WO2013029271A1 - 无卤树脂组合物以及使用其制作覆铜板的方法 - Google Patents

无卤树脂组合物以及使用其制作覆铜板的方法 Download PDF

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Publication number
WO2013029271A1
WO2013029271A1 PCT/CN2011/079273 CN2011079273W WO2013029271A1 WO 2013029271 A1 WO2013029271 A1 WO 2013029271A1 CN 2011079273 W CN2011079273 W CN 2011079273W WO 2013029271 A1 WO2013029271 A1 WO 2013029271A1
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WIPO (PCT)
Prior art keywords
resin
parts
copper clad
halogen
free
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PCT/CN2011/079273
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English (en)
French (fr)
Inventor
何岳山
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广东生益科技股份有限公司
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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 US14/239,045 priority Critical patent/US9139750B2/en
Priority to KR1020147004403A priority patent/KR101597925B1/ko
Priority to AU2011376206A priority patent/AU2011376206B2/en
Priority to PCT/CN2011/079273 priority patent/WO2013029271A1/zh
Priority to EP11871425.2A priority patent/EP2752449B1/en
Publication of WO2013029271A1 publication Critical patent/WO2013029271A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09D171/12—Polyphenylene oxides
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • 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
    • 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
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
    • Y10T156/1062—Prior to assembly
    • Y10T156/1075—Prior to assembly of plural laminae from single stock and assembling to each other or to additional lamina

Definitions

  • Halogen-free resin composition and method for producing the same using the same
  • the present invention relates to a resin composition, and more particularly to a resin-free composition and a method of producing a copper clad laminate therewith. Background technique
  • a printed wiring board is developed toward a higher degree of multilayer printed wiring board while being more precisely wired.
  • an effective method is to lower the dielectric constant of the material used.
  • an effective method is to use a material with a lower dielectric loss tangent (dielectric loss).
  • An object of the present invention is to provide a resin-free composition which can satisfy not only by reacting a reaction type allylphenoxycyclotriphosphazene or vinylphenoxycyclotriphosphazene having a very low water absorption rate into a thermosetting resin. Halogen-free flame retardant requirements, and can improve the electrical properties of the system.
  • Another object of the present invention is to provide a method for producing a copper clad laminate using the above resin-free composition, which has a single copper sheet which satisfies halogen-free requirements, has excellent heat resistance and moisture resistance, and has low dielectric loss. Etc.
  • the present invention provides a resin-free composition which is calculated based on the total weight of the solid component, and includes the components and their contents: Reactive allylphenoxycyclotriphosphazene or vinylphenoxy 5-50 parts of base ring triphosphazene, 15-85 parts of thermosetting resin, 1-35 parts of crosslinking curing agent, Crosslinking curing accelerator 0-5 parts, and filler 0-100 parts.
  • m represents an integer from 3 to 25, and the number of X and X is 0 to 2 m of meta-allyl phenoxy O-allylphenoxy: And m-vinylphenoxy: , Y number is l ⁇ 2m,
  • thermosetting resin includes one or more of the following resins:
  • An epoxy resin comprising bisphenol A epoxy resin, bisphenol F epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy, biphenyl epoxy, naphthol epoxy, and phosphorus-containing epoxy resin;
  • a benzoxazine resin comprising a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine tree, a dicyclopentadiene type benzoxazine resin, and a phenolphthalein type benzoxazine resin;
  • a cyanate resin comprising a bisphenol A type cyanate resin, a dicyclopentadiene type cyanate tree, and a novolac type cyanate resin;
  • a bismaleimide resin comprising 4,4'-diphenylmethane bismaleimide, and an allyl-modified diphenylmethane bismaleimide
  • a reactive polyphenylene ether resin having a number average molecular weight of from 1,000 to 7,000, the reactive group of which is a hydroxyl group or a double bond
  • the hydrocarbon resin is composed of a styrene-butadiene styrene resin having a molecular weight of 11,000 or less, a bisphenol-based polybutadiene resin having a polar group, and a copolymer of maleic anhydride grafted butadiene and styrene.
  • the crosslinking curing agent is selected from one or more of a mixture of dicyandiamide, an aromatic amine, an acid anhydride, a phenolic compound, a triallyl isocyanurate, and a phosphorus-containing phenolic aldehyde.
  • the crosslinking curing accelerator is 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, DMP-30 (tris-(dimethylaminomethyl)), six-fold Tetraamine, dicumyl peroxide, tert-butyl peroxybenzoate, 2,5-bis(2-ethylhexanoyl peroxy)-2,5-dimethylhexane, acetylacetonate, And a mixture of one or more of the acid salts.
  • the filler is selected from one or more of the group consisting of aluminum hydroxide, magnesium hydroxide, zeolite, wollastonite, silica, magnesia, silicate 4 bow, carbonate 4, clay, talc, and mica.
  • the present invention provides a method of producing a copper clad laminate using the above resin-free composition, comprising the steps of:
  • Step 1 Take 5 ⁇ 50 parts of the reaction type allylphenoxycyclotriphosphazene or vinylphenoxycyclotriphosphazene, dissolve in a solvent, and completely dissolve at normal temperature or medium temperature;
  • Step 2 taking 15 ⁇ 85 parts of the corresponding thermosetting resin, 1 ⁇ 35 parts of the crosslinking curing agent, 0 ⁇ 5 parts of the crosslinking curing accelerator and 0 ⁇ 100 parts of the filler are added to the above obtained solution, and the glue is obtained by stirring;
  • Step 3 Select a flat surface E-glass cloth, uniformly apply the above glue, and then bake into a B-stage prepreg;
  • Step 4 According to the size of the press, the B-stage prepreg is cut into suitable sizes, several sheets are neatly stacked, and a piece of copper foil is placed on top and bottom, and placed in a vacuum hot press for pressing to obtain a copper clad plate.
  • the solvent is one or more of a benzene and a ketone solvent; the intermediate temperature is 80 °C.
  • the temperature is set according to the boiling point of the solvent used for the glue, the temperature range is 85-175 ° C, and the baking time is 5-20 minutes.
  • the pressing process adopts a stepwise pressing (step heating and boosting) method, and the specific steps are as follows: 15 minutes from room temperature to 150 ° C for 30 minutes, then 5 minutes to 180 ° C to maintain 2 Hours, the last 30 minutes to cool to room temperature; pressure for 1 minute from zero to 0.6Mpa for 20 minutes, then 1 minute to l.OMpa for 2.5 hours; post-treatment conditions for 200 ⁇ 245 °C for 1 to 5 hours .
  • the flame retardant requirement can be satisfied. It can also improve the electrical properties of the system: Reduce and stabilize Dk (dielectric constant) and Df (dielectric loss factor), making it possible to achieve halogen-free high-frequency high-speed substrate materials.
  • the obtained copper clad laminate meets halogen-free requirements and has excellent resistance. Heat and moisture resistance, low dielectric loss and so on.
  • the resin-free composition provided by the present invention is calculated by total weight of solids, and includes components and content thereof: reactive allyl phenoxycyclotriphosphazene or vinyl phenoxycyclotriphosphazene 5-50 Parts, 15-85 parts of thermosetting resin, 1-35 parts of crosslinking curing agent, 0-5 parts of crosslinking curing accelerator, and 0-100 parts of filler.
  • n represents an integer from 3 to 25, X : , and the number of X is 0 to 2 m -
  • the above-mentioned reactive allylphenoxycyclotriphosphazene and vinylphenoxycyclotriphosphazene are phosphazene compounds, and the water absorption rate is extremely low, and the present invention utilizes the reactive group carried therein to react with a specific thermosetting resin. It can realize halogen-free flame retardant of high-frequency high-speed materials without affecting its excellent dielectric constant and dielectric loss tangent performance.
  • the thermosetting resin includes one or more of the following resins: an epoxy resin including a bisphenol A epoxy resin, a bisphenol F epoxy resin, a dicyclopentadiene (DCPD) epoxy resin, and a trisphenol ring. Oxygen, biphenyl epoxy, naphthol epoxy, and phosphorus-containing epoxy resin; benzoxazine resin, including bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, dicyclopentane An ene benzoxazine resin, a phenolphthalein type benzoxazine resin, etc.; a cyanate resin comprising a bisphenol A type cyanate resin, a dicyclopentadiene type cyanate resin, a phenolic type cyanate resin, or the like Bismaleimide tree, which includes 4,4'-diphenylmethane bismaleimide, and allyl-modified diphenylmethane bismaleimide; reactive polyphenylene ether; Resin
  • the reactive polyphenylene ether resin has a number average molecular weight of 1000-7000, the reactive group is a hydroxyl group, a double bond, etc.; a hydrocarbon resin, a B-butyl styrene-butadiene resin having a molecular weight of 11,000 or less, and a polar group-containing ethylene; Polybutadiene resin And a copolymer of maleic anhydride grafted butadiene and styrene.
  • the crosslinking curing agent is selected from one or more of a mixture of dicyandiamide, an aromatic amine, an acid anhydride, a phenolic compound, a isocyanuric acid triene ester, and a phosphorus-containing phenolic aldehyde.
  • the crosslinking curing accelerator is 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, DMP-30 (tris-(dimethylaminomethyl)), six-fold Tetraamine, dicumyl peroxide, tert-butyl peroxybenzoate, 2,5-bis(2-ethylhexanoyl peroxy)-2,5-dimethylhexane, acetylacetonate, And a mixture of one or more of the acid salts.
  • the filler is selected from the group consisting of: one of general-purpose inorganic fillers such as aluminum hydroxide, magnesium hydroxide, zeolite, wollastonite, silica, magnesia, silicate 4 bow, carbonate 4, clay, talc and mica. Or a plurality of kinds, the inorganic filler may be appropriately dose-adjusted according to the purpose of use, and the amount thereof is preferably 100-100 parts by weight based on 100 parts by weight of the total of the organic solids of the components in the halogen-free resin composition. It is preferably 25-100 parts by weight.
  • general-purpose inorganic fillers such as aluminum hydroxide, magnesium hydroxide, zeolite, wollastonite, silica, magnesia, silicate 4 bow, carbonate 4, clay, talc and mica.
  • the inorganic filler may be appropriately dose-adjusted according to the purpose of use, and the amount thereof is preferably 100-100 parts by weight based on 100 parts
  • a prepreg and a copper clad laminate are prepared by using the above-mentioned resin-free composition, and the prepreg produced includes: a base material and a resin-free composition coated thereon, the base material is a fiberglass cloth, etc., and an E-glass cloth is preferable;
  • the copper clad laminate produced includes: a plurality of laminated prepregs, and a copper foil provided on one or both sides of the laminated prepreg.
  • the obtained copper clad laminate satisfies halogen-free requirements, has excellent heat resistance and moisture resistance, and has low dielectric loss.
  • the method for producing a copper clad laminate using the above halogen-free resin composition comprises the following steps: Step 1. Take 5 to 50 parts of the reactive allylphenoxycyclotriphosphazene or vinylphenoxycyclotriphosphazene, and dissolve The solvent such as benzene or ketone is completely dissolved at normal temperature or medium temperature; the solvent may be one or more of benzene and ketone solvents, the normal temperature is normal temperature in the prior art, and the medium temperature refers to 80. °C temperature range.
  • Step 2 taking 15 ⁇ 85 parts of the corresponding thermosetting resin, 1 ⁇ 35 parts of the crosslinking curing agent, 0 ⁇ 5 parts of the crosslinking curing accelerator and 0 ⁇ 100 parts of the filler are added to the above obtained solution, and the glue is obtained by stirring;
  • Step 3 Select a flat surface E-glass cloth, uniformly coat the above glue, and then bake the B-stage prepreg; during the baking of the B-stage prepreg, the temperature is set according to the boiling point of the solvent used for the glue.
  • the temperature range is 85 ⁇ 175°C, and the baking time is 5 ⁇ 20 minutes (min).
  • Step 4 According to the size of the press, the B-stage prepreg is cut into suitable sizes, and several sheets are neatly stacked, and a piece of copper foil is placed on the upper and lower sides, and placed in a vacuum hot press for pressing to obtain a copper clad plate.
  • the pressing process adopts stepwise pressing (step heating and boosting).
  • the specific steps are as follows: 15 minutes from room temperature to 150 ° C for 30 minutes, then 5 minutes to 180 ° C for 2 hours ( Hr ), the temperature is cooled to room temperature in the last 30 minutes; the pressure is raised from zero to 0.6Mpa for 20 minutes, and then raised to l.OMpa for 2.5 hours in 1 minute; the post-treatment condition is 200 ⁇ 245°C. Keep it for 1 ⁇ 5 hours.
  • the dielectric constant, the glass transition temperature, the peel strength, the flammability resistance, the water absorption property, the punching property and the like of the above-mentioned copper clad laminate were measured and described and described in detail in the following examples.
  • Example 1 The embodiments of the present invention are described in detail below, but the present invention is not limited to the scope of the embodiments.
  • Example 1 Example 1:
  • DCPD epoxy resin was HP-7200H (DIC), equivalent 275-280
  • DCPD phenolic resin 20 g selected DCPD phenolic resin was Nihon Petro) -chemical DPP-600M
  • an appropriate amount of imidazole and 2,5-bis(2-ethylhexanoyl peroxy) and mix and mix to obtain a glue.
  • a 300 x 300 cm, smooth, flat E-glass cloth was applied, and the above glue was uniformly applied, and baked in an oven at 155 ° C for 7 minutes to obtain a prepreg.
  • Step-by-step (step-by-step heating and boosting) program suppression in which 15 minutes from room temperature to 150 ° C for 30 min, then 5 min to 180 ° C for 2 hr, the last 30 min to cool the room temperature; pressure lmin from zero to 0.6Mpa is kept for 20min, then lmin is raised to l.OMpa for 2.5hr.
  • Table 2 The basic properties of the obtained copper clad laminate are as shown in Table 2:
  • DCPD benzoxazine 40 g selected DCPD benzoxazine for MT36000 (Huntsman)
  • DCPD epoxy resin 20 g selected DCPD epoxy resin for HP-7200H (DIC) ), equivalent 275-280
  • styrene/maleic anhydride 10g selected anhydride is EF-30, Sartomer
  • appropriate amount of imidazole and 2,5-di(2-ethylhexanoyl peroxy) stirring Mix well to obtain a glue.
  • a 300 x 300 cm, smooth, flat E-glass cloth was applied, and the above glue was uniformly applied, and baked in an oven at 155 ° C for 7 min to obtain a prepreg.
  • Five prepregs with trimmed edges were superimposed, and 35 ⁇ m of copper foil was attached to the top and bottom, and pressed in a vacuum hot press to obtain a copper clad laminate.
  • Stepped (step-by-step heating and boosting) program suppression of which 15 minutes from the room The temperature was raised to 150 ° C for 30 min, then 5 min to 190 ° C for 2 hr, and the last 30 min to cool the room temperature; the pressure Imin was raised from zero to 0.6 Mpa for 20 min, then Imin was raised to l.OMpa for 2.5 hr.
  • Table 1 The basic properties of the obtained copper clad laminate are shown in Table 1.
  • DCPD cyanate was LONZA-Primaset BADCy
  • 4,4'-diphenylmethane bismaleimide 20 g was LONZA-Primaset BADCy
  • DCPD epoxy resin 20g Selected DCPD epoxy resin is HP-7200H (DIC), equivalent 275-280
  • appropriate amount of aluminum acetylacetonate and mix and mix to obtain the glue.
  • a 300 X 300 cm, smooth, flat E-glass cloth was applied, and the above glue was uniformly applied, and baked in an oven at 155 ° C for 7 minutes to obtain a prepreg.
  • Stepwise (step-by-step heating and boosting) program is used, in which 15 minutes from room temperature to 150 ° C for 30 min, then 5 min to 210 ° C for 2 hr, the last 30 min to cool the room temperature; pressure Imin rises from zero to 0.6Mpa is kept for 20min, then Imin is raised to l.OMpa for 2.5hr.
  • the basic properties of the obtained copper clad laminate are shown in Table 1.
  • Stepwise (step-by-step heating and boosting) program is used, in which 15 minutes from room temperature to 150 ° C for 30 min, then 5 min to 190 ° C for 2 hr, last 30 min to cool room temperature; pressure Imin rises from zero to 0.6Mpa is kept for 20min, then Imin is raised to l.OMpa for 2.5hr.
  • Table 1 Comparative Example 1:
  • Step by step Heating and boosting) program pressing, wherein, 15 minutes from room temperature to 150 ° C for 30 min, then 5 min to 190 ° C for 2 hr, the last 30 min to cool the room temperature; pressure lmin from zero to 0.6 Mpa for 20 min, Then lmin was raised to l.OMpa for 2.5 hr.
  • Table 1 The basic properties of the obtained copper clad laminate are shown in Table 1.
  • stepwise (step heating and boosting) program in which it is raised from room temperature to 150 ° C for 15 min, then raised to 190 ° C for 5 min for 5 min, and cooled to room temperature for the last 30 min; the pressure lmin rises from zero to 0.6Mpa is kept for 20min, then lmin is raised to l.OMpa for 2.5hr.
  • Table 1 The basic properties of the obtained copper clad laminate are shown in Table 1.
  • Glass transition temperature Measured according to the differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-650 2.4.25.
  • dielectric loss factor According to the resonance method using the strip line, the dielectric loss factor at 1 GHz is measured according to IPC-TM-650 2.5.5.5.
  • the halogen-free flame retardant can be achieved without lowering the dielectric properties (the halogen content is within the range of the JPCA halogen-free standard), and has excellent heat resistance and also has good properties. Machinability.

Abstract

一种无卤树脂组合物以及使用其制作覆铜板的方法，以固体组分总重量份计算，该无卤树脂组合物包括组分及其含量为：反应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈5-50份、热固性树脂15-85份、交联固化剂1-35份、交联固化促进剂0-5份、及填料0-100份。本发明通过在热固性树脂中引入吸水率极低的反应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈，既能满足无卤阻燃要求，又能改良体系电性能，使得高频高速基板材料无卤化成为可能，所制得的覆铜板满足无卤要求，具有优异的耐热性和耐湿性，介电损耗低等优点。

Description

无卤树脂组合物以及使用其制作覆铜板的方法 技术领域
本发明涉及一种树脂组合物， 尤其涉及一种无 树脂组合物以及使用 其制作覆铜板的方法。 背景技术
近年来， 随着电子设备、 高密度电子仪器组件和高密度印刷线路板布 线中用到的半导体器件的集成技术、 接合技术和装配技术的发展， 电子设 备得到了不断进步， 尤其是在那些使用宽带的电子设备如移动通信装置上 有了快速的发展。
印刷线路板作为这种电子设备的一个构成， 向着更高程度的多层印刷 线路板的同时更为精密布线发展。 为了将信号传输速度提高到加速信息处 理所需要的水平， 有效方法是降低所使用材料的介电常数， 为了降低传输 损耗， 有效办法是使用较低介电损耗正切（介电损耗） 的材料。
电子技术迅速发展的同时， 人们也越来越最求环境保护， 但传统的高 频高速材料基本上是使用卤化物、 锑化物等来达到阻燃目的， 含卤化物的 覆铜板着火燃烧时， 不但发烟量大， 气味难闻， 而且会放出毒性大、 腐蚀 性强的 化氢气体， 不仅污染环境， 也危害人体健康； 目前工业上普遍使 用含磷有菲型化合物 DOPO或 ODOPB对应的环氧树脂来实现普通 FR-4 来达到阻燃， 但是含磷有菲型化合物 DOPO或 ODOPB依然有较大的吸水 率， 对高频高速材料的介电常数、 介质损耗角正切有极大的影响。 发明内容
本发明的目的在于提供一种无 树脂组合物， 通过在热固性树脂中引 入吸水率极低的反应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈， 既能满足无卤阻燃要求， 又能改良体系电性能。
本发明的另一目的在于提供一种使用上述无 树脂组合物制作覆铜板 的方法， 筒单， 所制得的覆铜板满足无卤要求， 具有优异的耐热性和耐湿 性， 介电损耗低等优点。
为实现上述目的， 本发明提供一种无 树脂组合物， 以固体组分总重 量份计算， 其包括组分及其含量为： 反应型烯丙基苯氧基环三磷腈或乙烯 基苯氧基环三磷腈 5-50份、 热固性树脂 15-85份、 交联固化剂 1-35份、 交联固化促进剂 0-5份、 及填料 0-100份。
所述反应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈的化学结 构式如下所示：
式
Figure imgf000003_0001
中 m表示 3-25的整数， X , X数量为 0~2m 间烯丙基苯氧基
Figure imgf000003_0002
邻烯丙基苯氧基：
Figure imgf000003_0003
及间乙烯基苯氧基： , Y 数量为 l~2m ,
X+Y=2m。
所述热固性树脂包括下述树脂中的一种或多种：
环氧树脂， 其包括双酚 A环氧树脂、 双酚 F环氧树脂、 双环戊二烯环 氧树脂、 三酚环氧、 联苯环氧、 萘酚环氧以及含磷环氧树脂；
苯并噁嗪树脂， 其包括双酚 A型苯并噁嗪树脂、 双酚 F型苯并噁嗪树 月旨、 双环戊二烯型苯并噁嗪树脂、 及酚酞型苯并噁嗪树脂；
氰酸酯树脂， 其包括双酚 A 型氰酸酯树脂、 双环戊二烯型氰酸酯树 月旨、 及酚醛型氰酸酯树脂；
双马来酰亚胺树脂， 其包括 4,4' -二苯甲烷双马来酰亚胺、 以及烯丙 基改性二苯甲烷双马来酰亚胺；
数均分子量为 1000-7000 的反应型聚苯醚树脂， 其反应基团为羟基或 双键 及
碳氢树脂， 由分子量 11000 以下的乙婦基丁苯树脂、 带极性基团的乙 婦基聚丁二烯树脂以及马来酸酐接枝丁二烯与苯乙烯的共聚物组成。
所述交联固化剂选自双氰胺、 芳香胺、 酸酐、 酚类化合物、 异氰尿酸 三烯酯以及含磷酚醛中的一种或多种混合。 所述交联固化促进剂为 2 -甲基咪唑、 2 -乙基- 4 -甲基咪唑、 2 -苯 基咪唑、 DMP-30 (三- (二甲胺基甲基） ) 、 六次甲基四胺、 过氧化二异 丙苯、 过氧化苯甲酸叔丁酯、 2,5-二（2-乙基己酰过氧） -2,5-二甲基己烷、 乙酰丙酮酸盐、 及辞酸盐中的一种或多种的混合物。
所述填料选自氢氧化铝、 氢氧化镁、 沸石、 硅灰石、 二氧化硅、 氧化 镁、 硅酸 4弓、 碳酸 4弓、 粘土、 滑石及云母中的一种或多种。
进一步， 本发明还提供一种使用上述无 树脂组合物制作覆铜板的方 法， 包括如下步骤：
步骤 1、 取反应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈 5~50份， 溶于溶剂中， 在常温或中温条件下完全溶解；
步骤 2、 取相应的热固性树脂 15~85份、 交联固化剂 1~35份、 交联固 化促进剂 0~5 份及填料 0~100份加入上述所得溶液中， 搅拌均勾得到胶 液；
步骤 3、 选取表面平整的 E-玻纤布， 均匀涂覆上述胶液， 然后烘制成 B-阶半固化片；
步骤 4、 根据压机大小， 将 B-阶半固化片切成合适的尺寸， 数张整齐 叠加， 并上下各放一张铜箔， 置于真空热压机中进行压制， 得到覆铜板。
所述溶剂为苯类及酮类溶剂中的一种或多种； 所述中温为 80°C。 所述步骤 3烘制 B-阶半固化片的过程中， 温度根据胶液所用溶剂的沸 点来设置， 温度范围为 85~175 °C , 烘片时间为 5~20分钟。
所述步骤 4 中， 压制工艺采用阶梯式压制 （分步升温及升压） 法， 具 体步骤为： 15分钟从室温升至 150°C保持 30分钟， 然后 5分钟升至 180°C 保持 2小时， 最后 30分钟降温至室温； 压力 1分钟从零升至 0.6Mpa保压 20分钟， 然后 1分钟升至 l.OMpa保压 2.5小时； 后处理条件为 200~245 °C 保持 1~5小时。
本发明的有益效果： 本发明通过在热固性树脂中引入吸水率极低的反 应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈， 既能满足无 阻燃 要求， 又能改良体系电性能： 降低、 稳定 Dk (介电常数）和 Df (介质损 耗因数） ， 使得高频高速基板材料无卤化成为可能， 所制得的覆铜板满足 无卤要求， 具有优异的耐热性和耐湿性， 介电损耗低等优点。 具体实施方式
本发明提供的无 树脂组合物， 以固体总重量份计算， 其包括组分及 其含量为： 反应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈 5-50 份、 热固性树脂 15-85份、 交联固化剂 1-35份、 交联固化促进剂 0-5份、 及填料 0-100份。
所述反应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈的化学结 构式如 示：
Figure imgf000005_0001
式中 m表示 3-25的整数， X ： , X数量为 0~2m-
、 间烯丙基苯氧基
Figure imgf000005_0002
邻烯丙基苯氧基： 对乙烯基苯氧基
Figure imgf000005_0003
及间乙烯基苯氧基: Y数量为 l~2m; 所述 X+Y=2m。
上述反应型烯丙基苯氧基环三磷腈及乙烯基苯氧基环三磷腈为磷腈化 合物， 吸水率极低， 本发明利用其所带的反应型基团与特定的热固性树脂 反应， 可实现高频高速材料无卤阻燃， 且不影响其优良的介电常数及介质 损耗角正切性能。
所述热固性树脂包括下述树脂中的一种或多种： 环氧树脂， 其包括双 酚 A环氧树脂、 双酚 F环氧树脂、 双环戊二烯（DCPD )环氧树脂、 三酚 环氧、 联苯环氧、 萘酚环氧以及含磷环氧树脂等； 苯并噁嗪树脂， 其包括 双酚 A型苯并噁嗪树脂、 双酚 F型苯并噁嗪树脂、 双环戊二烯型苯并噁嗪 树脂、 酚酞型苯并噁嗪树脂等； 氰酸酯树脂， 其包括双酚 A 型氰酸酯树 脂、 双环戊二烯型氰酸酯树脂、 酚醛型氰酸酯树脂等； 双马来酰亚胺树 月旨， 其包括 4,4' -二苯甲烷双马来酰亚胺、 以及烯丙基改性二苯甲烷双马 来酰亚胺等； 反应性聚苯醚树脂； 及碳氢树脂。 其中所述反应性聚苯醚树 脂数均分子量为 1000-7000, 反应基团为羟基、 双键等； 碳氢树脂， 由分 子量 11000 以下的乙婦基丁苯树脂、 带极性基团的乙烯基聚丁二烯树脂以 及马来酸酐接枝丁二烯与苯乙烯的共聚物组成。
所述的交联固化剂选自双氰胺、 芳香胺、 酸酐、 酚类化合物、 异氰尿 酸三烯酯以及含磷酚醛中的一种或多种混合。
所述交联固化促进剂为 2 -甲基咪唑、 2 -乙基- 4 -甲基咪唑、 2 -苯 基咪唑、 DMP-30 (三- (二甲胺基甲基） ) 、 六次甲基四胺、 过氧化二异 丙苯、 过氧化苯甲酸叔丁酯、 2,5-二（2-乙基己酰过氧） -2,5-二甲基己烷、 乙酰丙酮酸盐、 及辞酸盐中的一种或多种的混合物。
所述填料选自： 氢氧化铝、 氢氧化镁、 沸石、 硅灰石、 二氧化硅、 氧 化镁、 硅酸 4弓、 碳酸 4弓、 粘土、 滑石及云母等通用的无机填料中的一种或 多种， 该无机填料可以随使用目的作适当的剂量调整， 其用量以上述无卤 树脂组合物中的组分的有机固形物总量 100重量份计算， 以 0-100重量份 为宜， 最佳以 25-100重量份。
采用上述的无 树脂组合物制作半固化片及覆铜板等， 其所制作的半 固化片包括： 基料及涂覆其上的无 树脂组合物， 基料为玻纤布等， 可优 选 E-玻纤布； 其所制作的覆铜板， 包括： 数张叠合的半固化片、 及设于叠 合后的半固化片的一面或两面上的铜箔。 所制得的覆铜板满足无卤要求， 具有优异的耐热性和耐湿性， 介电损耗低等优点。
使用上述无卤树脂组合物制作覆铜板的方法， 包括如下步骤： 步骤 1、 取反应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈 5~50份， 溶于苯类、 酮类等的溶剂中， 在常温或中温条件下完全溶解； 溶 剂可为苯类及酮类溶剂中的一种或多种， 常温为现有技术中的常温， 中温 指的是 80°C的温度范围。
步骤 2、 取相应的热固性树脂 15~85份、 交联固化剂 1~35份、 交联固 化促进剂 0~5 份及填料 0~100份加入上述所得溶液中， 搅拌均勾得到胶 液；
步骤 3、 选取表面平整的 E-玻纤布， 均匀涂覆上述胶液， 然后烘制成 B-阶半固化片； 烘制 B-阶半固化片的过程中， 温度根据胶液所用溶剂的沸 点来设置， 温度范围为 85~175°C , 烘片时间为 5~20分钟（min ) 。
步骤 4、 根据压机大小， 将 B-阶半固化片切成合适的尺寸， 数张整齐 叠加， 并上下各放一张铜箔， 置于真空热压机中进行压制， 得到覆铜板。 该步骤中， 压制工艺采用阶梯式压制 （分步升温及升压） 法， 具体步骤 为： 15分钟从室温升至 150°C保持 30分钟， 然后 5分钟升至 180°C保持 2 小时（hr ) , 最后 30分钟降温至室温； 压力 1分钟从零升至 0.6Mpa保压 20分钟， 然后 1分钟升至 l.OMpa保压 2.5小时； 后处理条件为 200~245°C 保持 1~5小时。
针对上述制成的覆铜板测其介电常数、 玻璃化转变温度、 剥离强度、 耐燃烧性、 吸水性、 沖孔性等， 如下述实施例进一步给予详加说明与描 述。
兹将本发明实施例详细说明如下， 但本发明并非局限在实施例范围。 实施例 1:
将溶剂、 六氯环三磷腈、 烯丙基苯酚 （以邻烯丙基苯酚为主要成 分） 、 缚酸剂加入反应装置内， 搅拌， 通入氮气保护， 加热至 50~120°C , 再向反应装置中加入催化剂， 反应 5-16 小时后冷却至室温， 抽滤， 对滤 液进行加压蒸馏， 蒸发溶剂， 得到棕色粉末或粘稠状产物。 取上述产物 30g溶于有机溶剂后， 加入 DCPD环氧树脂 50g (所选 DCPD环氧树脂为 HP-7200H ( DIC ) , 当量 275-280 ) 、 DCPD 酚醛树脂 20g (所选 DCPD 酚醛树脂为 Nihon Petro-chemical DPP-600M ) 、 适量的咪唑和 2,5-二 ( 2- 乙基己酰过氧） ， 搅拌混合均勾得到胶液。 选取 300 x 300cm、 表面光 洁、 平整的 E-玻纤布， 均匀涂覆上述胶液， 在烘箱中 155 °C下烘烤 7min 制得半固化片。 将 5 张裁去毛边的半固化片叠加， 上下附上 35 μ ιη 的铜 箔， 置于真空热压机中压制得到覆铜板。 采用阶梯式（分步升温及升压） 程序压制， 其中， 15 分钟从室温升至 150°C保持 30min, 然后 5min升至 180°C保持 2hr, 最后 30min降温室温； 压力 lmin从零升至 0.6Mpa保压 20min, 然后 lmin升至 l.OMpa保压 2.5hr。 所制得的覆铜板基本性能如表 实施例 2:
将溶剂、 六氯环三磷腈、 烯丙基苯酚 （以邻烯丙基苯酚为主要成 分） 、 缚酸剂加入反应装置内， 搅拌， 通入氮气保护， 加热至 50~120°C , 再向反应装置中加入催化剂， 反应 5-16 小时后冷却至室温， 抽滤， 对滤 液进行加压蒸馏， 蒸发溶剂， 得到棕色粉末或粘稠状产物。 取上述产物 30g溶于有机溶剂后， 加入 DCPD苯并噁嗪 40g (所选 DCPD苯并噁嗪为 MT36000 ( Huntsman ) ) 、 DCPD环氧树脂 20g (所选 DCPD环氧树脂为 HP-7200H ( DIC ) , 当量 275-280 ) 、 苯乙烯 /顺丁烯二酸酐 10g (所选酸 酐为 EF-30, Sartomer ) 、 适量的咪唑和 2,5-二（2-乙基己酰过氧） ， 搅拌 混合均匀得到胶液。 选取 300 x 300cm、 表面光洁、 平整的 E-玻纤布， 均 匀涂覆上述胶液， 在烘箱中 155°C下烘烤 7min制得半固化片。 将 5张裁去 毛边的半固化片叠加， 上下附上 35 μ ιη的铜箔， 置于真空热压机中压制得 到覆铜板。 采用阶梯式（分步升温及升压）程序压制， 其中， 15分钟从室 温升至 150°C保持 30min, 然后 5min升至 190°C保持 2hr, 最后 30min降 温室温； 压力 Imin从零升至 0.6Mpa保压 20min, 然后 Imin升至 l.OMpa 保压 2.5hr。 所制得的覆铜板基本性能如表一。
实施例 3:
将溶剂、 六氯环三磷腈、 烯丙基苯酚 （以邻烯丙基苯酚为主要成 分） 、 缚酸剂加入反应装置内， 搅拌， 通入氮气保护， 加热至 50~120°C , 再向反应装置中加入催化剂， 反应 5-16 小时后冷却至室温， 抽滤， 对滤 液进行加压蒸馏， 蒸发溶剂， 得到棕色粉末或粘稠状产物。 取上述产物 30g 溶于有机溶剂后， 加入 DCPD 氰酸酯 30g (所选 DCPD 氰酸酯为 LONZA-Primaset BADCy ) 、 4,4' -二苯甲烷双马来酰亚胺 20g、 DCPD环 氧树脂 20g (所选 DCPD 环氧树脂为 HP-7200H ( DIC ) , 当量 275- 280 ) 、 适量的乙酰丙酮酸铝， 搅拌混合均勾得到胶液。 选取 300 X 300cm, 表面光洁、 平整的 E-玻纤布， 均匀涂覆上述胶液， 在烘箱中 155 °C下烘烤 7min制得半固化片。 将 5 张裁去毛边的半固化片叠加， 上下附 上 35 μ ιη的铜箔， 置于真空热压机中压制得到覆铜板。 采用阶梯式（分步 升温及升压）程序压制， 其中， 15分钟从室温升至 150°C保持 30min, 然 后 5min升至 210°C保持 2hr, 最后 30min降温室温； 压力 Imin从零升至 0.6Mpa保压 20min, 然后 Imin升至 l.OMpa保压 2.5hr。 所制得的覆铜板 基本性能如表一。
实施例 4:
将溶剂、 六氯环三磷腈、 烯丙基苯酚 （以邻烯丙基苯酚为主要成 分） 、 缚酸剂加入反应装置内， 搅拌， 通入氮气保护， 加热至 50~120°C , 再向反应装置中加入催化剂， 反应 5-16 小时后冷却至室温， 抽滤， 对滤 液进行加压蒸馏， 蒸发溶剂， 得到棕色粉末或粘稠状产物。 取上述产物 30g 溶于有机溶剂后， 加入反应性聚苯醚树脂 50g (所选反应性聚苯醚树 月旨 MX9000, SABIC ) 、 DCPD 环氧树脂 20g (所选 DCPD 环氧树脂为 HP-7200H ( DIC ) , 当量 275-280 ) 、 适量的咪唑和 2,5-二（2-乙基己酰过 氧） ， 搅拌混合均匀得到胶液。 选取 300 x 300cm、 表面光洁、 平整的 E- 玻纤布， 均匀涂覆上述胶液， 在烘箱中 155°C下烘烤 7min制得半固化片。 将 5张裁去毛边的半固化片叠加， 上下附上 35 μ ιη的铜箔， 置于真空热压 机中压制得到覆铜板。 采用阶梯式（分步升温及升压）程序压制， 其中， 15分钟从室温升至 150°C保持 30min, 然后 5min升至 190°C保持 2hr, 最 后 30min降温室温； 压力 Imin从零升至 0.6Mpa保压 20min, 然后 Imin 升至 l.OMpa保压 2.5hr。 所制得的覆铜板基本性能如表一。 比较例 1:
将溶剂、 六氯环三磷腈、 乙烯基苯酚（对乙烯基苯酚与间乙烯基苯酚
50/50 混合物） 、 缚酸剂加入反应装置内， 搅拌， 通入氮气保护， 加热至 50~120°C , 再向反应装置中加入催化剂， 反应 5-16 小时后冷却至室温， 抽滤， 对滤液进行加压蒸馏， 蒸发溶剂， 得到棕色粉末或粘稠状产物。 取 上述产物 30g溶于有机溶剂后， 加入 DCPD氰酸酯 30g (所选 DCPD氰酸 酯为 LONZA-Primaset BADCy ) 、 4,4' -二苯甲烷双马来酰亚胺 20g、 DCPD环氧树脂 20g (所选 DCPD环氧树脂为 HP-7200H ( DIC ) , 当边的 半固化片叠加， 上下附上 35 μ ιη的铜箔， 置于真空热压机中压制得到覆铜 板。 采用阶梯式（分步升温及升压）程序压制， 其中， 15分钟从室温升至 150°C保持 30min, 然后 5min升至 190°C保持 2hr, 最后 30min降温室温； 压力 lmin从零升至 0.6Mpa保压 20min, 然后 lmin升至 l.OMpa保压 2.5hr。 所制得的覆铜板基本性能如表一。
比较例 2:
将溶剂、 六氯环三磷腈、 乙烯基苯酚（对乙烯基苯酚与间乙烯基苯酚
50/50 混合物） 、 缚酸剂加入反应装置内， 搅拌， 通入氮气保护， 加热至 50~120°C , 再向反应装置中加入催化剂， 反应 5-16 小时后冷却至室温， 抽滤， 对滤液进行加压蒸馏， 蒸发溶剂， 得到棕色粉末或粘稠状产物。 取 上述产物 30g溶于有机溶剂后， 加入反应性聚苯醚树脂 50g (所选反应性 聚苯醚树脂 MX9000, SABIC ) 、 DCPD环氧树脂 20g (所选 DCPD环氧 树脂为 HP-7200H ( DIC ) , 当量 275-280 ) 、 适量的咪唑和 2,5-二（2-乙 基己酰过氧） ， 搅拌混合均勾得到胶液。 选取 300 x 300cm、 表面光洁、 平整的 E-玻纤布， 均匀涂覆上述胶液， 在烘箱中 155°C下烘烤 7min制得 半固化片。 将 5张裁去毛边的半固化片叠加， 上下附上 35 μ ιη的铜箔， 置 于真空热压机中压制得到覆铜板。 采用阶梯式（分步升温及升压）程序压 制， 其中， 15分钟从室温升至 150°C保持 30min, 然后 5min升至 190°C保 持 2hr, 最后 30min降温室温； 压力 lmin从零升至 0.6Mpa保压 20min, 然后 lmin升至 l.OMpa保压 2.5hr。 所制得的覆铜板基本性能如表一。
、 特性评估
Figure imgf000009_0001
°c,
DMA)
剥离强度
( 1/20Z, >1.4 >1.4 >1.0 >1.0 >1.0 >1.0 N/mm )
耐燃烧
( 1.60mm V-1 V-0 V-0 V-0 V-0 V-0
)
耐浸焊性
〇 Δ 〇 〇 〇 〇 (分层）
吸水性
0.11 0.10 0.13 0.11 0.12 0.10 (%)
介电常数
(RC50, 4.0 4.2 3.8 3.6 3.7 3.5 1GHZ)
介电损耗
(RC50, 0.010 0.009 0.005 0.003 0.005 0.003 1GHZ)
T-300/min >60 >60 >120 >120 >120 >120 沖孔性 〇 Δ 〇 〇 Δ 〇 以上特性的测试方法如下：
(1) 、 玻璃化转变温度（Tg) ： 根据差示扫描量热法 （DSC) , 按 照 IPC-TM-650 2.4.25 所规定的 DSC方法进行测定。
(2) 、 耐燃烧性（难燃性） ： 依据 UL 94法测定。
(3) 、 耐浸焊性： 将在 121°C、 105Kpa 的加压蒸煮处理装置内保持 2 小时后的试样（ 100 X 100mm的基材）浸在加热至 260°C的焊锡槽中 20 秒钟， 以肉眼观察（hi)有无分层， （h2)有无发生白斑或起皱， 表中的 符号〇示无变化， Δ示发生白斑， X示发生分层。
(4) 、 吸水性： 按照 IPC-TM-650 2.6.2.1方法进行测定。
(5) 、 介质损耗因数： 根据使用条状线的共振法， 按照 IPC-TM-650 2.5.5.5测定 1GHz下的介质损耗因数。
(6) 、 沖孔性： 将 1.60mm厚的基材放于一定图形的沖模上进行沖 孔， 以肉眼观察（hi ) 孔边无白圏， （h2) 孔边有白圏， （h3) 孔边裂 开， 表中的分别以符号〇、 Δ、 X表示。
由上述结果可知， 依据本发明可达到不降低介电性能的基础上达到无 卤阻燃 （卤素含量在 JPCA 无卤标准要求范围内 ) , 且具有优异的耐热 性， 同时也具有较好的可加工性。
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成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。

Claims

权 利 要 求
1、 一种无 树脂组合物， 以固体组分总重量份计算， 其包括组分及 其含量为： 反应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈 5-50 份、 热固性树脂 15-85份、 交联固化剂 1-35份、 交联固化促进剂 0-5份、 及填料 0-100份。
2、 如权利要求 1 所述的无卤树脂组合物， 其中， 所述反应型烯丙基 苯氧基环三 腈或乙婦基苯氧基环三磷腈的化学结构式如下所示：
Figure imgf000012_0001
式中 m表示 3-25的整数， X , X数量为 0~2m- 间烯丙基苯氧基
Figure imgf000012_0002
、 邻烯丙基苯氧基 、 对乙烯基苯氧基
Figure imgf000012_0003
及间乙烯基苯氧基: Y 数量为 l~2m ,
X+Y=2m。
3、 如权利要求 1 所述的无卤树脂组合物， 其中， 所述热固性树脂包 括下述树脂中的一种或多种：
环氧树脂， 其包括双酚 A环氧树脂、 双酚 F环氧树脂、 双环戊二烯环 氧树脂、 三酚环氧、 联苯环氧、 萘酚环氧以及含磷环氧树脂；
苯并噁嗪树脂， 其包括双酚 A型苯并噁嗪树脂、 双酚 F型苯并噁嗪树 脂、 双环戊二烯型苯并噁嗪树脂、 及酚酞型苯并噁嗪树脂；
氰酸酯树脂， 其包括双酚 A 型氰酸酯树脂、 双环戊二烯型氰酸酯树 月旨、 及酚醛型氰酸酯树脂；
双马来酰亚胺树脂， 其包括 4,4' -二苯甲烷双马来酰亚胺、 以及烯丙 基改性二苯甲烷双马来酰亚胺；
数均分子量为 1000-7000 的反应型聚苯醚树脂， 其反应基团为羟基或 双键； 及
碳氢树脂， 由分子量 11000 以下的乙婦基丁苯树脂、 带极性基团的乙 婦基聚丁二烯树脂以及马来酸酐接枝丁二烯与苯乙烯的共聚物组成。
4、 如权利要求 1 所述的无 树脂组合物， 其中， 所述交联固化剂选 自双氰胺、 芳香胺、 酸酐、 酚类化合物、 异氰尿酸三烯酯以及含磷酚醛中 的一种或多种混合。
5、 如权利要求 1 所述的无 树脂组合物， 其中， 所述交联固化促进 剂为 2 -甲基咪唑、 2 -乙基- 4 -甲基咪唑、 2 -苯基咪唑、 三 -（二甲胺 基甲基） 、 六次甲基四胺、 过氧化二异丙苯、 过氧化苯甲酸叔丁酯、 2,5- 二（2-乙基己酰过氧） -2,5-二甲基己烷、 乙酰丙酮酸盐、 及辞酸盐中的一 种或多种的混合物。
6、 如权利要求 1 所述的无 树脂组合物， 其中， 所述填料选自氢氧 化铝、 氢氧化镁、 沸石、 硅灰石、 二氧化硅、 氧化镁、 硅酸 4弓、 碳酸钙、 粘土、 滑石及云母中的一种或多种。
7、 一种使用如权利要求 1 所述的无 树脂组合物制作覆铜板的方 法， 包括如下步骤：
步骤 1、 取反应型烯丙基苯氧基环三磷腈或乙烯基苯氧基环三磷腈 5~50份， 溶于溶剂中， 在常温或中温条件下完全溶解；
步骤 2、 取相应的热固性树脂 15~85份、 交联固化剂 1~35份、 交联固 化促进剂 0~5 份及填料 0~100份加入上述所得溶液中， 搅拌均勾得到胶 液；
步骤 3、 选取表面平整的 E-玻纤布， 均匀涂覆上述胶液， 然后烘制成 B-阶半固化片；
步骤 4、 根据压机大小， 将 B-阶半固化片切成合适的尺寸， 数张整齐 叠加， 并上下各放一张铜箔， 置于真空热压机中进行压制， 得到覆铜板。
8、 如权利要求 7 所述的覆铜板的制作方法， 其中， 所述溶剂为苯类 及酮类溶剂中的一种或多种； 所述中温为 80°C。
9、 如权利要求 7 所述的覆铜板的制作方法， 其中， 所述步骤 3 烘制
B-阶半固化片的过程中， 温度根据胶液所用溶剂的沸点来设置， 温度范围 为 85~175 °C , 烘片时间为 5~20分钟。
10、 如权利要求 7所述的覆铜板的制作方法， 其中， 所述步骤 4中， 压制工艺采用阶梯式压制法， 具体步骤为： 15分钟从室温升至 150°C保持 分钟， 然后 5分钟升至 180°C保持 2小时， 最后 30分钟降温至室温； 1分钟从零升至 0.6Mpa保压 20分钟， 然后 1分钟升至 l.OMpa保压 小时； 后处理条件为 200~245 °C保持 1-5小时。
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