WO2020132858A1 - 树脂组合物、印刷电路用预浸片及覆金属层压板 - Google Patents

树脂组合物、印刷电路用预浸片及覆金属层压板 Download PDF

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WO2020132858A1
WO2020132858A1 PCT/CN2018/123416 CN2018123416W WO2020132858A1 WO 2020132858 A1 WO2020132858 A1 WO 2020132858A1 CN 2018123416 W CN2018123416 W CN 2018123416W WO 2020132858 A1 WO2020132858 A1 WO 2020132858A1
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resin composition
metal
composition according
printed circuit
resin
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PCT/CN2018/123416
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English (en)
French (fr)
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孟运东
方克洪
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广东生益科技股份有限公司
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Priority to PCT/CN2018/123416 priority Critical patent/WO2020132858A1/zh
Publication of WO2020132858A1 publication Critical patent/WO2020132858A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • the present disclosure relates to the technical field of printed circuit boards. Specifically, the present disclosure relates to a resin composition, a prepreg for printed circuits, and a metal-clad laminate.
  • Metal-clad laminate is a plate-like material made by dipping electronic glass fiber cloth or other reinforcing materials with resin solution, covering metal foil on one or both sides and hot pressing. It is called metal-clad laminate. Referred to simply as metal-clad laminate or metal-clad plate, such as copper-clad laminate or copper-clad plate (Copper Clad Laminate, CCL). Metal-clad laminates such as copper-clad laminates are the base laminates used to manufacture printed circuit boards (PCBs). PCBs are one of the important components in the electronics industry. Almost every kind of electronic equipment, from electronic watches and calculators to computers, communication electronic equipment and military weapon systems, as long as there are integrated circuits and other electronic components, for the electrical interconnection between them, printed boards must be used. . The metal-clad laminate is mainly responsible for the functions of conduction, insulation and support on the entire printed circuit board.
  • the printed circuit board is required to develop in the direction of high precision, high density, high performance, microporous and thin Come faster.
  • the CCL largely determines the performance of the PCB.
  • An object of the present disclosure is to provide a resin composition, a prepreg for a printed circuit obtained by infiltrating the resin composition with a reinforcing material such as glass fiber cloth (abbreviated as glass fiber cloth for short), and a pre-precursor for the printed circuit
  • a reinforcing material such as glass fiber cloth (abbreviated as glass fiber cloth for short)
  • a pre-precursor for the printed circuit The dip-coated metal-clad laminate makes the metal-clad laminate have at least one of characteristics such as low dielectric loss factor, high heat resistance, and low coefficient of thermal expansion.
  • Another object of the present disclosure is to provide an insulating board including the prepreg for printed circuits and a printed circuit board including the prepreg for printed circuits, the insulating board or the metal-clad laminate,
  • the insulating board or the metal-clad laminate has one of characteristics such as low dielectric loss factor, high heat resistance, and low coefficient of thermal expansion.
  • the present disclosure provides a resin composition comprising:
  • the weight ratio of the silicon alkyne resin, the cyanate compound and the maleimide compound is (5-95): (5-70): (5-70).
  • the silicon alkyne resin is represented by the following formula:
  • n is an integer between 1 and 5;
  • R 1 and R 2 are each independently a group selected from the group consisting of hydrogen, C 1-6 alkyl, or C 3-6 cycloalkyl.
  • the silicon alkyne resin has a number average molecular weight of 250 to 10,000.
  • the cyanate compound is selected from 2,2-bis(4-cyanophenyl)propane, bis(3,5-dimethyl-4-cyanophenyl)methane , Any one or a combination of at least two of prepolymers or monomers of 2,2-bis(4-cyanophenyl)ethane.
  • the cyanate compound is selected from the group consisting of 2,2-bis(4-cyanophenyl)propane and bis(3,5-dimethyl-4-cyanophenyl) A combination of methane, or a combination of bis(3,5-dimethyl-4-cyanophenyl)methane and 2,2-bis(4-cyanophenyl)ethane.
  • the maleimide compound contains at least one structure represented by the following formula in its molecular structure:
  • the maleimide compound contains at least two structures represented by the following formula in its molecular structure:
  • the maleimide compound is selected from the group consisting of: 4,4'-diphenylmethane bismaleimide, phenmethane maleimide oligomer, m-phenylene Bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide Maleimide, 4-methyl-1,3-phenylenebismaleimide and 1,6-bismaleimide-(2,2,4-trimethyl)hexane Any one or a combination of at least two.
  • the resin composition further includes an accelerator, wherein the content of the accelerator in the resin composition is 0.01-5 wt%.
  • the accelerator is selected from the group consisting of peroxides, metal salts of acetylacetone, metal salts of naphthenic acid, vanadium pentoxide, amines, quaternary ammonium salts, imidazole, triphenylphosphine, Any one or a mixture of at least two of boron trifluoride complex, metal salt of n-octanoic acid or isooctanoic acid, acetylacetone, naphthenic acid, metal salt of stearic acid and salicylic acid.
  • the resin composition further includes a filler.
  • the filler is selected from alumina, titania, mica, silica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, hydrogen Any one or at least two of clays such as magnesium oxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, and silicon carbide Species mixture.
  • clays such as magnesium oxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, and silicon carbide Species mixture.
  • the resin composition further includes a flame retardant.
  • the resin composition further includes a solvent.
  • the present disclosure provides a prepreg for a printed circuit, the prepreg for a printed circuit including a reinforcing material and the resin composition as described in any one of the above adhered to it after being dried by infiltration .
  • the present disclosure provides an insulating board containing at least one prepreg for a printed circuit as described above.
  • the present disclosure provides a metal-clad laminate including at least one prepreg for a printed circuit and a metal foil as described above.
  • the present disclosure provides a printed circuit board, the printed circuit board comprising: at least one prepreg for a printed circuit as described above, or at least one insulating board as described above, Or at least one metal-clad laminate as described above.
  • a resin composition a prepreg for a printed circuit obtained by infiltrating the resin composition with a reinforcing material, and a metal-clad laminate or an insulating board containing the prepreg for a printed circuit, and A printed circuit board including the prepreg for printed circuits, the insulating board, or the metal-clad laminate, so that the metal-clad laminate can have at least a low dielectric loss factor, high heat resistance, low coefficient of thermal expansion, etc.
  • the resin composition is sometimes referred to as an adhesive hereinafter.
  • all numerical characteristics are within the error range of the measurement, for example, within ⁇ 10%, or within ⁇ 5%, or within ⁇ 1% of the defined value.
  • composition means that it may have other components besides the components, and these other components endow the prepreg with different characteristics.
  • “comprising”, “including” or “containing” in the present disclosure may also include “consisting essentially of” and may be replaced by “for” or “consisting of" ....composition”.
  • the resin composition containing a solvent may also be referred to as resin glue.
  • the present disclosure can provide a resin composition including:
  • the weight ratio of the silicon alkyne resin, the cyanate compound and the maleimide compound is (5-95): (5-70): (5-70).
  • the silicon alkyne resin may be a resin whose molecular main chain contains a silicon element, a benzene ring, and an alkyne structure.
  • the silicon alkyne resin can be represented by the following formula:
  • n is an integer between 1 and 5;
  • R'and R" are each independently a group selected from the group consisting of hydrogen, C 1-6 alkyl, or C 3-6 cycloalkyl.
  • the silicon alkyne resin can be represented by the following formula
  • n is an integer between 1 and 5;
  • R 1 and R 2 are each independently a group selected from the group consisting of hydrogen, C 1-6 alkyl, or C 3-6 cycloalkyl.
  • the two alkynyl groups on the benzene ring may be in the ortho, meta or para position.
  • the silicon alkyne resin can be obtained by polymerizing diethynylbenzene and dichlorosilane.
  • it can be obtained by Grignard polymerization of diethynylbenzene and dichlorosilane.
  • diethynylbenzene may include 1,2-diethynylbenzene, 1,3-diethynylbenzene, and 1,4-diethynylbenzene.
  • Examples of the dichlorosilane may include R′R′′SiCl 2 , or R 1 R 2 SiCl 2 , wherein R′, R′′, R 1 and R 2 are each independently a group selected from the group consisting of : Hydrogen, C 1-6 alkyl or C 3-6 cycloalkyl.
  • dichlorosilane may include methyldichlorosilane and dichlorodimethylsilane.
  • Examples of the C 1-6 alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, various pentyl groups, and various hexyl groups.
  • Examples of C 3-6 cycloalkyl may include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • the number average molecular weight of the silicon alkyne resin may be about 250 to 10,000, preferably about 500 to 2000.
  • Low molecular weight silicon alkyne resins are more soluble in solvents and have better compatibility with polyphenylene ether resins, which can reduce the risk of resin phase separation and facilitate the formation of interpenetrating network structures.
  • the reaction time of too low molecular weight silicon alkyne resin is too long, which is not conducive to the curing process of the resin system.
  • the weight ratio of the silicon alkyne resin in the resin composition has a significant influence on the flame retardant performance of the resin composition.
  • the weight ratio of the silicon alkyne resin to the sum of the silicon alkyne resin, cyanate ester compound and maleimide compound is greater than 70%, the system can achieve V-0 resistance without the use of flame retardants Burning.
  • the present disclosure does not limit the cyanate compound used.
  • Examples of the cyanate compound may be selected from 2,2-bis(4-cyanophenyl)propane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2,2-bis(4 -Any one or a combination of at least two of prepolymers or monomers of cyanate such as cyanophenyl)ethane.
  • the number average molecular weight of the cyanate ester prepolymer may be 200 to 10,000.
  • the molecular weight is too low, the viscosity of the resin is too low, and a longer curing time is required, which is not conducive to hot press processing.
  • the molecular weight is too large, the viscosity of the resin is too large, which is not conducive to the wetting of the reinforcing material, and the fluidity is poor during hot pressing, and it is easy to generate holes and the like.
  • 400 to 6000 are preferred.
  • Examples of typical but non-limiting combinations may be: a combination of 2,2-bis(4-cyanophenyl)propane and bis(3,5-dimethyl-4-cyanophenyl)methane, or bis A combination of (3,5-dimethyl-4-cyanophenyl)methane and 2,2-bis(4-cyanophenyl)ethane.
  • the cyanate compound has relatively weak heat resistance and better dielectric properties than maleimide compounds, but inferior to silicon alkyne resins.
  • the cyanate compound has the best processability in the processing of metal-clad plates such as copper-clad plates, which helps to reduce the crystallinity of the silicon alkyne resin and maleimide compound and improve the fluidity of the resin composition, but excessive cyanide
  • the acid ester compound has poor toughness and heat resistance.
  • the present disclosure does not limit the maleimide compound used.
  • the maleimide compound contains at least one structure represented by the following formula in its molecular structure, and preferably contains at least two structures represented by the following formula in its molecular structure:
  • maleimide compound may be selected from 4,4'-diphenylmethane bismaleimide, phenmethane maleimide oligomer, m-phenylene bismaleimide, bisphenol A Diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl -1,3-phenylene bismaleimide and 1,6-bismaleimide-(2,2,4-trimethyl) hexane any one or a combination of at least two .
  • the phenylmethane maleimide oligomer is a resin material having the following molecular structure, where n is 0, 1, 2, 3, 4 or 5, preferably a mixture of materials with different degrees of polymerization.
  • the maleimide compound has good heat resistance, but poor solubility. Excessive use will cause precipitation and agglomeration, resulting in reduced adhesion of metal-clad plates such as copper-clad plates and poor toughness.
  • the resin composition also contains an accelerator to meet the needs of different curing conditions.
  • the content of the accelerator in the above resin composition may be about 0.01 to 5 wt%.
  • the accelerator may be selected from: peroxides, metal salts of acetylacetone, metal salts of naphthenic acid, vanadium pentoxide, amines, quaternary ammonium salts, imidazole, triphenylphosphine, boron trifluoride complex, n-octanoic acid Or any one or a mixture of at least two of isooctanoic acid metal salt, acetylacetone, naphthenic acid, stearic acid metal salt and salicylic acid.
  • Examples of the peroxide may include: dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, isopropyl peroxide-tert-butyl carbonate, 2,5-dimethyl-2,5 -Di-tert-butylcumylperoxyhexyne-3, 2,5-dimethyl 2,5-di-tert-butylperoxyhexane, p-montane peroxide, 1,1-bis(tert-amyl Peroxy) cyclohexane, diisopropylbenzene hydroperoxide, benzoyl peroxide or benzoyl peroxide derivatives.
  • Examples of amines may include aniline.
  • the metal in the metal salt of n-octanoic acid or isooctanoic acid, the metal salt of stearic acid, the metal salt of acetylacetone and the metal salt of naphthenic acid may independently be alkali metal, alkaline earth metal or transition metal, for example, potassium, calcium, sodium , Magnesium, aluminum, zinc, iron, cobalt, etc.
  • Examples of the metal salt of isooctanoic acid may include zinc isooctanoate.
  • a solvent can also be added to the resin composition to reduce the resin viscosity during the impregnation process.
  • Such a solvent is not particularly limited, but preferably contains one or more aromatic hydrocarbon-based solvents.
  • aromatic hydrocarbon-based solvent toluene, xylene, mesitylene and the like are preferably used. These aromatic hydrocarbon solvents may be used alone or in combination of two or more.
  • an aromatic hydrocarbon-based solvent may be used in combination.
  • the combined solvent is not particularly limited, and specific examples include alcohols such as methanol, ethanol, and butanol; ethyl cellosolve and butyl solvent Fibers, glycol monomethyl ether, carbitol, butyl carbitol and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; methoxyethyl acetic acid Ester, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate and other esters; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl- Nitrogen-containing solvents such as 2-pyrrolidone can be used alone or in combination of two or more.
  • the aromatic hydrocarbon-based solvent is used as a mixed solvent in combination with another
  • the content of the solvent in the resin composition may be 10-99.5 wt%, preferably about 20-99 wt%.
  • fillers such as fillers may be added to the resin composition.
  • the filler is not particularly limited, and specifically, alumina, titanium oxide, mica, silica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, hydrogen Alumina, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay and other clays, talc, aluminum borate, silicon carbide, etc. These fillers may be used alone or in combination of two or more.
  • the shape of the filler is not particularly limited, but a spherical shape is preferred. There is a certain limit to the particle size of the filler, and the particle size is preferably 0.01 to 30 ⁇ m, more preferably 0.1 to 15 ⁇ m.
  • the particle size of the filler is 0.01 ⁇ m or less, the fluidity of the resin composition decreases, and therefore, the moldability when producing prepregs and metal-clad laminates deteriorates, voids and the like are likely to occur, or the surface area of the filler becomes large. Therefore, The reduction in the bonding area between the metal and the resin will reduce the peel strength of the printed wiring board, which is not preferable.
  • the particle diameter exceeds 30 ⁇ m, the insulation reliability of the wiring room of the printed wiring board or the insulating layer is lowered, which is not preferable.
  • the content of the filler in the resin composition may be about 1 to 90% by weight, preferably about 5 to 80% by weight.
  • a flame retardant can also be added to the resin composition.
  • flame retardant it is preferable to use flame retardants such as bromine-based, phosphorus-based, and metal hydroxide.
  • brominated flame retardants are: brominated bisphenol A epoxy resin and brominated phenol novolac epoxy resin, brominated epoxy resins such as hexabromobenzene, pentabromotoluene, ethylene bis (pentabromo Phenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclo Dodecane, bis(tribromophenoxy)ethane, brominated polyphenylene oxide, brominated polystyrene and 2,4,6-tris(tribromophenoxy)-1,3,5-triazine
  • brominated flame retardants tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A dimethacrylate
  • phosphorus-based flame retardants are: triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylyl phosphate, and m-phenylenedi Aromatic phosphates such as phenol bis(diphenyl phosphate); phosphonates such as divinyl phenylphosphonate, diallyl phenylphosphonate and bis(1-butenyl) phenylphosphonate ; Phosphate esters such as phenyl diphenyl phosphate, methyl diphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives; bis(2-allyl Phenoxy)phosphazene, phosphazene and phosphazene compounds such as phosphazene; melamine phosphate, melamine pyrophosphat
  • metal hydroxide flame retardants examples include magnesium hydroxide or aluminum hydroxide.
  • the flame retardant may be used alone or in combination of two or more.
  • the content of the flame retardant in the resin composition may be about 1 to 40% by weight, preferably about 2 to 30% by weight.
  • the resin composition may further contain various additives.
  • auxiliary agent include filler dispersants, defoamers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, and lubricants. These additives can be used alone, or any two or more of them can be used in combination.
  • the resin composition of the present disclosure can be compounded, stirred, and mixed with silicon alkyne resin, cyanate compound, and maleimide compound, as well as optional accelerators, solvents, fillers, flame retardants, and dispersion by known methods Any one or a mixture of at least two of agents, defoamers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants and lubricants.
  • the resin composition is formulated into a resin glue, and then the resin glue is used to infiltrate the reinforcing material, and the prepreg is obtained by drying.
  • the metal-clad laminate can be prepared by hot pressing the prepreg and metal foil such as copper foil or aluminum foil in a vacuum press.
  • Examples of the reinforcing material may include: glass fiber cloth, glass fiber non-woven cloth, organic non-woven cloth, and the like.
  • wetting can be carried out under heating. Heating is performed so that the temperature of the resin glue solution is lower than the boiling point of the solvent used. Preferably, the temperature of the resin glue solution during wetting is about 50-90°C, further preferably about 55-85°C.
  • the present disclosure may also provide a prepreg for a printed circuit, the prepreg for a printed circuit including a reinforcement material and the resin combination described in any one of the above attached to the prepreg after being dried by infiltration Thing.
  • the present disclosure may also provide an insulating board or a metal-clad laminate that contains at least one prepreg for a printed circuit as described above.
  • the present disclosure may also provide a printed circuit board, the printed circuit board comprising: at least one prepreg for a printed circuit as described above, or at least one insulation as described above Board, or at least one metal-clad laminate as described above.
  • a resin composition a prepreg for a printed circuit obtained by infiltrating the resin composition with a reinforcing material, and a metal-clad laminate or an insulating board containing the prepreg for a printed circuit, and A printed circuit board including the prepreg for printed circuits, the insulating board, or the metal-clad laminate, so that the metal-clad laminate can have at least a low dielectric loss factor, high heat resistance, low coefficient of thermal expansion, etc.
  • the silicon alkyne resins used in Examples and Comparative Examples were prepared as follows.
  • the organic phase was sufficiently washed with water until it was neutral, then dried, filtered, and toluene was distilled off to obtain the silicon phenylene resin (ie, the silicon alkyne resin used in the examples and comparative examples (number average molecular weight 1200, mobile phase for GPC test THF), hereinafter referred to as PSA1200).
  • PSA1200 the silicon alkyne resin used in the examples and comparative examples (number average molecular weight 1200, mobile phase for GPC test THF), hereinafter referred to as PSA1200).
  • the silicon alkyne resin, the cyanate compound and the maleimide compound, and the accelerator are sufficiently dissolved in the solvent and mixed uniformly, and then the filler is added And/or flame retardant, mix well to get glue.
  • the E-type glass fiber cloth produced by Nitto Spinning Co., Ltd.
  • the model number 1080 is evenly impregnate the above glue solution, and bake it in a blast oven at 155°C for 3 minutes to prepare a prepreg.
  • Laminate samples (hereinafter sometimes referred to as copper-clad laminates or copper-clad laminates).
  • PSA1200 the silicon alkyne resin obtained in the preparation example
  • CE01PS Bisphenol A type cyanate prepolymer (number average molecular weight: 3000), produced by Tianqi Chemical;
  • CE01MO Bisphenol A cyanate monomer, produced by Tianqi Chemical
  • BMI-E 3,3’-dimethyl-5,5’-diethyl-4,4’-diphenylmethane bismaleimide, produced by Jiangsu Feixiang Chemical;
  • BMI-1000 4,4’-diphenylmethane bismaleimide, produced by Yamato in Japan;
  • BMI-50P phenylmethane maleimide oligomer, produced by KI in Japan;
  • Zinc isooctanoate reagent, commercially available
  • DQ1028L spherical silica, D50 about 3.0 ⁇ m, produced by Jiangsu Lianrui;
  • SC2050 spherical silica, D50 about 0.5 ⁇ m, provided by Toyota Tsusho, Japan;
  • BT-93w Add-on bromine flame retardant, produced by American Yabao;
  • XP7866 Addition type phosphorus flame retardant, produced by American Yabao;
  • Aluminum hydroxide OL-104, produced by American Yabao;
  • DMF N,N-dimethylformamide, industrial product, commercially available
  • Toluene industrial products, commercially available.
  • Td Thermal decomposition temperature
  • CTE Coefficient of thermal expansion
  • thermal expansion ratio at 50-260°C the test uses a static thermal analyzer (TMA) test, the test is in accordance with the standard IPC-TM-650 2.4.24, where the Z axis represents the thickness direction of the laminate sample, X The axis represents the length direction of the laminate sample, and the Y axis represents the width direction of the laminate sample.
  • TMA static thermal analyzer
  • D50 represents the average particle diameter, which means that when the cumulative volume distribution curve based on the particle diameter is obtained by taking the total volume of the particles as 100%, the particle diameter of the point corresponding to 50% of the volume is used, which uses laser diffraction and scattering Method for determination of particle size distribution.
  • the test results of the samples of this example are higher than the Tg and Td of the printed circuit boards commonly used in the industry.
  • the dielectric dissipation factor of copper-clad laminate shows that it will have good application performance in high-frequency high-speed laminates, and its CTE in all directions, 50-260 °C thermal expansion ratio and thermal stress performance is excellent.
  • a resin composition a prepreg for a printed circuit obtained by infiltrating the resin composition with a glass fiber cloth, a metal-clad laminate or an insulating board containing the prepreg for a printed circuit, and including The printed circuit board for the printed circuit prepreg, the insulating board or the metal-clad laminate, so that the metal-clad laminate can have at least low dielectric loss factor, high heat resistance, low thermal expansion coefficient and other characteristics
  • One of them preferably has a low dielectric loss factor, high heat resistance, and low coefficient of thermal expansion.
  • V-0 flame retardant performance can be achieved, making it suitable for applications requiring flame retardancy.

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Abstract

一种树脂组合物、印刷电路用预浸片及覆金属层压板。所述树脂组合物包含：硅芳炔树脂、氰酸酯化合物和马来酰亚胺化合物。通过使用树脂组合物，制得的覆金属层压板可以至少具有低介电损耗因数、高耐热性、低热膨胀系数等特性中的一个。

Description

树脂组合物、印刷电路用预浸片及覆金属层压板 技术领域
本公开涉及印制电路板技术领域。具体地，本公开涉及一种树脂组合物、印刷电路用预浸片及覆金属层压板。
背景技术
覆金属层压板是将电子玻璃纤维布或其它增强材料浸以树脂液，一面或双面覆以金属箔并经热压而制成的一种板状材料，被称为覆金属箔层压板，简称为覆金属层压板或覆金属板，例如覆铜层压板或覆铜板(Copper Clad Laminate，CCL)。覆金属层压板如覆铜板是制造印制电路板(Printed Circuit Board，简称PCB)的基层压板料，PCB是电子工业的重要部件之一。几乎每种电子设备，小到电子手表、计算器，大到计算机，通讯电子设备，军用武器系统，只要有集成电路等电子元器件，为了它们之间的电气互连，都要使用印制板。覆金属层压板在整个印制电路板上，主要担负着导电、绝缘和支撑三个方面的功能。
随着电子设备向小型化、多功能化、高性能化及高可靠性方面的迅速发展，要求印制电路板朝着高精度、高密度、高性能、微孔化和薄型化方向的发展越来越快。而CCL在很大程度上决定了PCB的性能。
印制电路板高精度、高密度、高性能、微孔化、薄型化和多层化的发展趋势要求覆金属板如覆铜板具有更高的热性能和力学性能。如电子产品中越来越多的应用到多层板，为保证多层电路板性能稳定可靠，这就需要层压有具有低介电损耗因数、高耐热性、低热膨胀系数等特性。
发明内容
本公开的一个目的在于提供一种树脂组合物、通过用增强材料如玻璃纤维布(简称玻纤布)浸润所述树脂组合物得到的印刷电路用预浸片及以及包含所述印刷电路用预浸片的覆金属层压板，使得覆金属层压板至少具有低介电损耗因数、高耐热性、低热膨胀系数等特性中的一个。
本公开的另一个目的在于提供一种包含所述印刷电路用预浸片的绝缘板和包含所述印刷电路用预浸片、所述绝缘板或所述覆金属层压板的印制电路板，其中所述绝缘板或覆金属层压板具有低介电损耗因数、高耐热性、低热膨胀系数等特性中的一个。
因此，在一个方面，本公开提供一种树脂组合物，所述树脂组合物包含：
硅芳炔树脂；
氰酸酯化合物；和
马来酰亚胺化合物，
其中所述硅芳炔树脂、所述氰酸酯化合物与所述马来酰亚胺化合物的重量比为(5-95)∶(5-70)∶(5-70)。
根据本公开的一个实施方案，所述硅芳炔树脂由下式表示：
Figure PCTCN2018123416-appb-000001
其中
n为1至5之间的整数；并且
R 1和R 2各自独立地是选自由以下各项组成的组中的基团：氢、C 1-6烷基或C 3-6环烷基。
根据本公开的另一个实施方案，所述硅芳炔树脂的数均分子量为250至10000。
根据本公开的另一个实施方案，所述氰酸酯化合物选自2，2-双(4-氰酸苯基)丙烷、双(3，5-二甲基-4-氰酸苯基)甲烷、2，2-双(4-氰酸苯基)乙烷的预聚体或单体中的任意一种或至少两种的组合。
根据本公开的另一个实施方案，所述氰酸酯化合物选自：2，2-双(4-氰酸苯基)丙烷和双(3，5-二甲基-4-氰酸苯基)甲烷的组合，或双(3，5-二甲基-4-氰酸苯基)甲烷和2，2-双(4-氰酸苯基)乙烷的组合。
根据本公开的另一个实施方案，所述马来酰亚胺化合物在其分子结构中含有至少一个下式所示的结构：
Figure PCTCN2018123416-appb-000002
根据本公开的另一个实施方案，所述马来酰亚胺化合物在其分子结构中含有至少两个下式所示的结构：
Figure PCTCN2018123416-appb-000003
根据本公开的另一个实施方案，所述马来酰亚胺化合物选自：4，4’-二苯甲烷双马来酰亚胺、苯甲烷马来酰亚胺低聚物、间亚苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3，3’-二甲基-5，5’-二乙基-4，4’-二苯基甲烷双马来酰亚胺、4-甲基-1，3-亚苯基双马来酰亚胺及1，6-双马来酰亚胺-(2，2，4-三甲基)己烷中的任意一种或至少两种的组合。
根据本公开的另一个实施方案，所述树脂组合物还包含促进剂，其中所述促进剂在所述树脂组合物中的含量为0.01-5重量％。
根据本公开的另一个实施方案，所述促进剂选自：过氧化物、乙酰丙酮的金属盐、环烷酸的金属盐、五氧化钒、胺、季铵盐、咪唑、三苯基膦、三氟化硼络合物、正辛酸或异辛酸的金属盐、乙酰丙酮、环烷酸、硬脂酸的金属盐和水杨酸中的任意一种或至少两种的混合物。
根据本公开的另一个实施方案，所述树脂组合物还包含填料。
根据本公开的另一个实施方案，所述填料选自：氧化铝、氧化钛、云母、二氧化硅、氧化铍、钛酸钡、钛酸钾、钛酸锶、钛酸钙、碳酸铝、氢氧化镁、氢氧化铝、硅酸铝、碳酸钙、硅酸钙、硅酸镁、氮化硅、氮化硼、煅烧粘土等粘土、滑石、硼酸铝和碳化硅中的任意一种或至少两种的混合物。
根据本公开的另一个实施方案，所述树脂组合物还包含阻燃剂。
根据本公开的另一个实施方案，所述树脂组合物还包含溶剂。
在另一个方面，本公开提供一种印刷电路用预浸片，所述印刷电路用预浸片包括增强材料及通过浸润干燥后附着在其上的如上面中任何一项所述的树脂组合物。
在再一个方面，本公开提供一种绝缘板，所述绝缘板含有至少一张如上面所述的印刷电路用预浸片。
在又一个方面，本公开提供一种覆金属层压板，所述覆金属层压板包括至少一张如上面所述的印刷电路用预浸片和金属箔。
在再一个方面，本公开提供一种印制电路板，所述印制电路板包含：至少一张如上面所述的印刷电路用预浸片，或至少一张如上面所述的绝缘板，或至少一张如上面 所述的覆金属层压板。
根据本公开，可以提供一种树脂组合物、通过用增强材料浸润所述树脂组合物得到的印刷电路用预浸片及包含所述印刷电路用预浸片的覆金属层压板或绝缘板，以及包含所述印刷电路用预浸片、所述绝缘板或所述覆金属层压板的印制电路板，使得覆金属层压板可以至少具有低介电损耗因数、高耐热性、低热膨胀系数等特性中的一个。
具体实施方式
下面将结合本公开的具体实施方案，对本公开实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施方案和/或实施例仅仅是本公开一部分实施方案和/或实施例，而不是全部的实施方案和/或实施例。基于本公开中的实施方案和/或实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方案和/或所有其他实施例，都属于本公开保护的范围。
在下面的描述中，层和膜可以互换地使用。树脂组合物在下文中有时也称作胶粘剂。
本公开中，所有数值特征都指在测量的误差范围之内，例如在所限定的数值的±10％之内，或±5％之内，或±1％之内。
本公开所述的“包含”、“包括”或“含有”，意指其除所述组份外，还可以具有其他组份，这些其他组份赋予所述预浸片不同的特性。除此之外，本公开所述的“包含”、“包括”或“含有”，还可以包括“基本上由......组成”，并且可以替换为“为”或“由......组成”。
在本公开中，如果没有具体指明，量、比例等是按重量计的。
在本公开中，包含溶剂的树脂组合物也可以称为树脂胶液。
如上所述，本公开可以提供一种树脂组合物，所述树脂组合物包含：
硅芳炔树脂；
氰酸酯化合物；和
马来酰亚胺化合物，
其中所述硅芳炔树脂、所述氰酸酯化合物与所述马来酰亚胺化合物的重量比为(5-95)∶(5-70)∶(5-70)。
硅芳炔树脂
硅芳炔树脂可以是分子主链含有硅元素、苯环和炔烃结构的树脂。
硅芳炔树脂可以由下式表示：
Figure PCTCN2018123416-appb-000004
其中
n为1至5之间的整数；
R’和R”各自独立地是选自由以下各项组成的组中的基团：氢、C 1-6烷基或C 3-6环烷基。
优选地，硅芳炔树脂可以由下式表示
Figure PCTCN2018123416-appb-000005
其中
n为1至5之间的整数；并且
R 1和R 2各自独立地是选自由以下各项组成的组中的基团：氢、C 1-6烷基或C 3-6环烷基。
在上述式中，在苯环上的两个炔基可以处于邻位、间位或对位。硅芳炔树脂可以二乙炔基苯与二氯硅烷聚合得到。例如，可以通过二乙炔基苯与二氯硅烷通过格氏反应聚合得到。
二乙炔基苯的实例可以包括1，2-二乙炔基苯、1，3-二乙炔基苯和1，4-二乙炔基苯。
二氯硅烷的实例可以包括R’R”SiCl 2，或R 1R 2SiCl 2，其中R’、R”、R 1和R 2各自独立地是选自由以下各项组成的组中的基团：氢、C 1-6烷基或C 3-6环烷基。
二氯硅烷的具体实例可以包括甲基二氯硅烷和二氯二甲基硅烷。
C 1-6烷基的实例可以包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、各种戊基和各种己基。C 3-6环烷基的实例可以包括环丙基、环丁基、环戊基和环己基。
硅芳炔树脂的数均分子量可以为约250至10000，优选约500至2000。低分子量的硅芳炔树脂在溶剂中更易溶解，而且与聚苯醚树脂的相容性更好，可以降低树脂析出分相的风险，有利于更好地形成互穿网络结构。但是，过低分子量的硅芳炔树脂的反应时间太久，不利于树脂体系的固化加工。
硅芳炔树脂在树脂组合物中的重量比对树脂组合物的阻燃性能具有明显的影响。当硅芳炔树脂相对于硅芳炔树脂、氰酸酯化合物和马来酰亚胺化合物之和的重量比大 于70％时，该体系能在不使用阻燃剂的条件下达到V-0阻燃。
氰酸酯化合物
本公开对所用的氰酸酯化合物没有限制。
氰酸酯化合物的实例可以选自2，2-双(4-氰酸苯基)丙烷、双(3，5-二甲基-4-氰酸苯基)甲烷、2，2-双(4-氰酸苯基)乙烷等氰酸酯的预聚体或单体中的任意一种或至少两种的组合。
氰酸酯的预聚体的数均分子量可以为200至10000。过低的分子量时树脂的粘度太低，且需要更久的固化时间，不利于热压加工。过大的分子量时，树脂的粘度太大，不利于对增强材料的浸润，并在热压时流动性差，易产生孔洞等。为了更好的适应覆金属板如覆铜板生产的工艺要求，优选400至6000。
典型但非限制性的组合的实例可以为：2，2-双(4-氰酸苯基)丙烷和双(3，5-二甲基-4-氰酸苯基)甲烷的组合，或双(3，5-二甲基-4-氰酸苯基)甲烷和2，2-双(4-氰酸苯基)乙烷的组合。
氰酸酯化合物在这三种树脂组分中，其耐热性相对较弱，介电性能优于马来酰亚胺化合物，但劣于硅芳炔树脂。氰酸酯化合物在覆金属板如覆铜板加工中的工艺性最佳，有助于降低硅芳炔树脂和马来酰亚胺化合物的结晶性，改善树脂组合物的流动性，但过量的氰酸酯化合物的韧性和耐热性较差。
马来酰亚胺化合物
本公开对所用的马来酰亚胺化合物没有限制。
马来酰亚胺化合物在其分子结构中含有至少一个下式所示的结构，优选在其分子结构中含有至少两个下式所示的结构：
Figure PCTCN2018123416-appb-000006
马来酰亚胺化合物的实例可以选自4，4’-二苯甲烷双马来酰亚胺、苯甲烷马来酰亚胺低聚物、间亚苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3，3’-二甲基-5，5’-二乙基-4，4’-二苯基甲烷双马来酰亚胺、4-甲基-1，3-亚苯基双马来酰亚胺及1，6-双马来 酰亚胺-(2，2，4-三甲基)己烷中的任意一种或至少两种的组合。
苯甲烷马来酰亚胺低聚物为如下分子结构的树脂材料，其中n为0、1、2、3、4或5，优选为不同聚合度材料的混合物。
Figure PCTCN2018123416-appb-000007
马来酰亚胺化合物的耐热性较好，但溶解性差。过量使用时会有析出团聚等现象，造成覆金属板如覆铜板的粘结性降低，韧性变差。
促进剂
任选地，树脂组合物还包含促进剂，应对不同的固化条件的需求。
在含有促进剂的情况下，促进剂在上述树脂组合物中的含量可以为约0.01-5重量％。
促进剂可以选自：过氧化物、乙酰丙酮的金属盐、环烷酸的金属盐、五氧化钒、胺、季铵盐、咪唑、三苯基膦、三氟化硼络合物、正辛酸或异辛酸的金属盐、乙酰丙酮、环烷酸、硬脂酸的金属盐和水杨酸中的任意一种或至少两种的混合物。
过氧化物的实例可以包括：过氧化二枯基、叔丁基过氧化枯基、过氧化二叔丁基、过氧化异丙基碳酸叔丁酯、2，5-二甲基-2，5-二叔丁基枯基过氧基己炔-3、2，5-二甲基2，5-二叔丁基过氧化己烷、过氧化对孟烷，1，1-双(叔戊基过氧)环己烷、过氧化氢二异丙基苯、过氧化苯甲酰或过氧化苯甲酰衍生物。胺的实例可以包括苯胺。
正辛酸或异辛酸的金属盐、硬脂酸的金属盐、乙酰丙酮的金属盐和环烷酸的金属盐中的金属可以独立为碱金属、碱土金属或过渡金属，例如，钾、钙、钠、镁、铝、锌、铁、钴等。异辛酸的金属盐的实例可以包括异辛酸锌。
为了更好地适应浸渍等加工工艺，该树脂组合物中还可以加入溶剂，以降低浸渍过程中的树脂粘度。
作为这种溶剂，没有特别限定，优选为含有芳香族烃系溶剂的一种以上。作为芳香族烃系溶剂的具体例，优选使用甲苯、二甲苯、均三甲苯等。这些芳香族烃系溶剂 可以单独使用一种，也可以两种以上组合使用。
另外，如果含有芳香族烃系溶剂，则可以进一步并用其它溶剂，作为并用的溶剂，没有特别限定，作为具体例，可列举：甲醇、乙醇、丁醇等醇类；乙基溶纤剂、丁基溶纤剂、乙二醇单甲醚、卡必醇、丁基卡必醇等醚类；丙酮、甲基乙基酮、甲基异丁酮、环己酮等酮类；甲氧基乙基醋酸酯、乙氧基乙基醋酸酯、丁氧基乙基醋酸酯、醋酸乙酯等酯类；N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮等含氮类等溶剂，这些溶剂可以单独使用一种，也可以两种以上组合使用。另外，在芳香族烃系溶剂中并用其它溶剂做成混合溶剂时的混合比例，优选芳香族烃系溶剂为总溶剂中的50重量％以上。
在含有溶剂的情况下，溶剂在树脂组合物中的含量可以为10-99.5重量％，优选约20-99重量％。
为了由该树脂组合物制得的覆金属层压板具有更好的模量和耐热性，该树脂组合物中可以加入填料如填料。
填料没有特别限定，具体而言，可使用氧化铝、氧化钛、云母、二氧化硅、氧化铍、钛酸钡、钛酸钾、钛酸锶、钛酸钙、碳酸铝、氢氧化镁、氢氧化铝、硅酸铝、碳酸钙、硅酸钙、硅酸镁、氮化硅、氮化硼、煅烧粘土等粘土、滑石、硼酸铝、碳化硅等。这些填料可以单独使用，也可以两种以上并用。对填料的形状没有特别的限制，但优选球型。对填料的粒径有一定的限制，使用粒径优选为0.01至30μm、更优选为0.1至15μm的填料。
填料的粒径为0.01μm以下时，树脂组合物的流动性下降，因此，制作预浸片及覆金属层压板时的成型性变差，容易产生空隙等，或填料的表面积变大，因此，金属和树脂的粘接面积减少，会导致印刷线路板的剥离强度下降，因此不优选。另一方面，粒径超过30μm时，会导致印刷线路板的配线间或绝缘层的绝缘可靠性下降，因此不优选。
在含有填料的情况下，填料在树脂组合物中的含量可以为约1至90重量％，优选为约5至80重量％。
为了更好地满足阻燃等要求，该树脂组合物中还可以加入阻燃剂。
作为阻燃剂，优选使用溴类、磷类、金属氢氧化物等阻燃剂。
溴类阻燃剂的实例为：溴化双酚A型环氧树脂及溴化苯酚酚醛清漆型环氧树脂等溴化环氧树脂、六溴苯、五溴甲苯、亚乙基双(五溴苯基)、亚乙基双四溴邻苯二甲酰亚胺、1，2-二溴-4-(1，2-二溴乙基)环己烷、四溴环辛烷、六溴环十二烷、双(三溴苯氧基)乙烷、溴化聚苯醚、溴化聚苯乙烯及2，4，6-三(三溴苯氧基)-1，3，5-三嗪等溴化添加型阻燃剂；三溴苯基马来酰亚胺、丙烯酸三溴苯酯、甲基丙烯酸三溴苯酯、四溴双酚A型二甲基丙烯酸酯、丙烯酸五溴苄酯及溴化苯乙烯等含不饱和双键基团的溴化反应型阻燃剂等。
磷类阻燃剂的实例为：磷酸三苯酯、磷酸三甲酚酯、磷酸三(二甲苯)酯、磷酸甲酚二苯酯、磷酸甲酚二-2，6-二甲苯酯及间苯二酚双(二苯基磷酸酯)等芳香族类磷酸酯；苯基膦酸二乙烯酯、苯基膦酸二烯丙酯及苯基膦酸双(1-丁烯基)酯等膦酸酯；二苯基磷酸苯酯、二苯基磷酸甲酯、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物衍生物等磷酸酯；双(2-烯丙基苯氧基)磷腈、二甲酚磷腈等磷腈化合物；磷酸三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、聚磷酸蜜白胺、聚磷酸铵、含磷乙烯基苄基化合物及红磷等磷类阻燃剂。
金属氢氧化物阻燃剂的实例为氢氧化镁或氢氧化铝。
另外，上述阻燃剂可以单独使用一种，也可以两种以上组合使用。
在含有阻燃剂的情况下，阻燃剂在树脂组合物中的含量可以为约1至40重量％，优选为约2至30重量％。
另外，树脂组合物还可以还含有各种助剂。作为助剂的具体例，可以举出填料分散剂、消泡剂、抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂、润滑剂等。这些助剂可以单独使用，也可以任何两种或者更两种混合使用。
本公开的树脂组合物可以通过公知的方法如配合、搅拌、混合硅芳炔树脂、氰酸酯化合物和马来酰亚胺化合物、以及任选的促进剂、溶剂、填料、阻燃剂、分散剂、消泡剂、抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂和润滑剂中的任意一种或至少两种的混合物来制备。
通过机械搅拌、乳化或球磨分散，将树脂组合物配制成树脂胶液，然后采用该树脂胶液浸润增强材料，经烘干得预浸片。将该预浸片和金属箔如铜箔或铝箔在真空压机中热压可以制备覆金属层压板。
增强材料的实例可以包括：玻璃纤维布、玻纤无纺布以及有机无纺布等。
为了降低树脂胶液的粘度，可以在加热下进行浸润。进行加热使得树脂胶液的温度小于所用溶剂的沸点，优选浸润时树脂胶液的温度为约50-90℃，进一步优选约55-85℃。
在另一方面，本公开还可以提供一种印刷电路用预浸片，所述印刷电路用预浸片包括增强材料及通过浸润干燥后附着在其上的上面中任何一项所述的树脂组合物。
在再一方面，本公开还可以提供一种绝缘板或覆金属层压板，所述绝缘板或覆金属层压板含有至少一张如上面所述的印刷电路用预浸片。
在又一方面，本公开还可以提供一种印制电路板，所述印制电路板包含：至少一张如上面所述的印刷电路用预浸片，或至少一张如上面所述的绝缘板，或至少一张如上面所述的覆金属层压板。
根据本公开，可以提供一种树脂组合物、通过用增强材料浸润所述树脂组合物得到的印刷电路用预浸片及包含所述印刷电路用预浸片的覆金属层压板或绝缘板，以及包含所述印刷电路用预浸片、所述绝缘板或所述覆金属层压板的印制电路板，使得覆金属层压板可以至少具有低介电损耗因数、高耐热性、低热膨胀系数等特性中的一个。
实施例
下面通过具体实施方式来进一步说明本公开的技术方案。但是，这些实施例是为了举例说明本公开，而不应当理解为限制本公开。
制备例
实施例和对比例中所用的硅芳炔树脂如下制备。
在充满氮气的反应釜中加入3.5份镁粉(化学纯，上海国药集团化学试剂有限公司)，和40份四氢呋喃(THF)溶剂，在室温下搅拌并滴加13.5份溴乙烷(化学纯，上海国药集团化学试剂有限公司)和40份THF的混合溶液，滴加完成后于50℃保温1h。然后在冰水冷浴条件下，滴加7.5份1，3-二乙炔基苯(山东胶州市精细化工有限公司)和40份THF溶剂的混合物，滴加完毕后，于65℃保温1h。然后再次冷却，在冰水冷浴条件下滴加5.5份二氯二甲基硅烷(化学纯，浙江新安化工集团有限公司，蒸馏后使用)和40mlTHF的混合物，滴加完毕后分别于40℃和70℃保温1h。反应完成后，蒸除反应物中的THF，并与冰水冷浴条件下滴加7.2份冰醋酸和50份甲苯溶剂的混合物，充分 搅拌后再滴加140份2.0％稀盐酸水溶液，充分搅拌后分离出上层有机相。将有机相充分水洗至中性，然后干燥，过滤，并蒸除甲苯，得到硅苯炔树脂(即，实施例和对比例中所用的硅芳炔树脂(数均分子量1200，GPC测试的流动相为THF)，以下简称PSA1200)。
实施例1-7与对比例1-3
按照表1或表2中所示的量(重量份)，将硅芳炔树脂，氰酸酯化合物和马来酰亚胺化合物，以及促进剂在溶剂中充分溶解，并混合均匀，然后加入填料和/或阻燃剂，混合均匀，得到胶液。取型号为1080的E型玻璃纤维布(日东纺生产)均匀浸渍上述胶液，在鼓风烘箱中于155℃烘烤3min制得预浸片。分别将4张或8张上述预浸片重叠，上下覆18μm反转铜箔(苏州福田金属有限公司生产)，于真空热压机中在3MPa压力和210℃温度下压制90min得到两种厚度的层压板样品(以下，有时也称为覆铜层压板或覆铜板)。
树脂组合物中组分的量和树脂组合物的测试结果示于下表1和2。
表1
Figure PCTCN2018123416-appb-000008
表2
Figure PCTCN2018123416-appb-000009
PSA1200：制备例所得的硅芳炔树脂；
CE01PS：双酚A型氰酸酯预聚体(数均分子量：3000)，天启化学生产；
CE01MO：双酚A型氰酸酯单体，天启化学生产；
BMI-E：3，3’-二甲基-5，5’-二乙基-4，4’-二苯基甲烷双马来酰亚胺，江苏飞翔化工生产；
BMI-1000：4，4’-二苯甲烷双马来酰亚胺，日本大和生产；
BMI-50P：苯甲烷马来酰亚胺低聚物，日本KI生产；
异辛酸锌：试剂，市售；
DQ1028L：球型二氧化硅，D50约3.0μm，江苏联瑞生产；
SC2050：球型二氧化硅，D50约0.5μm，日本丰田通商提供；
BT-93w：添加型溴系阻燃剂，美国雅宝生产；
XP7866：添加型磷系阻燃剂，美国雅宝生产；
氢氧化铝：OL-104，美国雅宝生产；
DMF：N，N-二甲基甲酰胺，工业品，市售；
甲苯：工业品，市售。
测试表中所述性能的方法如下：
1)玻璃化转变温度Tg：使用动态热机械分析(DMA)测试，按照IPC-TM-6502.4.24所规定的DMA测试方法；
2)热分解温度(Td)：使用热失重分析(TGA)测试，按照标准IPC-TM-650 2.4.24.6；
3)剥离强度(PS)：指在室温下将每毫米铜箔剥离覆铜板所需的拉力；
4)介电常数(Dk)和介电损耗因数(Df)：10GHz使用谐振腔法(SPDR)法测定，按照标准IPC-TM-650 2.5.5.5。
5)阻燃性：按照UL94“50W(20mm)垂直燃烧试验：V-0、V-1和V-2”测试方法测试。
6)热膨胀系数(CTE)和50-260℃热膨胀比例：测试采用静态热分析仪(TMA)测试，测试按照标准IPC-TM-650 2.4.24，其中Z轴表示层压板样品的厚度方向，X轴表示层压板样品的长度方向，而Y轴表示层压板样品的宽度方向。50-260℃热膨胀比例是在层压板样品的Z轴方向测量得到的。
7)热应力：将覆铜层压板漂浮在熔融状态的锡液表面，温度288℃，以分层或气泡的时间作为测试结果。
8)D50：表示平均粒径，是指将粒子的总体积作为100％而求出基于粒径的累积度数分布曲线时，刚好相当于体积为50％的点的粒径，其使用激光衍射散射法的粒度分布测定。
有上述实施例和对比例测试结果可知，该实施例样品的Tg和Td的测试结果都高 于行业中常用印制电路板的Tg和Td。覆铜层压板的介电损耗因数结果说明其在高频高速层压板中将具有很好应用性能，并且其在各个方向上的CTE、50-260℃热膨胀比例和热应力表现优异。
如上，可以提供一种树脂组合物、通过用玻纤布浸润所述树脂组合物得到的印刷电路用预浸片及包含所述印刷电路用预浸片的覆金属层压板或绝缘板，以及包含所述印刷电路用预浸片、所述绝缘板或所述覆金属层压板的印制电路板，使得覆金属层压板可以至少具有低介电损耗因数、高耐热性、低热膨胀系数等特性中的一个，优选同时具有低介电损耗因数、高耐热性、低热膨胀系数。同时，通过添加阻燃剂，可以达到V-0级阻燃性能，使得其适宜于需要阻燃的应用中。
显然，本领域的技术人员可以对本公开实施例进行各种改动和变型而不脱离本公开的精神和范围。这样，倘若本公开的这些修改和变型属于本公开权利要求及其等同技术的范围之内，则本公开也意图包含这些改动和变型在内。

Claims (18)

  1. 一种树脂组合物，所述树脂组合物包含：
    硅芳炔树脂；
    氰酸酯化合物；和
    马来酰亚胺化合物，
    其中所述硅芳炔树脂、所述氰酸酯化合物与所述马来酰亚胺化合物的重量比为(5-95)∶(5-70)∶(5-70)。
  2. 根据权利要求1所述的树脂组合物，其中所述硅芳炔树脂由下式表示：
    Figure PCTCN2018123416-appb-100001
    其中
    n为1至5之间的整数；并且
    R 1和R 2各自独立地是选自由以下各项组成的组中的基团：氢、C 1-6烷基或C 3-6环烷基。
  3. 根据权利要求1所述的树脂组合物，其中所述硅芳炔树脂的数均分子量为250至10000。
  4. 根据权利要求1所述的树脂组合物，其中所述氰酸酯化合物选自2，2-双(4-氰酸苯基)丙烷、双(3，5-二甲基-4-氰酸苯基)甲烷或2，2-双(4-氰酸苯基)乙烷的预聚体或单体中的任意一种或至少两种的组合。
  5. 根据权利要求1所述的树脂组合物，其中所述氰酸酯化合物选自：2，2-双(4-氰酸苯基)丙烷和双(3，5-二甲基-4-氰酸苯基)甲烷的组合，或双(3，5-二甲基-4-氰酸苯基)甲烷和2，2-双(4-氰酸苯基)乙烷的组合。
  6. 根据权利要求1所述的树脂组合物，其中所述马来酰亚胺化合物在其分子结构中含有至少一个下式所示的结构：
    Figure PCTCN2018123416-appb-100002
  7. 根据权利要求1所述的树脂组合物，其中所述马来酰亚胺化合物在其分子结构中含有至少两个下式所示的结构：
    Figure PCTCN2018123416-appb-100003
  8. 根据权利要求1所述的树脂组合物，其中所述马来酰亚胺化合物选自：4，4’-二苯甲烷双马来酰亚胺、苯甲烷马来酰亚胺低聚物、间亚苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3，3’-二甲基-5，5’-二乙基-4，4’-二苯基甲烷双马来酰亚胺、4-甲基-1，3-亚苯基双马来酰亚胺及1，6-双马来酰亚胺-(2，2，4-三甲基)己烷中的任意一种或至少两种的组合。
  9. 根据权利要求1所述的树脂组合物，所述树脂组合物还包含促进剂，其中所述促进剂在所述树脂组合物中的含量为0.01-5重量％。
  10. 根据权利要求9所述的树脂组合物，其中所述促进剂选自：过氧化物、乙酰丙酮的金属盐、环烷酸的金属盐、五氧化钒、胺、季铵盐、咪唑、三苯基膦、三氟化硼络合物、正辛酸或异辛酸的金属盐、乙酰丙酮、环烷酸、硬脂酸的金属盐和水杨酸中的任意一种或至少两种的混合物。
  11. 根据权利要求1所述的树脂组合物，所述树脂组合物还包含填料。
  12. 根据权利要求11所述的树脂组合物，其中所述填料选自：氧化铝、氧化钛、云母、二氧化硅、氧化铍、钛酸钡、钛酸钾、钛酸锶、钛酸钙、碳酸铝、氢氧化镁、氢氧化铝、硅酸铝、碳酸钙、硅酸钙、硅酸镁、氮化硅、氮化硼、煅烧粘土等粘土、滑石、硼酸铝和碳化硅中的任意一种或至少两种的混合物。
  13. 根据权利要求1所述的树脂组合物，所述树脂组合物还包含阻燃剂。
  14. 根据权利要求1所述的树脂组合物，所述树脂组合物还包含溶剂。
  15. 一种印刷电路用预浸片，所述印刷电路用预浸片包括增强材料及通过浸润干燥后附着在其上的如权利要求1至13中任何一项所述的树脂组合物。
  16. 一种绝缘板，所述绝缘板含有至少一张如权利要求15所述的印刷电路用预浸片。
  17. 一种覆金属层压板，所述覆金属层压板包括至少一张如权利要求15所述的印刷电路用预浸片和金属箔。
  18. 一种印制电路板，所述印制电路板包含：至少一张如权利要求15所述的印刷电路用预浸片，或至少一张如权利要求16所述的绝缘板，或至少一张如权利要求17 所述的覆金属层压板。
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CN102020770A (zh) * 2010-11-23 2011-04-20 华东理工大学 一种含硅的芳醚芳炔聚合物及其制备方法
CN102115600A (zh) * 2010-11-26 2011-07-06 苏州生益科技有限公司 一种热固性树脂组合物、半固化片及层压板
CN103582664A (zh) * 2011-05-27 2014-02-12 三菱瓦斯化学株式会社 树脂组合物、预浸料、以及层压板
CN103724999A (zh) * 2013-05-30 2014-04-16 广东生益科技股份有限公司 一种氰酸酯树脂组合物及其用途
CN108395532A (zh) * 2018-02-12 2018-08-14 华东理工大学 改性氰酸酯树脂及其制备方法

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CN102020770A (zh) * 2010-11-23 2011-04-20 华东理工大学 一种含硅的芳醚芳炔聚合物及其制备方法
CN102115600A (zh) * 2010-11-26 2011-07-06 苏州生益科技有限公司 一种热固性树脂组合物、半固化片及层压板
CN103582664A (zh) * 2011-05-27 2014-02-12 三菱瓦斯化学株式会社 树脂组合物、预浸料、以及层压板
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