a length of 60 mm, a width of 4 mm, and a thickness of 0.25 mm was taken as a sample, the direction of the glass warp yarn was X direction, the direction of the glass fiber weft yarn was Y direction, and the sample was baked in an oven at 105 ° C for 1 hour. Cool to room temperature in a desiccator. The measurement was carried out by a thermal analysis mechanical method (TMA) at a heating rate of 10 ° C/min, and the temperature was raised from room temperature to 300 ° C, and the temperature was raised twice. After the first temperature increase, the temperature was cooled to room temperature, and the sample was again subjected to the second temperature rise. The coefficient of thermal expansion in the plane direction at a secondary temperature rise of 50 ° C to 130 ° C, in ppm/°C.
  • TMA thermal analysis mechanical method
  • Moisture and heat resistance A laminate having a length of 50 mm, a width of 50 mm, and a thickness of 1.0 mm was taken as a sample, and the sample was treated with a high pressure cooking tester at 121 ° C and two atmospheres for 2 hours or 3 hours, and then the sample was at 288 ° C. The tin furnace is immersed in tin, and the time of no foaming is recorded. If it is more than 300 s, the heat and humidity resistance is passed.
  • Peel strength A metal foil laminate having a length of 50 mm and a width of 50 mm was taken as a sample, and a sample strip having a metal foil width of 3.0 mm was prepared by etching on the sample by tape or the like.
  • the peel strength of the metal foil-clad laminate is obtained in units of N/mm by applying pressure in a vertical direction at a speed of 50 mm/min using an anti-stripping instrument or other equivalent instrument to peel the metal foil.
  • Flexural modulus A laminate with a length of 76.2 mm and a width of 25.4 mm was used as a sample, and the material was tested by a material testing machine. The span was 25.4 mm, the test speed was 0.76 mm/min, and the maximum bending strength was converted into a bending mold according to the formula. Quantity, the unit is GPa.
  • SEM Scanning Electron Microscopy
  • a high molecular weight resin having a structure represented by the formula (1), the formula (2), the formula (3), and the formula (4) and having a weight average molecular weight of 100,000 or more and 200,000 or less is added (D).
  • k, l, m and n are molar fractions, k + l + m + n ⁇ 1, 0 ⁇ k ⁇ 0.30, 0.01 ⁇ l ⁇ 0.20, 0.10 ⁇ m ⁇ 0.60, 0 ⁇ n ⁇ 0.60,
  • the Tg of the laminate can be increased, and the XY coefficient of thermal expansion of the laminate can be effectively reduced, and at the same time, the modulus can be lowered, and when used as a prepreg, The stress caused by the difference in thermal expansion between the chip component and the printed circuit board during solder heating is alleviated, so that weld cracks which are easily generated in the joint portion are reduced.

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Abstract

本发明提供一种树脂组合物，使用该树脂组合物制备的预浸料、层压板以及覆金属箔层压板具有良好的耐热性、耐湿热性和低的热膨胀系数及模量。本发明的树脂组合物含有：环氧树脂（A）、氰酸酯树脂（B）、双马来酰亚胺树脂（C）、具有以式（1）、式（2）、式（3）和式（4）表示的结构、重均分子量在10万以上20万以下的高分子量树脂（D）以及无机填充材料（E）。

Description

树脂组合物、预浸料、层压板以及覆金属箔层压板 技术领域
本发明涉及用于电子产品的封装件技术领域，尤其涉及一种树脂组合物及使用其制备的预浸料、层压板以及覆金属箔层压板。
背景技术
封装形式的发展，封装密度越来越高，如POP封装(封装体叠层技术)，MCP封装(多芯片封装)，对封装基板的热膨胀系数(CTE)和刚性的要求越来越高。对于封装形态单一的封装形式，如BGA封装(球栅阵列封装)，低XY向CTE和高刚性的封装基板能显示出降低翘曲的效果。
对于封装形态复杂的封装形式，由于其固定性，对不同部位的翘曲要求不同，显然不适用。同时，芯片等元件在安装过程中产生的热应力不能得到缓解，焊接部位极易产生开裂，使电路失效。
发明内容
出于低翘曲的要求，对封装基板提出低热膨胀系数、高刚性的要求，随着封装密度越来越高，热膨胀系数越来越低、刚性越来越高成为趋势。对于封装形态单一的封装形式，能显示出降低翘曲的效果，但对于封装形态复杂的封装形式，由于其固定性，显然不适用。同时，芯片等元件在安装过程中产生的热应力不能得到缓解，焊接部位极易产生开裂，使电路失效。
另外，封装基板在高温高湿下容易吸湿，在高温加工过程中，水分蒸发导致树脂与树脂之间、树脂与基材之间以及树脂与金属箔之间存在空洞，导致电路失效。使用环境温度的不断提高，对封装基板的耐热性提出更高的要求。
本发明的目的在于提供一种树脂组合物，使用该树脂组合物制备的预浸料、层压板以及覆金属箔层压板具有低的XY向热膨胀系数和模量，同时，具有良好的耐热性和耐湿热性。
为实现上述目的，本发明采用如下技术手段：
本发明的一个方面提供一种树脂组合物，含有环氧树脂(A)、氰酸酯树脂(B)、双马来酰亚胺树脂(C)、具有以式(1)、式(2)、式(3)和式(4)表 示的结构、重均分子量在10万以上20万以下的高分子量树脂(D)以及无机填充材料(E)，
Figure PCTCN2017119902-appb-000001
k：l：m：n为摩尔分率，其中，k+l+m+n≤1，0≤k≤0.30，0.01≤l≤0.20，0.10≤m≤0.60，0≤n≤0.60；式(2)中，R 1为氢原子或1-8个碳原子的烷基；式(3)中，R 2、R 3各自独立的为氢原子或1-8个碳原子的烷基；式(4)中，R 4为氢原子或1-8个碳原子的烷基，R 5为Ph(苯基)、-COO(CH 2) 2Ph或-COOCH 2Ph。
可选地，所述R 1为氢原子或甲基；所述R 2为氢原子或甲基；所述R 3为1-8个碳原子的烷基；所述R 4为氢原子或甲基。
可选地，所述高分子量树脂(D)含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为5～60质量％。
可选地，所述高分子量树脂(D)的环氧值在0.10eq/kg～0.80eq/kg范围内；优选地，所述高分子量树脂(D)的环氧值在0.35eq/kg～0.70eq/kg范围内；进一步优选地，所述高分子量树脂(D)的环氧值在0.40eq/kg～0.65eq/kg范围内。
可选地，所述环氧树脂(A)的含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为20～80质量％，优选 为30～70质量％，更优选为40～60质量％。
可选地，所述氰酸酯树脂(B)的含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺(C)的总含量100质量％为15～70质量％，优选为20～60质量％，更优选为20～50质量％。
可选地，所述双马来酰亚胺树脂(C)的含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为5～50质量％，优选为10～40质量％。
可选地，所述无机填料(E)的含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为10～300质量％，优选为30～270质量％，进一步优选为50～250质量％。
本发明的另一个方面提供一种预浸料，所述预浸料包括基材及通过浸渍或涂覆而附着于基材上的上述树脂组合物。
本发明的另一个方面提供一种层压板，所述的层压板包括至少一张上述预浸料。
本发明的另一个方面提供一种覆金属箔层压板，所述的覆金属箔层压板包括至少一张上述预浸料及覆于预浸料一侧或两侧的金属箔。
发明效果：本发明提供的树脂组合物具有良好的耐热性、耐湿热性和低的热膨胀系数及模量的优点，使用该树脂组合物制备的预浸料、层压板以及覆金属箔层压板具有良好的耐热性、耐湿热性和低的热膨胀系数及模量，有助于降低封装载板的翘曲，适合于封装形态多变的封装件。
具体实施方式
为了更好地说明本发明，对本发明的某些具体实施方式进行详细的说明，但本发明的实施方式不限定于这些，在权利要求书的范围内可进行不同的变形。
-树脂组合物-
本发明的树脂组合物含有环氧树脂(A)、氰酸酯树脂(B)、双马来酰亚胺树脂(C)、高分子量树脂(D)和无机填充材料(E)以及任选的促进剂(F)和其他添加剂。下面，将详细描述各个成分。
环氧树脂(A)
环氧树脂(A)是本发明的树脂组合物中的基体树脂，其选自分子结构中含 有至少两个环氧基的有机化合物，可以选自双酚A型环氧树脂、双酚F型环氧树脂、线性酚醛型环氧树脂、甲酚酚醛型环氧树脂、双酚A酚醛型环氧树脂、四甲基双酚F型环氧树脂、双酚M型环氧树脂、双酚S型环氧树脂、双酚E型环氧树脂、双酚P型环氧树脂、三官能酚型环氧树脂、四官能酚型环氧树脂、萘型环氧树脂、萘酚型环氧树脂、萘酚酚醛型环氧树脂、蒽型环氧树脂、酚酞型环氧树脂、苯氧基型环氧树脂、降冰片烯型环氧树脂、金刚烷型环氧树脂、茐型环氧树脂、联苯型环氧树脂、双环戊二烯型环氧树脂、双环戊二烯酚醛型环氧树脂、芳烷基型环氧树脂、芳烷基酚醛型环氧树脂、分子中含有亚芳基醚结构的环氧树脂、脂环族环氧树脂、多元醇型环氧树脂、含硅环氧树脂、含氮环氧树脂、含磷环氧树脂、缩水甘油胺环氧树脂、缩水甘油酯环氧树脂等中的任意一种或者至少两种的混合物。
为了使树脂组合物具有更高的耐热和阻燃性以及更低的热膨胀系数，本发明所述的环氧树脂进一步优选线性酚醛型环氧树脂、甲酚酚醛型环氧树脂、萘酚型环氧树脂、萘酚酚醛型环氧树脂、蒽型环氧树脂、酚酞型环氧树脂、联苯型环氧树脂、芳烷基型环氧树脂、芳烷基酚醛型环氧树脂、分子中含有亚芳基醚结构的环氧树脂中的任意一种或者至少两种的混合物，特别优选线性酚醛型环氧树脂、甲酚酚醛型环氧树脂、萘酚酚醛型环氧树脂、蒽型环氧树脂、酚酞型环氧树脂、芳烷基酚醛型环氧树脂、分子中含有亚芳基醚结构的环氧树脂中的任意一种或者至少两种的混合物。
特别地，若环氧树脂(A)至少具有式(5)所示结构的联苯型环氧树脂，为了使清漆状态下的树脂组合物不会出现树脂析出等影响加工的情况，式(5)所示结构的联苯型环氧树脂的含量相对于环氧树脂总含量100质量％为0～80质量％，优选为0～60质量％。
Figure PCTCN2017119902-appb-000002
式(5)中，R 6、R 7、R 8、R 9各自独立地为氢原子、取代或未取代的具有1-5个碳原子的直链或支链烷基，x为20以下的整数。
树脂组合物中的环氧树脂(A)的含量可相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为20～80质量％，优选为30～70质量％，更优选为40～60质量％，可以在保证树脂组合物具有较好加工性的同时，不过份降低树脂组合物的刚性和耐热性。
氰酸酯树脂(B)
氰酸酯树脂(B)是本发明树脂组合物中的热固性树脂成分，与环氧树脂(A)配合使用，可以提高树脂组合物的粘合力，尤其是对金属箔的附着力以及耐热性和介电特性等。对树脂组合物中氰酸酯树脂(B)的含量进行限定，可选地，氰酸酯树脂(B)的含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为15～70质量％，优选为20～60质量，更优选为20～50质量％。若氰酸酯树脂的含量高于70质量％，由于极性基团氰酸酯基的引入而导致层压板吸水率提高，耐湿热性变差，若氰酸酯树脂的含量低于15质量％，由于氰酸酯基自聚产物三嗪环含量降低而导致层压板介电性能降低，玻璃化转变温度降低。
氰酸酯树脂(B)可以选自分子结构中含有至少两个氰酸酯基的氰酸酯单体或氰酸酯预聚物，优选选自双酚A型氰酸酯树脂、双酚F型氰酸酯树脂、双酚M型氰酸酯树脂、双酚S型氰酸酯树脂、双酚E型氰酸酯树脂、双酚P型氰酸酯树脂、线性酚醛型氰酸酯树脂、萘酚型氰酸酯树脂、萘酚酚醛型氰酸酯树脂、双环戊二烯型氰酸酯树脂、芳烷基型氰酸酯树脂、芳烷基酚醛型氰酸酯树脂、双酚A型氰酸酯预聚物、双酚F型氰酸酯预聚物、双酚M型氰酸酯预聚物、双酚S型氰酸酯预聚物、双酚E型氰酸酯预聚物、双酚P型氰酸酯预聚物、线性酚醛型氰酸酯预聚物、萘酚型氰酸酯预聚物、萘酚酚醛型氰酸酯预聚物、双环戊二烯型氰酸酯预聚物、芳烷基型氰酸酯预聚物或芳烷基酚醛型氰酸酯预聚物中的一种或者至少两种的混合物。
双马来酰亚胺树脂(C)
本发明的树脂组合物中，双马来酰亚胺树脂(C)主要起到使层压板树脂组合物的力学性能、耐热性、平面方向热膨胀系数更为优异。
对本发明所述的马来酰亚胺化合物没有特别的限定，可以选自分子结构中 含有至少一个马来酰亚胺基团的化合物，优选分子结构中含有至少两个马来酰亚胺基团的化合物，进一步优选自N-苯基马来酰亚胺、N-(2-甲基苯基)马来酰亚胺、N-(4-甲基苯基)马来酰亚胺、N-(2,6-二甲基苯基)马来酰亚胺、二(4-马来酰亚胺基苯基)甲烷、2,2-二(4-(4-马来酰亚胺基苯氧基)-苯基)丙烷、二(3,5-二甲基-4-马来酰亚胺基苯基)甲烷、二(3-乙基-5-甲基-4-马来酰亚胺基苯基)甲烷、二(3,5-二乙基-4-马来酰亚胺基苯基)甲烷、聚苯基甲烷双马来酰亚胺(Polyphenylmethanebismaleimide)、含联苯结构的马来酰亚胺、N-苯基马来酰亚胺预聚物、N-(2-甲基苯基)马来酰亚胺预聚物、N-(4-甲基苯基)马来酰亚胺预聚物、N-(2,6-二甲基苯基)马来酰亚胺预聚物、二(4-马来酰亚胺基苯基)甲烷预聚物、2,2-二(4-(4-马来酰亚胺基苯氧基)-苯基)丙烷预聚物、二(3,5-二甲基-4-马来酰亚胺基苯基)甲烷预聚物、二(3-乙基-5-甲基-4-马来酰亚胺基苯基)甲烷预聚物、二(3,5-二乙基-4-马来酰亚胺基苯基)甲烷预聚物、聚苯基甲烷双马来酰亚胺预聚物、含联苯结构的马来酰亚胺预聚物、N-苯基马来酰亚胺和胺类化合物的预聚物、N-(2-甲基苯基)马来酰亚胺和胺类化合物的预聚物、N-(4-甲基苯基)马来酰亚胺和胺类化合物的预聚物、N-(2,6-二甲基苯基)马来酰亚胺和胺类化合物的预聚物、二(4-马来酰亚胺基苯基)甲烷和胺类化合物的预聚物、2,2-二(4-(4-马来酰亚胺基苯氧基)-苯基)丙烷和胺类化合物的预聚物、二(3,5-二甲基-4-马来酰亚胺基苯基)甲烷和胺类化合物的预聚物、二(3-乙基-5-甲基-4-马来酰亚胺基苯基)甲烷和胺类化合物的预聚物、二(3,5-二乙基-4-马来酰亚胺基苯基)甲烷和胺类化合物的预聚物、含联苯结构的马来酰亚胺和胺类化合物的预聚物、或聚苯基甲烷双马来酰亚胺和胺类化合物的预聚物中的任意一种或者至少两种的混合物，最优选二(4-马来酰亚胺基苯基)甲烷、2,2-二(4-(4-马来酰亚胺基苯氧基)-苯基)丙烷、含联苯结构的马来酰亚胺、聚苯基甲烷双马来酰亚胺或二(3-乙基-5-甲基-4-马来酰亚胺基苯基)甲烷、含联苯结构的马来酰亚胺中的任意一种或者至少两种的混合物。
双马来酰亚胺(C)的含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％可以为5～50质量％，优选为10～40质量％。
高分子量树脂(D)
高分子量树脂(D)是一种环氧改性丙烯酸酯类树脂，在本发明树脂组合物中主要起到低弹性树脂成分作用。具体地，高分子量树脂(D)是具有以式(1)、 式(2)、式(3)和式(4)表示的结构、重均分子量在10万以上20万以下的树脂。
Figure PCTCN2017119902-appb-000003
k、l、m和n为摩尔分率，其中，k+l+m+n≤1，0≤k≤0.30，0.01≤l≤0.20，0.10≤m≤0.60，0≤n≤0.60；式(2)中，R 1为氢原子或1-8个碳原子的烷基；式(3)中，R 2、R 3各自独立的为氢原子或1-8个碳原子的；式(4)中，R 4为氢原子或1-8个碳原子的烷基，R 5为Ph(苯基)或-COOCH 2Ph或-COOCH 2CH 2Ph。
可选地，所述R 1为氢原子或甲基；所述R 2为氢原子或甲基；所述R 3为1-8个碳原子的烷基；所述R 4为氢原子或甲基。
具有式(1)、式(2)、式(3)和式(4)结构的高分子量树脂(D)中，式(1)式(2)、式(3)和式(4)结构的顺序并没有限定，且式(1)、式(2)、式(3)或式(4)结构可以连续也可以不连续。
高分子量树脂(D)中式(1)结构含有氰基，在高温反应下能与氰酸酯树脂(B)和双马来酰亚胺树脂(C)相互反应，氰基的引入能提高树脂组合物、预浸料、层压板以及覆金属箔层压板的耐热性。
高分子量树脂(D)中式(2)结构含有环氧基，能提高高分子量树脂(D) 与树脂组合物的固化强度，从而提高树脂组合物的耐热性和耐湿热性。对于环氧基的含量，高分子量树脂(D)中式(2)结构的含量可以在0.01～0.20(以摩尔分数计)，而高分子量树脂(D)的环氧值可以在0.10eq/kg～0.80eq/kg的范围内，优选在0.35eq/kg～0.70eq/kg的范围内，更优选在0.40eq/kg～0.65eq/kg的范围内。环氧值是1kg高分子量树脂(D)中环氧基的当量数。若环氧值低于0.10eq/kg，则高分子量树脂(D)在树脂组合物中的相容性降低，树脂组合物、预浸料、层压板以及覆金属箔层压板的耐热性和耐湿热性会下降。若环氧值高于0.80eq/kg，则高分子量树脂(D)使树脂组合物的交联密度增大而弹性下降、模量提高。
高分子量树脂(D)中式(2)和式(3)结构含有酯基，式(4)结构可以含有酯基，酯基吸湿性强，但式(2)结构酯基与环氧化缩水甘油基相连，式(4)结构中的酯基含有苯环结构，均能提高树脂组合物的结合强度，树脂组合物的固化物在吸湿的情况下，仍具有较好的耐湿热性，由此，可以提高树脂组合物、预浸料、层压板以及覆金属箔层压板的耐湿热性。
高分子量树脂(D)重均分子量在10万以上20万以下。若高分子量树脂(D)重均分子量在10万以下，则高分子量树脂(D)的耐热性变差，且预浸料发粘，影响储存和后序加工，并难以起到低弹性和良好耐湿热性的作用。若高分子量树脂(D)重均分子量在20万以上，则树脂组合物的清漆液(甲阶段状态)粘度过大，影响无机填料(E)在树脂组合物中的分散均匀性和对基材的浸润性，同时高分子量树脂(D)与树脂组合物其他组分的熔融流动性差异大，层压板(固化后)存在高分子量树脂(D)树脂层。
高分子量树脂(D)含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为5～60质量％。若高分子量树脂(D)的含量低于5质量％，则高分子量树脂(D)在树脂组合物中不能形成有效的或大型的连续相，不能起到降低模量的作用，若高分子量树脂(D)的含量高于60质量％，则高分子量树脂(D)在树脂组合物中不能均匀分散，且清漆状态的树脂组合物粘度过高导致难以有效浸润基材。
对于高分子量树脂(D)的重均分子量低于10万且含量高于60质量％的情况，由于高分子量树脂(D)本身的熔融流动性较低，并不影响无机填料的均匀分散；对于高分子量树脂(D)的重均分子量高于20万且含量低于5质量％的 情况，由于高分子量树脂(D)本身的熔融流动性较高，仍会影响无机填料的均匀分散。
无机填料(E)
树脂组合物中含有无机填料(E)，可以提高树脂组合物和层压板的耐热性和耐湿热性，也可以提高层压板和覆金属箔层压板的尺寸稳定性和降低热膨胀系数。
无机填料(E)的种类并没有限定，可以选自结晶型二氧化硅、熔融二氧化硅、无定形二氧化硅、球形二氧化硅、空心二氧化硅、氢氧化铝、氢氧化镁、勃姆石、氧化钼、钼酸锌、二氧化钛、氧化锌、氮化硼、氮化铝、碳化硅、氧化铝、复合硅微粉、玻璃粉、短玻璃纤维或空心玻璃等中的一种或者多种。为了使树脂组合物具有更高的耐热性、耐湿热性和尺寸稳定性，优选结晶型二氧化硅、熔融二氧化硅、无定形二氧化硅、球形二氧化硅、空心二氧化硅、氢氧化铝、氢氧化镁、勃姆石、氮化硼、氮化铝、碳化硅、氧化铝、复合硅微粉、玻璃粉、短玻璃纤维或空心玻璃中的一种或者多种，进一步优选球形二氧化硅。
可选地，所述无机填料(E)的含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为10～300质量％，优选为30～270质量％，进一步优选为50～250质量％。
为了提高无机填料(E)与树脂组合物的相容性，可以加入偶联剂进行表面处理。对偶联剂没有限定，一般选自硅烷偶联剂，对硅烷偶联剂的种类没有限定，可以列举环氧基硅烷偶联剂、氨基硅烷偶联剂、乙烯基硅烷偶联剂、苯乙烯基硅烷偶联剂、异丁烯基硅烷偶联剂、丙烯基硅烷偶联剂、脲基硅烷偶联剂、巯基硅烷偶联剂、氯丙基硅烷偶联剂、硫化基硅烷偶联剂、异氰酸盐基硅烷偶联剂等。
促进剂(F)及其他添加剂
为了使树脂组合物完全固化，所述树脂组合物还需要加入促进剂(F)，所述促进剂(F)选自可以促进氰酸酯树脂、环氧树脂固化的固化促进剂，其具体为铜、锌、钴、镍、锰之类的金属的有机盐、咪唑及其衍生物、叔胺等，可以是一种或者两种以上复合使用。
另外，为了使树脂组合物具有较好的加工性和使用性能，所述树脂组合物还需要加入各种添加剂，可以为阻燃剂、热稳定剂、光稳定剂、抗氧化剂、润 滑剂等。
本发明的树脂组合物可以通过溶解、混合、预聚、预反应、搅拌所述环氧树脂(A)、氰酸酯树脂(B)、双马来酰亚胺树脂(C)和高分子量树脂(D)等来制备。溶解树脂需要使用有机溶剂，只要使各种树脂能完全溶解、且混合时不发生分离即可，可以列举：甲醇、乙醇、乙二醇、丙酮、丁酮、甲基乙基甲酮、环己酮、甲苯、二甲苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、醋酸乙酯等。可以使用一种或多种溶剂。
-预浸料、层压板、覆金属箔层压板-
本发明的预浸料是由半固化状态的本发明的树脂组合物和基材形成。具体而言，预浸料是通过以下过程形成，即，清漆状态的树脂组合物浸润基材，经过加热使溶剂挥发并转变为半固化状态。
本发明对基材没有特别的限制，通常是纺织物、无纺布、粗纱、短纤维、纤维纸等，材质可以是无机纤维(例如E玻璃、D玻璃、L玻璃、M玻璃、S玻璃、T玻璃、NE玻璃、石英等玻璃纤维)或有机纤维(例如聚酰亚胺、聚酰胺、聚酯、聚苯醚、液晶聚合物等)，优选玻璃纤维布。
本发明的层压板包括至少一张上述的预浸料。
本发明的覆金属箔层压板包括至少一张上述的预浸料及覆于预浸料一侧或两侧的金属箔。例如可通过使1～20片预浸料重叠，并用在其单面或两面配置了铜及铝等金属箔的构成层压成形，从而制造覆金属箔层压板。
[实施例]
以下，利用实施例，对本公开进行具体的说明。
<树脂组合物原料>
环氧树脂(A1)：联苯芳烷型环氧树脂(Nippon Kayaku公司制“NC-3000-H”，式(5)所示结构)
环氧树脂(A2)：萘基型环氧树脂(DIC公司制“HP-6000”，式(6)所示结构)
Figure PCTCN2017119902-appb-000004
式(6)中的R 10为氢原子、甲基或乙基。
环氧树脂(A3)：双酚A型环氧树脂(三菱化学公司制“828US”)
氰酸酯树脂(B1)：双酚A型氰酸酯树脂(Lonza公司制“BA-3000S”)
氰酸酯树脂(B2)：酚醛型氰酸酯树脂(Lonza公司制“PT-30S”)
双马来酰亚胺树脂(C1)：双(3-乙基-5-甲基-4-双马来酰亚胺基苯基)甲烷(天益化工公司制“TY-2002”)
双马来酰亚胺树脂(C2)：二苯甲烷型双马来酰亚胺树脂(华鼎高分子合成树脂有限公司制)
高分子量树脂(D1)：环氧改性丙烯酸酯类树脂(Nagase ChemteX公司制“PMS-22-1”，重均分子量10万，环氧值0.63eq/kg)
高分子量树脂(D2)：环氧改性丙烯酸酯类树脂(Nagase ChemteX公司制“PMS-22-1改MW1”，重均分子量20万，环氧值0.63eq/kg)
高分子量树脂(D3)：环氧改性丙烯酸酯类树脂(Nagase ChemteX公司制“PMS-22-4”，重均分子10万，环氧值0.63eq/kg)
高分子量树脂(D4)：环氧改性丙烯酸酯类树脂(Nagase ChemteX公司制“PMS-22-4改MW1”，重均分子量20万，环氧值0.63eq/kg)
高分子量树脂(D5)：环氧改性丙烯酸酯类树脂(Nagase ChemteX公司制“PMS-19-5改MW1”，重均分子量10万，环氧值0.40eq/kg)
高分子量树脂(D6)：环氧改性丙烯酸酯类树脂(Nagase ChemteX公司制“PMS-22-5”，重均分子量10万，环氧值0.21eq/kg)
其中(D1)～(D6)具有以式(1)、式(2)、式(3)和式(4)表示的结构，k+l+m+n≤1，0≤k≤0.30，0.01≤l≤0.20，0.10≤m≤0.60，00≤n≤0.60。
高分子量树脂(D7)：环氧改性丙烯酸酯类树脂(Nagase ChemteX公司制 “PMS-22-5改EP1”，重均分子量10万，环氧值0.09eq/kg)，其中(D7)具有以式(1)、式(2)、式(3)和式(4)表示的结构，但环氧值低于0.10eq/kg。
高分子量树脂(D8)：环氧改性丙烯酸酯类树脂(Nagase ChemteX公司制“PMS-19-5”，重均分子量70万，环氧值0.40eq/kg)，其中(D8)具有以式(1)、式(2)、式(3)和式(4)表示的结构，但重均分子量高于20万。
无机填料(E1)：环氧基硅烷偶联剂改性球形二氧化硅(Admatechs公司制“SC2050-MB”，D50：0.5μm)
无机填料(E2)：环氧基硅烷偶联剂改性勃姆石(壹石通公司制“BG-611”，D50：0.5-1.0μm)
(F)促进剂
有机金属盐促进剂：辛酸锌(领先化学公司制，型号为“BICATZ”)
咪唑类促进剂：2-乙基-4-甲基咪唑(四国化成公司制“2E4MI”)
织布基材：玻璃纤维布(日东纺公司制2116玻璃纤维布，单重104g/m 2，厚度92μm)
本发明实施例、比较例中各组分均以固形物计算。
(预浸料)
将环氧树脂(A1)、(A2)和(A3)，氰酸酯(B1)和(B2)，双马来酰亚胺(C1)和(C1)，高分子量树脂(D1)、(D2)、(D3)、(D4)、(D5)、(D6)、(D7)和(D8)中的一种，无机填料(E1)和(E2)以及促进剂(F)按照表1(实施例)或表2(比较例)所示的质量份配合，用二甲基甲酰胺和丁酮溶解和稀释，制备出清漆状态的树脂组合物。
然后清漆状态的树脂组合物浸润日东纺制2116玻璃纤维布，并将其在165℃的鼓风烘箱中加热干燥7分钟，使清漆状态的树脂组合物转变为半固化状态的树脂组合物，厚度控制在130～140μm，由此制造出预浸料。
(覆金属箔层压板)
分别将2张、8张的上述预浸料叠合，并在其各自两侧压覆35μm厚度的电解铜箔，在压机中进行2小时固化，固化压力为45kg/cm 2，固化温度为240℃，获得厚度约为0.35mm、1.1mm的覆铜箔层压板。
(层压板)
覆金属箔层压板将金属箔蚀刻后，获得厚度约为0.25mm、1.0mm的层压板。
针对本发明使用所述树脂组合物制备的层压板以及覆金属箔层压板，检测其耐热性(Tg，T300)、耐湿热性以及平面方向热膨胀系数(CTE)，其测试结果如下述实施例进一步给予详加说明与描述。
表1和表2中物性数据的测试方法如下：
玻璃化转变温度(Tg)：取长为60mm、宽为8～12mm、厚为1.0mm的层压板作为样品，使用动态机械热分析仪(DMA)进行测量，升温速率10℃/min，结果取tanδ的转变峰温度，单位为℃。
T300带铜：取长为6.5mm、宽为6.5mm、厚为1.1mm的覆金属箔层压板作为样品，样品在105℃烘箱中烘2小时后在干燥器中冷却至室温。使用热分析机械法(TMA)进行测量，升温速率10℃/min，从室温升温至300℃，并在300℃保持10min，分层时间即为从恒温拐点到分层的时间，单位为min，对于在300℃以下开始分层的样品，记录开始分层时的温度，单位为℃。
XY向热膨胀系数：取长为60mm、宽为4mm、厚为0.25mm的层压板作为样品，玻纤经纱方向为X向，玻纤纬纱方向为Y向，样品在105℃烘箱中烘1小时后在干燥器中冷却至室温。使用热分析机械法(TMA)进行测量，升温速率10℃/min，从室温升温至300℃，进行两次升温，第一次升温结束冷却至室温后重新放样进行第二次升温，结果取第二次升温50℃到130℃下的平面方向热膨胀系数，单位为ppm/℃。
耐湿热性：取长为50mm、宽为50mm、厚为1.0mm的层压板作为样品，将样品用高压蒸煮试验机在121℃和两个大气压下处理2h或3h，然后将样品在288℃的锡炉中浸锡，记录不起泡的时间，若大于300s，则耐湿热性通过。
剥离强度：取长为50mm、宽为50mm的覆金属箔层压板作为样品，在样品上用贴胶带或其他办法利用蚀刻制备金属箔宽度为3.0mm的试样条。使用抗剥仪或其他等效仪器以50mm/min的速度在垂直方向施加压力，使金属箔剥离层压板，可得到覆金属箔层压板的剥离强度，单位为N/mm。
弯曲模量：取长为76.2mm、宽为25.4mm的层压板作为样品，采用材料试验机进行测量，跨距为25.4mm，试验速度0.76mm/min，最大弯曲强度按公式可换算得到弯曲模量，单位为GPa。
扫描电子显微镜(SEM)：观察层压板截面是否存在界面和填料是否分散均匀，采用扫描电子显微镜进行观察。样品预处理：层压板裁剪成比样品台稍小 的小样，并采用离子研磨等方法使剪切面平整，然后充分清洗剪切面的油污和充分干燥后，最后在研磨平整的剪切面上喷镀一层10nm左右的金属层，一般为金。在高真空条件下用扫描电子显微镜观察层压板截面的形貌，放大至能观察到无机填料的分散分布情况即可。若观察到浸润料间存在不含无机填料的树脂层，则判断存在界面，若观察到填料出现分散上出现团聚或分布上出现局部不均匀，则判断填料分散不均匀。
[表1(实施例)]
Figure PCTCN2017119902-appb-000005
Figure PCTCN2017119902-appb-000006
[表2(比较例)]
Figure PCTCN2017119902-appb-000007
Figure PCTCN2017119902-appb-000008
从表1和表2可以看出，当高分子量树脂(D)的重均分子量过高(比较例2)时，高分子量树脂(D)的熔融流动性差，层压板SEM截面存在界面，且影响无机填料的均匀分散；当高分子量树脂(D)的含量过高且重均分子量过高时(比较例7)时，层压板SEM截面存在界面，且影响无机填料的均匀分散；当高分子量树脂(D)的分子量过低或者含量过低(比较例8)时，对板材的Tg没有提高作用，且不存在降低XY轴CTE和模量的效果；当高分子量树脂(D)的结构不满足k+l+m+n≤1，0≤k≤0.30，0.01≤l≤0.20，0.10≤m≤0.60，0≤n≤0.60(比较例1、3-5、11)时，将影响层压板的耐热性和耐湿热性；当树脂组合物不含 氰酸酯或马来酰亚胺(比较例9和10)时，将影响层压板的耐热性和耐湿热性。
本发明的树脂组合物，由于添加具有以式(1)、式(2)、式(3)和式(4)表示的结构、重均分子量在10万以上20万以下的高分子量树脂(D)，其中，k、l、m和n为摩尔分率，k+l+m+n≤1，0≤k≤0.30，0.01≤l≤0.20，0.10≤m≤0.60，0≤n≤0.60，在不影响层压板耐热性高和耐湿热性的基础上，可以提高层压板的Tg，并有效降低层压板的XY向热膨胀系数，同时，可以降低模量，当用作预浸料时，使芯片元件和印刷电路板在焊接加热时由于热膨胀差发生的应力得到缓和，使得接合部原来易产生的焊接裂纹得到降低。
以上实施例，并非对本发明的组合物的含量作任何限制，凡是依据本发明的技术实质或组合物的重量份或含量对以上实施例所作的任何细微修改、等同变化与修饰，均仍属于本发明技术方案的范围内。
申请人声明，本发明通过上述实施例来说明本发明的详细组成，但本发明并不局限于上述详细组成，即不意味着本发明必须依赖上述详细组成才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (11)

  1. 一种树脂组合物，其特征在于，所述树脂组合物含有环氧树脂(A)、氰酸酯树脂(B)、双马来酰亚胺树脂(C)、具有以式(1)、式(2)、式(3)和式(4)表示的结构、重均分子量在10万以上20万以下的高分子量树脂(D)以及无机填充材料(E)，
    Figure PCTCN2017119902-appb-100001
    k、l、m和n为摩尔分率，其中，k+l+m+n≤1，0≤k≤0.30，0.01≤l≤0.20，0.10≤m≤0.60，0≤n≤0.60；式(2)中，R 1为氢原子或1-8个碳原子的烷基；式(3)中，R 2、R 3各自独立的为氢原子或1-8个碳原子的烷基；式(4)中，R 4为氢原子或1-8个碳原子的烷基，R 5为Ph(苯基)、-COO(CH 2) 2Ph或-COOCH 2Ph。
  2. 根据权利要求1所述的树脂组合物，其特征在于，所述R 1为氢原子或甲基；所述R 2为氢原子或甲基；所述R 3为1-8个碳原子的烷基；所述R 4为氢原子或甲基。
  3. 根据权利要求1或2所述的树脂组合物，其特征在于，所述高分子量树脂(D)含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树 脂(C)的总含量100质量％为5～60质量％。
  4. 根据权利要求1-3中任一项所述的树脂组合物，其特征在于，所述高分子量树脂(D)的环氧值在0.10eq/kg～0.80eq/kg范围内；优选地，所述高分子量树脂(D)的环氧值在0.35eq/kg～0.70eq/kg范围内；进一步优选地，所述高分子量树脂(D)的环氧值在0.40eq/kg～0.65eq/kg范围内。
  5. 根据权利要求1-4中任一项所述的树脂组合物，其特征在于，所述环氧树脂(A)的含量相对于所述环氧树脂(A)、氰酸酯(B)以及双马来酰亚胺(C)的总含量100质量％为20～80质量％，优选为30～70质量％，更优选为40～60质量％。
  6. 根据权利要求1-5中任一项所述的树脂组合物，其特征在于，所述氰酸酯树脂(B)的含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为15～70质量％，优选为20～60质量％，更优选为20～50质量％。
  7. 根据权利要求1-6中任一项所述的树脂组合物，其特征在于，所述双马来酰亚胺树脂(C)的含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为5～50质量％，优选为10～40质量％。
  8. 根据权利要求1-7中任一项所述的树脂组合物，其特征在于，所述无机填料(E)的含量相对于所述环氧树脂(A)、氰酸酯树脂(B)以及双马来酰亚胺树脂(C)的总含量100质量％为10～300质量％，优选为30～270质量％，进一步优选为50～250质量％。
  9. 一种预浸料，其特征在于，所述预浸料包括基材及通过浸渍或涂覆而附着于基材上的如权利要求1-8中任一项所述的树脂组合物。
  10. 一种层压板，其特征在于，所述层压板包括至少一张如权利要求9所述的预浸料。
  11. 一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括至少一张如权利要求9所述的预浸料及覆于预浸料一侧或两侧的金属箔。
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