WO2015180206A1 - 一种热固性树脂夹心预浸体、制备方法及覆铜板 - Google Patents

一种热固性树脂夹心预浸体、制备方法及覆铜板 Download PDF

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Publication number
WO2015180206A1
WO2015180206A1 PCT/CN2014/079599 CN2014079599W WO2015180206A1 WO 2015180206 A1 WO2015180206 A1 WO 2015180206A1 CN 2014079599 W CN2014079599 W CN 2014079599W WO 2015180206 A1 WO2015180206 A1 WO 2015180206A1
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WIPO (PCT)
Prior art keywords
filler
resin
thermosetting resin
mass
cloth
Prior art date
Application number
PCT/CN2014/079599
Other languages
English (en)
French (fr)
Inventor
柴颂刚
Original Assignee
广东生益科技股份有限公司
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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 EP14752247.8A priority Critical patent/EP3162561A4/en
Priority to US14/378,012 priority patent/US20160243798A1/en
Publication of WO2015180206A1 publication Critical patent/WO2015180206A1/zh

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Classifications

    • 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
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B15/092—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 comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0022—Glass fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/10—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
    • D06N3/103—Thermosetting synthetic rubbers
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/08—Inorganic fibres
    • 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
    • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
    • 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
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/026—Nanotubes or nanowires
    • 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

Definitions

  • the present invention relates to a thermosetting resin composition, and a copper clad laminate and a printed circuit wiring board produced therefrom.
  • fillers in the CCL industry have become an important means to improve the performance of CCL.
  • the development trend of fillers in the CCL industry is the continuous increase of filler content.
  • the high content of fillers leads to more excellent properties, such as lowering the coefficient of thermal expansion, increasing the thermal conductivity, increasing the strength, and so on.
  • Patent CN101973145 improves the adhesion of high filler content thermosetting resins to metal foils by applying a metal foil. It is proposed in Japanese Patent Laid-Open No. 2009-127014 to apply a thermosetting resin glue containing different amounts of inorganic fillers on both sides of a prepreg. The prepreg is coated on the side of the conductive layer and coated with a low inorganic filler content to improve adhesion to the metal foil.
  • both of these methods require the use of special gluing equipment, which increases production costs.
  • thermosetting resin sandwich prepreg is composed of an intermediate layer and an outer layer coated on both sides of the intermediate layer, the intermediate layer containing a high filler content thermosetting resin composition, and the outer layer contains a low filler content thermosetting resin composition.
  • the copper clad laminate prepared using the prepreg has good metal foil adhesion, good insulation, and uniform dielectric constant distribution.
  • the intermediate layer of the thermosetting resin sandwich prepreg comprises 20-80% by mass of filler, 20-70% by mass of reinforcing material, 0-30% by mass of thermosetting resin (filler+reinforced material+thermosetting resin total 100)
  • the prepreg layer includes 0-20% by mass of a filler, and 20-80% by mass of a thermosetting resin (filler + thermosetting resin total 100% by mass).
  • the reinforcing material is an inorganic or organic material
  • the inorganic material is a woven fabric or a non-woven fabric or paper of glass fiber, carbon fiber, boron fiber, or metal, wherein the glass fiber cloth or the non-woven fabric is E-glass, Q-type cloth, NE cloth, D-type cloth, S-type cloth, or high-silicone cloth
  • organic materials are polyester, polyamine, polyacrylic acid, polyimide, aramid, polytetrafluoroethylene, Or woven fabric or non-woven fabric or paper made of syndiotactic polystyrene.
  • the filler is selected from the group consisting of crystalline silica, molten silica, spherical silica, aluminum hydroxide, calcium carbonate, barium titanate, barium titanate, barium titanate Bismuth, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, titanium dioxide, glass powder, glass chopped fiber, talc, mica powder, carbon black, carbon nanotubes, graphene, metal powder, zinc molybdate, poly One or more of phenyl sulfide and PTFE powder, wherein the powder filler has a median particle diameter of 0.01 to 15 ⁇ ⁇ ; preferably, the powder filler has a median diameter of 0.5 to 10 ⁇ ⁇ .
  • the fiberglass cloth is a ⁇ -type fiberglass cloth, the corresponding filler has a Dk of 6.0-6.6, and the filler is selected from E glass frit; in another preferred embodiment, the fiberglass cloth is For NE type fiberglass cloth, the corresponding filler has a Dk of 4.4 to 4.6, and the filler is selected from NE glass powder.
  • the thermosetting resin comprises: epoxy resin, cyanate resin, phenolic resin, polyphenylene ether resin, polybutadiene resin, polybutadiene and styrene copolymer resin, polytetrafluoroethylene Vinyl resin, polybenzoxazine resin, polyimide, silicone resin, bismaleimide triazine resin (BT resin), LCP (Liquid Crystal Polymer) resin and bismaleimide resin One or more.
  • the outer layer of the prepreg has a thickness of 1 to 100 ⁇ m ; preferably, the outer layer of the prepreg has a thickness of 5 to 50 ⁇ m.
  • Another object of the present invention is to provide a method of fabricating a sandwich prepreg according to the present invention, which comprises the steps of:
  • Step 1 The reinforcing material is impregnated with a thermosetting resin glue having a filler content of 40-100% by mass (the mass % is a solid content of the thermosetting resin glue, excluding the solvent), to obtain a prepreg intermediate layer;
  • Step 2 Step 1
  • the obtained prepreg intermediate layer is further impregnated with a thermosetting resin glue having a filler content of 0 to 30% by mass to obtain a sandwich prepreg.
  • the amount of the thermosetting resin gum filler impregnated in the above step 2 is from 0 to 20%.
  • the centered prepreg is formed by a vertical or horizontal impregnation machine.
  • the copper clad laminate comprises: a prepreg, and a copper foil clad on both sides of the prepreg, the prepreg comprising a reinforcing material and a thermosetting resin composition adhered thereto by dipping and drying.
  • the reinforcing material is an inorganic or organic material
  • the inorganic material is a woven fabric or a non-woven fabric or paper of glass fiber, carbon fiber, boron fiber, or metal, wherein the glass fiber cloth or non-woven fabric E-glass, Q cloth, NE cloth, D cloth, S cloth, or high silica cloth
  • organic materials are polyester, polyamine, polyacrylic acid, polyimide, aramid, PTFE Or a woven or nonwoven fabric or paper made of syndiotactic polystyrene
  • the metal foil is copper, brass, aluminum, nickel, or an alloy of these metals or a composite metal foil, the thickness of the metal foil is 12- 150 ⁇ ⁇ .
  • the present invention has the following beneficial effects:
  • thermosetting resin sandwich prepreg used in the present invention wherein the interlayer contains a high filler content thermosetting
  • the resin composition has an outer layer containing a low filler content thermosetting resin composition, thereby improving the adhesion of the prepreg layer to the metal foil.
  • thermosetting resin sandwich prepreg used in the present invention can improve the insulation of the prepreg because the filler is concentrated in the middle and the outer layer is protected by a thermosetting resin excellent in insulation. Due to the protection of the outer layer thermosetting resin layer, the copper clad laminate of the present invention may use a poorly insulating filler such as a metal powder or a carbon powder; or a chemically resistant filler such as calcium carbonate or hydroxide may also be used. aluminum.
  • a poorly insulating filler such as a metal powder or a carbon powder
  • a chemically resistant filler such as calcium carbonate or hydroxide may also be used. aluminum.
  • the sandwich prepreg used in the present invention improves the uniformity of the horizontal direction of the copper clad laminate and improves the uniformity of the dielectric constant of the clad laminate.
  • FIG. 1 is a schematic view showing the structure of a thermosetting resin sandwich prepreg of the present invention. 1 is the middle layer and 2 is the outer layer. Specific form
  • the Dk used in the present invention means a dielectric constant, which is a value measured by the SPDR method at a frequency of 10 GHz.
  • the Df used in the present invention means a dielectric loss value which is tested by the SPDR method at a frequency of 10 GHz.
  • the resin composition used in the present invention means a composition comprising a resin and a curing agent.
  • an epoxy resin composition refers to a composition comprising an epoxy resin and a suitable curing agent.
  • Those skilled in the art can select a suitable curing agent and its amount depending on the resin to be used, and can also select a suitable organic solvent depending on the resin to be used and the curing agent.
  • the thermosetting resin includes: an epoxy resin, a cyanate resin, a phenol resin, a polyphenylene ether resin, a polybutadiene resin, a polybutadiene and a styrene copolymer resin, a polytetrafluoroethylene resin, Polybenzoxazine resin, polyimide, silicone-containing resin, bismaleimide triazine resin (BT resin), One or more of LCP (Liquid Crystal Polymer) resin and bismaleimide resin.
  • the filler used in the present invention refers to a filler material, referred to as a filler.
  • the purpose of using the filler in the copper clad laminate industry is not only to reduce the cost, but to improve the performance of the copper clad laminate, such as reduction of CTE, improvement of flame retardancy, thermal conductivity and Improvement of mechanical properties of the sheet, etc.
  • the filler is selected from the group consisting of crystalline silica, molten silica, spherical silica, aluminum hydroxide, calcium carbonate, barium titanate, barium titanate, barium titanate, nitrogen. Boron, aluminum nitride, silicon carbide, aluminum oxide, titanium dioxide, glass powder, glass chopped fiber, talc, mica powder, carbon black, carbon nanotubes, graphene, metal powder, zinc molybdate, polyphenylene sulfide And one or more of the PTFE powders, wherein the powder filler has a median particle diameter of 0.01 to 15 ⁇ ; preferably, the powder filler has a median particle diameter of 0.5 to 10 ⁇ .
  • the glue used in the present invention means a glue solution in which the resin composition of the present invention is dissolved in a suitable organic solvent.
  • the glue used in the present invention refers to a dispersion obtained by dissolving the resin composition of the present invention in a suitable organic solvent and then adding the filler.
  • a suitable dielectric constant (Dk) by adjusting the amount of filler in the pretreatment glue.
  • the glue Dk is the Dk of the dry gum obtained after the solvent is removed, which is only related to the amount of the resin composition and the filler, regardless of the amount of the solvent.
  • the dipping used in the present invention refers to the operation of dipping the fiberglass cloth into the glue and then drying the solvent through the gluing machine.
  • the high filler content resin has a Dk equal to 30% of the resin of the reinforcing material layer used, preferably Dk ⁇ 20% of the reinforcing material layer used, more preferably 10% of the reinforcing material layer used.
  • Dk equal to 30% of the resin of the reinforcing material layer used, preferably Dk ⁇ 20% of the reinforcing material layer used, more preferably 10% of the reinforcing material layer used.
  • the reinforcing material is an inorganic or organic material
  • the inorganic material is glass fiber, carbon.
  • Woven fabrics or nonwoven fabrics or papers of fibers, boron fibers, or metals in which the glass fiber cloth or nonwoven fabric is E-glass, Q-type cloth, NE cloth, D-type cloth, S-type cloth, or high-silicon Oxygen cloth; organic material is woven or non-woven fabric or paper made of polyester, polyamine, polyacrylic acid, polyimide, aramid, polytetrafluoroethylene, or syndiotactic polystyrene.
  • the Dk (10 GHz) of the glue having a high filler content is selected to be 6.0 to 6.6.
  • the Dk (10 GHz) of the high filler content is selected to be 4.4 to 4.6.
  • Thermosetting Resin A Represents a phenolic epoxy resin produced by American Lucerne Chemical Company (formerly American Burton Chemical Company and Baker Wright, Germany) under the trade name EPR627-MEK80 with an epoxy equivalent of 160 ⁇ 250g/eq.
  • Thermosetting Resin B Represents the bisphenol A type cyanate prepolymer produced by Shanghai Huifeng Company under the trade name HF-10.
  • the hardener represents the phenolic resin hardener produced by the American company Lucerne Chemical Co., Ltd., and the trade name is PHL6635M65.
  • the accelerator represents the 2MI produced by the Shikoku Chemicals Corporation of Japan.
  • Filler A represents the barium titanate of Shandong Guohua, the trade name is BT 300.
  • Filler B represents the composite silicon micropowder of Lianyungang Donghai Silicon Micropowder Co., Ltd., the trade name is DB1003.
  • the average particle size is 2-3 microns.
  • Filler C stands for carbon black powder produced by Degussa, Germany, under the trade name FW200.
  • the layer of reinforcing material is E glass cloth with a Dk of 6.6.
  • thermosetting epoxy resin varnish used for the production of a copper clad laminate was prepared by using methyl ethyl ketone, wherein the solid content was 65%.
  • the copper-clad substrates of Examples 1-4 were prepared in accordance with the following preparation procedures:
  • Glue Add the solvent to the ingredient container, and add the solution of the thermosetting resin, the curing agent solution and the curing accelerator separately after stirring; after stirring for 2 hours, add the filler, continue stirring for 4-8 hours, and then sample the test glue.
  • the gelation time (170 ° C constant temperature hot plate) is 200 to 300 seconds.
  • Impregnation The layer of reinforcing material immersed in the glue 1 and the glue 2 respectively is passed through a vertical or horizontal impregnation machine, and the sandwich pre-preparation is obtained by controlling the conditions of the extrusion wheel speed, the line speed, the air temperature and the furnace temperature. Dip.
  • Comparative Example 1-3 The solid component formulation is detailed in Table 2, and was prepared by using methyl ethyl ketone to prepare a thermosetting resin glue for use in a copper clad laminate, in which the solid content was 65%.
  • the preparation methods of Comparative Examples 1-3 are as follows:
  • Glue Add the solvent to the ingredient container, and add the solution of the thermosetting resin, the curing agent solution and the curing accelerator separately after stirring; after stirring for 2 hours, add the filler, continue stirring for 4-8 hours, and then sample the test glue.
  • the gelation time (170 ° C constant temperature hot plate) is 200 to 300 seconds.
  • Impregnation The layer of reinforcing material immersed in the glue is passed through a vertical or horizontal impregnation machine to obtain a sandwich prepreg by controlling the conditions of the extrusion speed, the line speed, the air temperature and the furnace temperature.
  • Pressing After the cut sandwich prepreg is combined with the copper foil, it is placed in a vacuum hot press, and a copper clad plate is finally produced according to a certain temperature, time and pressure.
  • the specific examples are as follows:
  • the copper-clad substrate of the present invention has a sandwich structure prepared by a specific process, and has better adhesion than the comparative example.
  • the copper-clad substrate of the present invention still has good insulation due to the protection of the outer insulating layer; corresponding to the comparative example 3, the conventional process, insulation Can not meet the requirements.
  • the copper-clad substrate of the present invention has a more uniform dielectric constant than the comparative example, so that the signal delay problem is greatly improved.

Abstract

提供一种热固性树脂夹心预浸体，以及由其制成的覆铜板和多层印制电路布线板。该热固性树脂夹心预浸体中间层含有高填料含量热固性树脂组合物，预浸体外层含有低填料含量热固性树脂组合物。使用该预浸体制备的覆铜板具有较好的与金属箔的粘合性、绝缘性和均匀的介电常数分布。

Description

一种热固性树脂夹心预浸体、 制备方法及覆铜板 技术领域
本发明涉及一种热固性树脂组合物， 以及由其制成的的覆铜板和印制电路 布线板。
背景技术
电子行业的无铅环保要求， 推动了填料在覆铜板行业中的应用， 使用填料 技术已成为提升覆铜板性能的重要手段， 填料在覆铜板行业应用的发展趋势是 填料含量的不断提升。 高含量的填料比例带来更多优异的性能， 如降低热膨胀 系数、 提高热导率、 增加强度等。
由于填料表面为惰性， 填料含量的提升会造成金属箔与热固性树脂组合物 的粘合力下降。 专利 CN101973145通过涂胶金属箔来改善高填料含量热固性树 脂与金属箔的粘合性。在日本松下电工株式会社的特开 2009-127014专利中提出 了在一张半固化片两侧涂布含不同含量无机填料的热固性树脂胶液。 半固化片 靠近导电层的一侧， 涂布低无机填料含量的胶液来提高与金属箔的粘合性。 然 而， 以上两种方式均需要使用特殊的涂胶设备， 增加了生产成本。
因此， 本领域存在寻求更佳的技术方案来解决上述问题的需要。
发明内容
针对本发明所要解决的技术问题， 本发明的目的之一在于提供了一种热固 性树脂夹心预浸体。 所述热固性树脂夹心预浸体由中间层和包覆在中间层两侧 的外层构成， 所述中间层含有高填料含量热固性树脂组合物， 所述外层含有低 填料含量热固性树脂组合物。 使用该预浸体制备的覆铜板具有良好的金属箔粘 合性、 良好的绝缘性和均匀的介电常数分布。 在一个实施方案中，所述热固性树脂夹心预浸体的中间层包括 20-80质量％ 填料， 20-70质量％增强材料， 0-30质量％热固性树脂（填料 +增强材料 +热固性 树脂共计 100质量％); 所述预浸体外层包括 0-20质量％填料， 20-80质量％热 固性树脂 （填料 +热固性树脂共计 100质量％)。
在一个实施方案中， 所述增强材料为无机或有机材料， 无机材料为玻璃纤 维、 碳纤维、 硼纤维、 或金属的机织织物或无纺布或纸， 其中的玻璃纤维布或 无纺布为 E-glass、 Q 型布、 NE 布、 D 型布、 S 型布、 或高硅氧布； 有机材料 为聚酯、 聚胺、 聚丙烯酸、 聚酰亚胺、 芳纶、 聚四氟乙烯、 或间规聚苯乙烯制 造的织布或无纺布或纸。
在又一个实施方案中， 所述填料选自有结晶型二氧化硅、 熔融型的二氧化 硅、 球型二氧化硅、 氢氧化铝、 碳酸钙、 钛酸锶、 钛酸钡、 钛酸锶钡、 氮化硼、 氮化铝、 碳化硅、 氧化铝、 二氧化钛、 玻璃粉、 玻璃短切纤维、 滑石粉、 云母 粉、 碳黑、 碳纳米管、 石墨烯、 金属粉、 钼酸锌、 聚苯硫醚和 PTFE 粉中的一 种或多种， 所述粉末填料的粒径中度值为 0.01〜15 μ ηι; 优选地， 所述粉末填料 的粒径中度值为 0.5〜10 μ ηι。
在一个优选实施方案中， 所述玻纤布为 Ε型玻纤布， 相应的填料的 Dk为 6.0-6.6, 填料选自 E玻璃粉； 在另一个优选实施方案中， 所述玻纤布为 NE型 玻纤布， 相应的填料的 Dk为 4.4〜4.6， 填料选自 NE玻璃粉。
在再一个实施方案中， 所述热固性树脂包括： 环氧树脂、 氰酸酯树脂、 酚 醛树脂、 聚苯醚树脂、 聚丁二烯树脂、 聚丁二烯与苯乙烯共聚物树脂、 聚四氟 乙烯树脂、 聚苯并恶嗪树脂、 聚酰亚胺、 含硅树脂、 双马来酰亚胺三嗪树脂 (BT 树脂)、 LCP(Liquid Crystal Polymer) 树脂和双马来酰亚胺树脂中的的一种或多 种。 在另一个实施方案中， 所述预浸体的外层厚度为 1〜100 μ ηι; 优选地， 所 述预浸体的外层厚度为 5〜50 μ m。
本发明的另一目的在于提供一种制作本发明所述的夹心预浸体的制作方 法， 其特征在于， 包括如下步骤：
步骤 1 ： 增强材料浸渍填料含量为 40-100质量％的热固性树脂胶液 （所述 质量％为热固性树脂胶液中固体成分含量， 不包括溶剂）， 得到预浸体中间层； 步骤 2 ： 步骤 1得到的预浸体中间层再浸渍填料含量为 0-30质量％的热固 性树脂胶液， 制得夹心预浸体。
在一个优选实施方案中， 上述步骤 2 中浸渍的热固性树脂胶液填料含量为 0-20%。
在另一个优选实施方案中， 所述夹心预浸体是通过立式或横式含浸机制成 的。
本发明的另一目的在于提供由本发明所述的夹心预浸体制备的覆铜板。 在一个实施方案中， 所述覆铜板包括： 预浸体、 及覆合于预浸体两面上的 铜箔， 预浸体包括增强材料及通过浸渍干燥后附着在其上的热固性树脂组合物。
在一个优选实施方案中， 所述增强材料为无机或有机材料， 无机材料为玻 璃纤维、 碳纤维、 硼纤维、 或金属的机织织物或无纺布或纸， 其中的玻璃纤维 布或无纺布为 E-glass、 Q 型布、 NE 布、 D 型布、 S 型布、 或高硅氧布； 有机 材料为聚酯、 聚胺、 聚丙烯酸、 聚酰亚胺、 芳纶、 聚四氟乙烯、 或间规聚苯乙 烯制造的织布或无纺布或纸； 所述金属箔， 为铜、 黄铜、 铝、 镍、 或这些金属 的合金或复合金属箔， 金属箔的厚度为 12-150 μ ηι。
与现有技术相比， 本发明具有如下有益效果：
(1)本发明采用的热固性树脂夹心预浸体， 其中间层含有高填料含量的热固 性树脂组合物， 外层含有低填料含量的热固性树脂组合物， 从而提高了预浸体 外层与金属箔的粘合性。
(2)本发明采用的热固性树脂夹心预浸体， 由于填料集中在中间， 外层有绝 缘性优异的热固性树脂保护， 因此可以提高预浸体的绝缘性。 由于有外层热固 性树脂层的保护， 本发明的覆铜板可以使用绝缘性不佳的填料， 如金属粉、 碳 系粉体； 也可使用耐化学性不佳的填料， 如碳酸钙、 氢氧化铝。
(3)同时， 本发明采用的夹心预浸体， 由于填料集中在中间层， 提高了覆铜 板水平方向的均匀性， 改善了覆铜板介电常数的均匀性。 附图说明
图 1是本发明的热固性树脂夹心预浸体的结构示意图。 1为中间层， 2为外 层。 具体实 式
本发明所用的 Dk是指介电常数， 在 10GHz频率下用 SPDR法测试的值。 本发明所用的 Df是指介电损耗， 在 10GHz频率下用 SPDR法测试的值。 本发明所用的树脂组合物是指包括树脂和固化剂的组合物。 例如， 环氧树 脂组合物是指包括环氧树脂和合适固化剂的组合物。 本领域技术人员能够根据 所用的树脂选择合适的固化剂及其量， 也能够根据所用的树脂及固化剂选择合 适的有机溶剂。
根据本发明， 所述热固性树脂包括： 环氧树脂、 氰酸酯树脂、 酚醛树脂、 聚苯醚树脂、 聚丁二烯树脂、 聚丁二烯与苯乙烯共聚物树脂、 聚四氟乙烯树脂、 聚苯并恶嗪树脂、 聚酰亚胺、 含硅树脂、 双马来酰亚胺三嗪树脂 (BT 树脂 )、 LCP(Liquid Crystal Polymer) 树脂和双马来酰亚胺树脂中的的一种或多种。 本发明所用的填料是指填充材料， 简称填料， 在覆铜板行业使用填料的目 的不只是为了降低成本， 而是为了提高覆铜板的性能， 如 CTE的降低、 阻燃性 的提高、 导热系数及板材力学性能的提高等。
根据本发明， 所述填料选自有结晶型二氧化硅、 熔融型的二氧化硅、 球型 二氧化硅、 氢氧化铝、 碳酸钙、 钛酸锶、 钛酸钡、 钛酸锶钡、 氮化硼、 氮化铝、 碳化硅、 氧化铝、 二氧化钛、 玻璃粉、 玻璃短切纤维、 滑石粉、 云母粉、 碳黑、 碳纳米管、 石墨烯、 金属粉、 钼酸锌、 聚苯硫醚和 PTFE粉中的一种或多种， 所述粉末填料的粒径中度值为 0.01〜15 μ ηι; 优选地， 所述粉末填料的粒径中度 值为 0.5〜10 μ ηι。
本发明所用的胶液是指将本发明的树脂组合物溶于合适有机溶剂的胶液。 优选地， 本发明所用的胶液是指将本发明的树脂组合物溶于合适有机溶剂后再 加入填料所获得的分散体系。 本领域技术人员能够通过调整所述预处理胶液中 填料的用量使得所述预处理胶液具有合适的介电常数 （Dk)。 在本发明中， 胶 液 Dk为胶液去掉溶剂后所得干胶的 Dk，该值仅与树脂组合物和填料的量有关， 而与溶剂的量无关。
本发明所用的浸胶是指将玻纤布浸入胶液中， 然后再经过上胶机进行烘干 溶剂的操作。
根据本发明， 所述高填料含量的树脂， 其 Dk等于所用增强材料层的 Dk士 30%的树脂， 优选所用增强材料层的 Dk±20%， 更优选所用增强材料层的 Dk士 10%。 Dk与玻纤布的 Dk越接近， 则介电常数在 X、 Y方向差别越小， 信号的 时延就越小。
根据本发明， 所述增强材料为无机或有机材料， 无机材料为玻璃纤维、 碳 纤维、 硼纤维、 或金属的机织织物或无纺布或纸， 其中的玻璃纤维布或无纺布 为 E-glass、 Q型布、 NE 布、 D 型布、 S 型布、 或高硅氧布； 有机材料为聚酯、 聚胺、 聚丙烯酸、 聚酰亚胺、 芳纶、 聚四氟乙烯、 或间规聚苯乙烯制造的织布 或无纺布或纸。
根据本发明， 所述增强材料层为 E型玻纤布时， 选择高填料含量的胶液的 Dk ( 10GHz) 为 6.0〜6.6。
根据本发明，所述增强材料层为 NE型玻纤布时，选择高填料含量的胶液的 Dk ( 10GHz) 为 4.4〜4.6。
实施例
为便于理解本发明， 本发明列举实施例如下。 本领域技术人员应该明了， 所述实施例仅仅是帮助理解本发明， 不应视为对本发明的具体限制。
实施例以及比较例中所用的各代号及其成份如下：
热固性树脂 A： 代表美国瀚森化工公司 （原美国波顿化学公司和德国贝克 莱特公司） 生产的酚醛环氧树脂， 商品名为 EPR627-MEK80, 其环氧当量介于 160〜250g/eq。
热固性树脂 B : 代表上海慧峰公司生产的双酚 A型氰酸酯预聚体， 商品名 为 HF-10。
硬化剂代表美国瀚森化工公司生产的酚醛树脂硬化剂， 商品名为 PHL6635M65。
促进剂代表日本四国化成公司生产的 2MI。
填料 A代表山东国瓷的钛酸钡， 商品名为 BT 300。
填料 B代表连云港东海硅微粉有限公司的复合硅微粉， 商品名为 DB1003 , 平均粒径为 2-3微米。
填料 C代表代表德国德古萨公司产的炭黑粉， 商品名为 FW200。
增强材料层为 E玻璃布， Dk为 6.6。
实施例 1-4
实施例 1-4固体成分配方组成详见表 1， 并且利用丁酮调制成制造覆铜板使 用的热固性环氧树脂清漆， 其中固体成分占 65%。
依照以下制备工艺制备实施例 1-4的覆铜箔基板：
( 1 ) 制胶： 将溶剂加入配料容器中， 搅拌下分别加入热固性树脂、 固化剂 溶液以及固化促进剂的溶液； 搅拌 2小时后， 加入填料， 继续搅拌 4-8小时后， 取样测试胶液的胶化时间 （170°C恒温热板） 为 200〜300秒。
(2 )含浸： 将分别浸过胶液 1和胶液 2的增强材料层通过立式或者横式含 浸机， 通过控制挤压轮速、 线速、 风温以及炉温等条件制得夹心预浸片。
(3 ) 压制： 将裁减好的夹心预浸片与铜箔组合好后， 放入真空热压机中， 按一定的温度， 时间和压力并最终制得覆铜箔板， 具体示范例为：
温度程式： 130 °C /30min+ 155 °C/30min+ 190 °C /90min+220 °C /60min； 压力程式：
25Kgf. cm-2/30min+5 OKgf . cm-2/30min+90Kgf. cm-2/ 120min+3 OKgf. cm-2/90min； 真空程式： 30mmHg/130min+800mmHg/130min。
通过上述程序， 采用 8张厚度为 0.2mm的半固化片层层相叠于 35μηι厚的 铜箔间， 经热压后即可制得 1.6mm厚的覆铜板。 得到覆铜箔板后， 对板材性能 进行测试， 表 3所示为板材性能对比。 1
Figure imgf000009_0001
比较例 1-3
比较例 1-3固体成分配方组成详见表 2， 并且利用丁酮调制成制造覆铜板使 用的热固性树脂胶液， 其中固体成分占 65%。 比较例 1-3的制备方法如下：
( 1 ) 制胶： 将溶剂加入配料容器中， 搅拌下分别加入热固性树脂、 固化剂 溶液以及固化促进剂的溶液； 搅拌 2小时后， 加入填料， 继续搅拌 4-8小时后， 取样测试胶液的胶化时间 （170°C恒温热板） 为 200〜300秒。
(2) 含浸： 将分别浸过胶液的增强材料层通过立式或者横式含浸机， 通过 控制挤压轮速、 线速、 风温以及炉温等条件制得夹心预浸片。 (3 ) 压制： 将裁减好的夹心预浸片与铜箔组合好后， 放入真空热压机中， 按一定的温度， 时间和压力并最终制得覆铜箔板， 具体示范例为：
温度程式： 130 °C /30min+ 155 °C/30min+ 190 °C /90min+220 °C /60min； 压力程式：
25Kgf. cm-2/30min+5 OKgf . cm-2/30min+90Kgf. cm-2/ 120min+3 OKgf. cm-2/90min； 真空程式： 30mmHg/130min+800mmHg/130min。
通过上述程序， 采用 8张厚度为 0.2mm的半固化片层层相叠于 35μηι厚的 铜箔间， 经热压后即可制得 1.6mm厚的覆铜板。
Figure imgf000010_0001
Figure imgf000010_0002
采用以下方法对实施例 1-4和比较例 1-3制备覆铜箔基板测量体积电阻率和 耐电化， 测试结果如表 3所示。 实施例 比较例 测试项目
1 2 3 4 1 2 3 玻璃强度（N/mm) 1. 6 1. 5 1. 8 1. 7 0. 8 1. 0 1. 2 体体积电阻率 4.2 X 4.0 X 4.2 X 4.2 X 4.0 X 4.0 X <104
(ΜΩ·ςηι) 108 108 108 108 108 108 电路基板 Dk 5.0 6.0 6.5 6.6 5.0 6.0 6.6 经向信号时延 /ps 10 9 8 7 35 38 47 纬向信号时延 /ps 9 8 7 7 16 18 17
由表 3 可知， 本发明的覆铜箔基板采用特定工艺制备的夹心结构， 相比比 较例有较好的粘合性。 如实施例 3 所示， 本发明的覆铜箔基板在使用导电填料 时， 由于有外层绝缘性层的保护依然有较好的绝缘性； 相对应的是比较例 3 采 用传统工艺， 绝缘性不能满足要求。 同时， 本发明的覆铜箔基板相比比较例有 更加均匀的介电常数， 因此信号时延问题得到极大的改善。 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 书
1、 一种热固性树脂夹心预浸体， 其由中间层和包覆在其两侧的外层构成， 所述中间层以填料 +增强材料 +热固性树脂共计 100质量％计包括 20-80质量％填 料、 20-70质量％增强材料、 0-30质量％热固性树脂； 所述外层以填料 +热固性 树脂共 100质量％计包括 0-20质量％填料、 20-80质量％热固性树脂。
2、 如权利要求 1所述的夹心预浸体， 其特征在于， 所述填料选自有结晶型 二氧化硅、 熔融型的二氧化硅、 球型二氧化硅、 氢氧化铝、 碳酸钙、 钛酸锶、 钛酸钡、 钛酸锶钡、 氮化硼、 氮化铝、 碳化硅、 氧化铝、 二氧化钛、 玻璃粉、 玻璃短切纤维、 滑石粉、 云母粉、 碳黑、 碳纳米管、 石墨烯、 金属粉、 钼酸锌、 聚苯硫醚和 PTFE粉中的一种或多种， 所述粉末填料的粒径中度值为 0.01〜15 μ ηι; 优选地， 所述粉末填料的粒径中度值为 0.5〜10 μ ηι。
3、 如权利要求 1或 2所述的夹心预浸体， 其特征在于， 所述预浸体的外层 厚度为 1〜100 μ ηι; 优选地， 所述预浸体的外层厚度为 5〜50 μ ηι。
4、 如权利要求 1-3任一项所述的夹心预浸体， 其特征在于， 所述的热固性 树脂包括： 环氧树脂、 氰酸酯树脂、 酚醛树脂、 聚苯醚树脂、 聚丁二烯树脂、 聚丁二烯与苯乙烯共聚物树脂、 聚四氟乙烯树脂、 聚苯并恶嗪树脂、 聚酰亚胺、 含硅树脂、 双马来酰亚胺三嗪树脂 (ΒΤ树脂)、 LCP (Liquid Crystal Polymer) 树 脂和双马来酰亚胺树脂中的的一种或多种。
5、 如权利要求 1-4任一项所述的夹心预浸体， 其特征在于， 所述增强材料 为 E型玻纤布或 NE型玻纤布， 使用 E型玻纤布的中间层相应的填料与热固性 树脂制备的胶液 Dk为 6.0〜6.6； 使用 NE型玻纤布的中间层相应的填料与热固 性树脂制备的胶液 Dk为 4.4〜4.6； 优选地， 使用 E型玻纤布的中间层填料的 Dk为 6.0〜6.6， 填料选自 E玻璃粉； 使用 NE型玻纤布的中间层填料的 Dk为
6、 一种制作如权利要求 1 -5任一项所述的夹心预浸体的制作方法， 其特征 在于， 包括如下步骤：
步骤 1 ： 20-70质量％的增强材料浸渍含 20-80质量％填料、 0-30质量％热 固性树脂的热固性树脂胶液， 均以填料 +增强材料 +热固性树脂共计 100质量％ 计， 得到预浸体；
步骤 2 ：步骤 1得到的预浸体浸渍以填料 +热固性树脂共 100质量％计填料 含量为 0-30%的热固性树脂胶液， 制得夹心预浸体。
7、 根据权利要求 6所述的制备方法， 其特征在于， 所述玻纤布为 E型玻纤 布， 相应的填料的 Dk为 6.0〜6.6， 填料选自 E玻璃粉； 优选地， 所述玻纤布为 NE型玻纤布， 相应的填料的 Dk为 4.4〜4.6， 填料选自 NE玻璃粉。
8、 根据权利要求 6或 7所述的制备方法， 其特征在于， 所述夹心预浸体是 通过立式或横式含浸机制成的。
9、 一种采用如权利要求 1-5任一项所述夹心预浸体制作的覆铜板， 其特征 在于， 其包括： 预浸体、 及覆合于预浸体两面上的铜箔， 预浸体包括增强材料 及通过浸渍干燥后附着在其上的热固性树脂组合物。
10、 如权利要求 9所述的覆铜板， 其特征在于， 所述增强材料为无机或有 机材料， 无机材料为玻璃纤维、 碳纤维、 硼纤维、 或金属的机织织物或无纺布， 其中的玻璃纤维布或无纺布为 E-glass、 Q 型布、 NE布、 D 型布、 S 型布、 或 高硅氧布； 有机材料为聚酯、 聚胺、 聚丙烯酸、 聚酰亚胺、 芳纶、 聚四氟乙烯、 或间规聚苯乙烯制造的织布或无纺布或纸； 所述金属箔， 为铜、 黄铜、 铝、 镍、 或这些金属的合金或复合金属箔， 金属箔的厚度为 12-150 μ ηι。
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CN109621554A (zh) * 2019-01-23 2019-04-16 江苏盖姆纳米材料科技有限公司 一种水油分离丝网以及利用该丝网制成的滤芯
CN113022049A (zh) * 2021-03-26 2021-06-25 重庆科技学院 一种新型覆铜板结构及其制作工艺
CN114311884A (zh) * 2021-12-15 2022-04-12 山东金宝电子股份有限公司 一种耐辐射抗老化覆铜箔层压板及其制备方法
CN114559721A (zh) * 2022-03-04 2022-05-31 西南科技大学 三明治结构高储能密度聚酰亚胺基复合薄膜及其制备方法

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