CN106928744B - A kind of composite material containing filler, sheet material and the circuit substrate containing it - Google Patents

A kind of composite material containing filler, sheet material and the circuit substrate containing it Download PDF

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Publication number
CN106928744B
CN106928744B CN201511028780.1A CN201511028780A CN106928744B CN 106928744 B CN106928744 B CN 106928744B CN 201511028780 A CN201511028780 A CN 201511028780A CN 106928744 B CN106928744 B CN 106928744B
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filler
fibre
thermoplastic
composite material
space network
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CN106928744A (en
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孟运东
苏晓声
方克洪
杨中强
苏民社
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/24—Acids; Salts thereof
    • 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
    • C08K7/06—Elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester 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
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Abstract

The invention belongs to circuit substrate technical field, it is related to a kind of composite material containing filler, sheet material and circuit substrate.The composite material containing filler includes space network material and the filler that is dispersed in space network material hole, wherein the space network material is mainly mutually overlapped or bonded by thermoplastic fibre.The composite material containing filler, which assigns the sheet material obtained using it and circuit substrate, has dielectric constant in X, Y-direction isotropism and low dielectric constant and dielectric loss and excellent mechanical property.

Description

A kind of composite material containing filler, sheet material and the circuit substrate containing it
Technical field
The invention belongs to circuit substrate technical field, be related to a kind of composite material containing filler, sheet material and containing it Circuit substrate.
Background technique
In recent years, with information communication device high performance, multifunction and the development of networking, for high-speed transfer And processing large capacity information, operation signal are intended to higher frequency, the frequency of use Continued of electronic product, it is desirable that substrate material The dielectric constant of material is lower and lower, and dielectric loss requirement is smaller and smaller, and the uniformity of substrate dielectric constant is required to get well.
Currently, high-frequency high-speed circuit substrate obtains good high frequency performance using the resin of low-k, these are low The resin of dielectric constant mainly has polyphenylene oxide, cyanate, the thermosetting property tree being only made of carbon hydrogen element containing unsaturated double-bond Rouge, polytetrafluoroethylene (PTFE) and polyimide resin etc., and generally using glass fabric as reinforcing material.But glass fibers Tie up cloth dielectric constant it is minimum can only accomplish 3.7, therefore, influenced by glass fabric dielectric constant is bigger than normal, resin/glass The dielectric constant of the circuit substrate of fiber cloth system production is difficult to reduce.
On the other hand, in current high-frequency circuit board, because reinforcing material is braided material, so that circuit substrate exists There are anisotropy in the direction XY of plane, i.e., different in the dielectric properties through broadwise of braided material node and braided material. Therefore, high-frequency signal is on high-frequency circuit board when transmitting, can because it is each to dielectric properties it is different and cause on each route The weak degree of signal is different, and signal transmission delay degree is different, eventually leads to stable signal transmission and goes wrong.
Thermoplasticity will be used between polyphenylene sulfide fabric and glass fabric reinforcing fiber layer by mentioning in CN101386218 Then eva film calorifies 290 DEG C of -330 DEG C of laminations using high-frequency electrical, obtains composite laminate as adhesive layer.After hot pressing, Polyphenylene sulfide fibre cuts into 0.20-80 millimeters of fiber after hot gas spring setting processing.EVA layer has been used in the invention, and And polyphenylene sulfide fibre is not suitable for the application of circuit substrate only by thermal cut-out.
US6218015 is cast into film after mixing using two kinds of polyflons with filler, to manufacture circuit substrate. The dielectric properties of substrate obtained by this method are excellent and respectively identical to performance.But film thicker obtained by the casting method is easy It cracks, yield rate is lower, and production efficiency is very low.
US4772509 is fabricated to prepreg using the thin film dipped polyimides of mushy expanded ptfe, so The production of circuit substrate is carried out afterwards.
US5652055 makes circuit substrate using the thin film dipped thermosetting resin of mushy expanded ptfe.It should Prior art is all made of the production that the higher thermosetting resin of dielectric loss carries out circuit substrate, compared to the electricity of pure polytetrafluoroethylene (PTFE) The dielectric properties of base board are poor.
CN102260378 is disclosed by the fluoropolymer dispersion emulsion of low-dielectric loss, powder filler and mushy swollen The composite material of swollen polytetrafluoroethylene film composition, and mention and will form prepreg after the drying of above-mentioned composite material, it then will be pre- Leaching material and copper foil obtain high-frequency circuit board in 350 DEG C of -400 DEG C of hot pressing.The invention using porous film as raw material, itself Intensity it is insufficient, and since the fluffy degree of film is inadequate, powder filler enters more difficult in its hole.
Applicant once attempted thermoplastic non-woven fabric or the direct hot pressing of thermoplastic fibre obtaining thin-film material.The film material Expect that toughness is fine, and fine with the caking property of the conductive layers such as copper foil, but because fiber is difficult to melt completely at the process conditions, it is thin There are gaps in membrane material, and gap has negative effect for the humidity resistance in circuit substrate application.
Summary of the invention
Based on the problems in prior art, one of the objects of the present invention is to provide a kind of composite materials containing filler.I.e. It incorporates fillers into the hole for the space network material being made of thermoplastic fibre and obtains the composite material containing filler.
Non-woven fabrics made of the space network material is mainly mutually overlapped or bonded as thermoplastic fibre is (non-woven Cloth), it can be sheet or bulk material.
The diameter of the thermoplastic resin fibre is generally 0.01 μm -500 μm, further preferably 0.1 μm -100 μm.
Preferably, the thermoplastic fibre refers to mainly melting temperature made of 100~600 DEG C of the thermoplastic resin Thermoplastic fibre, preferably mainly melting temperature thermoplastic fibre made of 200~500 DEG C of thermoplastic resin, further It is preferred that mainly selecting the preferred thermoplastic fine melting temperature thermoplastic fibre made of 260-360 DEG C of thermoplastic resin The reason of dimension, essentially consists in, and is conducive to the processing of subsequent CCL and pcb board.
Preferably, the thermoplastic fibre mainly by selected from liquid crystal polymer, polyimides, polytetrafluoroethylene (PTFE), polyphenylene oxide, Polyphenylene sulfide, polysulfones, polytrifluorochloroethylene, polyether-ether-ketone etc., polyester, polyacrylonitrile, polystyrene, polycarbonate, polyethylene, Thermoplastic fibre made of any one or at least two combination in polypropylene or polyamide etc..
In the present invention, it illustratively can choose following thermoplastic fibre:
The Dk of liquid crystalline polyester fiber is 2.5~3.0, and melting temperature is 260~350 DEG C, and polyester fiber (such as terylene) melts Melting temperature is 255~260 DEG C, and the Dk of polycarbonate is 3.0~3.2, and melting temperature is~135 DEG C, polyethylene fibre Melting temperature is 124~138 DEG C, and the melting temperature of polypropylene fibre is 165~173 DEG C, and Fypro softens at 170 DEG C, 215 DEG C of meltings, polyacrylonitrile fibre softening temperature are 190~230 DEG C, and the melting temperature of polyimide fiber is greater than 300 DEG C, are gathered Tetrafluoroethylene fiber melting temperature reaches 327 DEG C, 220 DEG C of polyphenylether fibre fusing point.Illustrative polyphenylether fibre can be by polyphenyl Ether addition polymerization alkene is prepared.
In addition to thermoplastic resin, the raw material of the thermoplastic fibre can also include that nanoparticle and superfine fibre etc. help Agent etc..
In the present invention, the space network material can mutually overlap or bonding group for single kind of thermoplastic fibre At, or at least two thermoplastic fibres mutually overlap or bond composition, such as can be first mainly by least two thermoplastics Property resin is blended obtains mixing thermoplastic fibre, then blended obtained thermoplastic fibre is mutually overlapped or is bonded, can also be with It is directly mutually to be overlapped or bonded by least two thermoplastic fibres.
In the present invention, the space network material is mainly mutually overlapped or is bonded by thermoplastic fibre, meaning Refer to, the space network material only mutually can be overlapped or be bonded by thermoplastic fibre, is also possible to thermoplasticity Fiber and other fibers are mutually overlapped or are bonded.Preferably, in the space network material, above-mentioned thermoplasticity is removed It can also include glass fibre, quartz fibre, carbon fiber, basalt fibre, boron fibre, metallic fiber or ceramics other than fiber In fiber etc. any one or at least two combination.
In the present invention, it is preferred to which having diameter in space network material, between thermoplastic fibre is about 0.1-60 The hole of μm (such as 5 μm, 10 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 50 μm or 60 μm).Stereoscopic graticule Pore size in shape structure is impossible all identical, and the pore diameter of the space network material refers to micro- The average value of maximum 20 pore diameters arrived under the microscope.Hole in space network is irregular shape, institute State the diameter that pore diameter refers to the maximum spherical that may pass through in hole.
In the present invention, the hole between thermoplastic fibre is the open pores with extraneous intercommunication, and pore diameter is to compound The processing of material and quality have highly important influence.Pore diameter is bigger, and filler easily enters hole, is conducive to process, But filler is excessive in hole, then will lead to the filler after hot pressing in composite material and excessively concentrate.Pore size and fibre diameter it Between ratio it is particularly significant, preferably interfiber pore diameter is 0.1~30 times of fibre diameter, for example, 0.2 times, 0.8 times, 3 times, 6 times, 12 times, 15 times, 19 times, 22 times, 26 times, 28 times etc..In order to be suitable for currently used filler and fiber, and take into account Processing, further preferred interfiber pore diameter are 0.1~50 μm.
The diameter of thermoplastic fibre and the porosity of space network determine the mean size of interfiber pore.That is phase Under the conditions of same porosity, the diameter of fiber is bigger, then interfibrous pore diameter is bigger.In the present invention, porosity is big The small number for determining filler that space network material can accommodate.The porosity of space network material is bigger, then The filer content of composite material is generally higher, but porosity is excessive, then filler distribution can be made uneven, and fill out in composite material Expect easy to fall off, reduces the intensity of composite material.In order to facilitate selection raw material, the porosity of the space network material is excellent It is selected as 30%-90%, further preferred porosity is 50% to 85%.
In the present invention, the thickness of the space network material is bigger, and filler is well into space network material The difficulty of material is bigger, and thickness is smaller, then space network material is weaker to the limitation capability of filler.Thermoplastic fibre is straight Diameter, porosity and application field are larger to the thickness effect of material, and specific thickness requirements are depending on the circumstances.It is preferred that vertical Body mesh material with a thickness of 10 μm -500 μm.
Preferably, in the present invention, the partial size of filler is less than the pore diameter between thermoplastic fibre.Preferably, filler Partial size D90 be 30 μm hereinafter, such as 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 7 μm, 11 μm, 15 μm, 18 μm, 21 μm, 24 μm or 27 μm, the D50 of further preferred filler is 0.1-5 μm, for example, 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 2.5 μm, 3 μm, 4 μm or 5 μm.
Preferably, the filler is inorganic filler and/or organic filler.
Preferably, the inorganic filler is selected from carbon black, silicon powder, aluminum oxide, titanate, metatianate, titanium dioxide Quartzy staple fiber less than 20 staple glass fibre, draw ratio less than 20 of titanium, draw ratio, draw ratio are less than the short fibre of 20 carbon fiber In metal powder etc. any one or at least two combination.
Preferably, the organic filler is selected from polyphenylene ether powder, pps powder, teflon resin powder, gathers In imide resin powder or rubber particle etc. any one or at least two combination.
Preferably, the wire feeding be functional filler, preferably dielectric ceramics filler, heat-resistant filler, fire-retardant filler, In heat filling, conductive filler, fluorescer, UV absorbent, magnetic fillers or reactive filler etc. any one or at least Two kinds of combination.
Preferably, the conductive filler is metal powder, draw ratio less than one of short fibre of 20 carbon fiber or at least two The combination of kind.
In the present invention, the composite material can also include other components in addition to space network material and filler, But it does not contain other thermoplastic resins and/or thermosetting resin, including for example in addition to other of thermoplastic fibre form The substance of any existence of thermoplastic resin, such as thermoplastic resin membrane, thermoplastic resin dispersion emulsion etc., Yi Jiqi His thermoplasticity and/or thermosetting resin.For example, the thermoplastic fibre is polytetrafluoroethylene fibre, it is described " not contain other Thermoplastic resin and/or thermosetting resin " refers to, i.e., without containing including for example in addition to other of polytetrafluoroethylene fibre form Polytetrafluoroethylene (PTFE) any existence substance, such as polytetrafluoroethylene film, polytetrafluoroethylene (PTFE) dispersion emulsion etc., and Other thermoplasticity and/or thermosetting resin.
The second object of the present invention is to provide a kind of sheet material, and the sheet material is by as described above containing the composite wood of filler The resin film that material hot pressing obtains.
By the composite material hot pressing as described above containing filler, in hot pressing, partial size is less than the filler of pore diameter During forming sheet material, it can be melted or the thermoplastic fibre of adhesion is firmly blocked or is adhered in hole, thermoplastic Property fiber in hot pressing, form resin film, and then obtain sheet material.
The present invention by using filler is dispersed in mainly mutually overlapped or bonded as thermoplastic fibre made of stereoscopic graticule In shape structural material, without the use of braided material (woven cloths), the composite material containing filler is made to assign the sheet material obtained using it Except having in addition to X, Y-direction isotropism, have the further advantage that
(1) since the space network material has flourishing pore structure and excellent mechanical property, make composite wood The intensity of material relative in prior art film or die casting film strength it is higher；
(2) since space network material has flourishing pore structure, filler can be evenly distributed in hole, Being uniformly distributed for filler is realized, composite material specific function is imparted；
(3) since uniform filling is dispersed in hole, composite material will not generate gap, avoid and directly adopt The shortcomings that composite material that thermoplastic fibre hot pressing obtains deteriorates its moisture-proof there are gap；
(4) and thermoplastic resin and filler mixed phase ratio are directlyed adopt, it is meltable since thermoplastic fibre heating surface area is big Melt, makes composite material be easier to bond with metal foil such as copper foil, the binding force of circuit substrate is improved, moreover, thermoplastic fibre Due to passing through fiber draw process, crystallinity and intensity are improved, this also significantly increases the intensity of composite material；
(5) it compared with traditional circuit board use bonding sheet production, incorporates fillers into space network material, can show Write the content for improving filler.
The third object of the present invention is to provide a kind of preparation method of sheet material, the described method comprises the following steps:
(1) it incorporates fillers into and mainly mutually overlaps or bond the space network material formed by thermoplastic fibre In hole；
(2) sheet material will be obtained by way of hot pressing by the lamination that at least a composite material containing filler is formed.
Non-woven fabrics made of the space network material is mainly mutually overlapped or bonded as thermoplastic fibre is (non-woven Cloth), it can be sheet or bulk material.
The diameter of the thermoplastic resin fibre is generally 0.01 μm -500 μm, further preferably 0.1 μm -100 μm.
Preferably, the thermoplastic fibre refers to mainly melting temperature made of 100~600 DEG C of the thermoplastic resin Thermoplastic fibre, preferably mainly melting temperature thermoplastic fibre made of 200~500 DEG C of thermoplastic resin, further It is preferred that mainly selecting the preferred thermoplastic fine melting temperature thermoplastic fibre made of 260-360 DEG C of thermoplastic resin The reason of dimension, essentially consists in, and is conducive to the processing of subsequent CCL and pcb board.
Preferably, the thermoplastic fibre mainly by selected from liquid crystal polymer, polyimides, polytetrafluoroethylene (PTFE), polyphenylene oxide, Polyphenylene sulfide, polysulfones, polytrifluorochloroethylene, polyether-ether-ketone etc., polyester, polyacrylonitrile, polystyrene, polycarbonate, polyethylene, Thermoplastic fibre made of any one or at least two combination in polypropylene or polyamide etc..
In the present invention, it illustratively can choose following such as Plasitc fibers:
The Dk of liquid crystalline polyester fiber is 2.5~3.0, and melting temperature is 260~350 DEG C, and polyester fiber (such as terylene) melts Melting temperature is 255~260 DEG C, and the Dk of polycarbonate is 3.0~3.2, and melting temperature is~135 DEG C, polyethylene fibre Melting temperature is 124~138 DEG C, and the melting temperature of polypropylene fibre is 165~173 DEG C, and Fypro softens at 170 DEG C, 215 DEG C of meltings, polyacrylonitrile fibre softening temperature are 190~230 DEG C, and the melting temperature of polyimide fiber is greater than 300 DEG C, are gathered Tetrafluoroethylene fiber melting temperature reaches 327 DEG C, 220 DEG C of polyphenylether fibre fusing point.Illustrative polyphenylether fibre can be by polyphenyl Ether addition polymerization alkene is prepared.
In addition to thermoplastic resin, the raw material of the thermoplastic fibre can also include that nanoparticle and superfine fibre etc. help Agent etc..
In the present invention, the space network material can mutually overlap or bonding group for single kind of thermoplastic fibre At, or at least two thermoplastic fibres mutually overlap or bond composition, such as can be first mainly by least two thermoplastics Property resin is blended obtains mixing thermoplastic fibre, then blended obtained thermoplastic fibre is mutually overlapped or is bonded, can also be with It is directly mutually to be overlapped or bonded by least two thermoplastic fibres.
In the present invention, the space network material is mainly mutually overlapped or is bonded by thermoplastic fibre, meaning Refer to, the space network material only mutually can be overlapped or be bonded by thermoplastic fibre, is also possible to thermoplasticity Fiber and other fibers are mutually overlapped or are bonded.Preferably, in the space network material, above-mentioned thermoplasticity is removed It can also include glass fibre, quartz fibre, carbon fiber, basalt fibre, boron fibre, metallic fiber or ceramics other than fiber In fiber etc. any one or at least two combination.
In the present invention, it is preferred to which having diameter in space network material, between thermoplastic fibre is about 0.1-60 The hole of μm (such as 5 μm, 10 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 50 μm or 60 μm).Stereoscopic graticule Pore size in shape structure is impossible all identical, and the pore diameter of the space network material refers to micro- The average value of maximum 20 pore diameters arrived under the microscope.Hole in space network is irregular shape, institute State the diameter that pore diameter refers to the maximum spherical that may pass through in hole.
In the present invention, the hole between thermoplastic fibre is the open pores with extraneous intercommunication, and pore diameter is to compound The processing of material and quality have highly important influence.Pore diameter is bigger, and filler easily enters hole, is conducive to process, But filler is excessive in hole, then will lead to the filler after hot pressing in composite material and excessively concentrate.Pore size and fibre diameter it Between ratio it is particularly significant, in space network material, preferred thermoplastic interfiber pore diameter be thermoplasticity fibre 0.1~30 times for tieing up diameter.In order to be suitable for currently used filler and fiber, and processing is taken into account, between further preferred fiber Pore diameter is 0.1~50 μm.
The diameter of thermoplastic fibre and the porosity of space network determine the mean size of interfiber pore.That is phase Under the conditions of same porosity, the diameter of fiber is bigger, then interfibrous pore diameter is bigger.In the present invention, porosity is big The small number for determining filler that space network material can accommodate.The porosity of space network material is bigger, then The filer content of composite material is generally higher, but porosity is excessive, then filler distribution can be made uneven, and fill out in composite material Expect easy to fall off, reduces the intensity of composite material.In order to facilitate selection raw material, the porosity of the space network material is excellent It is selected as 30%-90%, further preferred porosity is 50% to 85%.
In the present invention, the thickness of the space network material is bigger, and filler is well into space network material The difficulty of material is bigger, and thickness is smaller, then space network material is weaker to the limitation capability of filler.Thermoplastic fibre is straight Diameter, porosity and application field are larger to the thickness effect of material, and specific thickness requirements are depending on the circumstances.It is preferred that vertical Body mesh material with a thickness of 10 μm -500 μm.
Preferably, in the present invention, the partial size of filler is less than the pore diameter between thermoplastic fibre.Preferably, filler Partial size D90 be 30 μm hereinafter, such as 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 7 μm, 11 μm, 15 μm, 18 μm, 21 μm, 24 μm or 27 μm, the D50 of further preferred filler is 0.1-5 μm, for example, 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 2.5 μm, 3 μm, 4 μm or 5 μm.
Preferably, the filler is inorganic filler and/or organic filler.
Preferably, the inorganic filler is selected from carbon black, silicon powder, aluminum oxide, titanate, metatianate, titanium dioxide Titanium, draw ratio are less than any one in the quartzy staple fiber of 20 staple glass fibre, draw ratio less than 20 or metal powder etc. Or at least two combination.
Preferably, the organic filler is selected from polyphenylene ether powder, pps powder, teflon resin powder, gathers In imide resin powder or rubber particle etc. any one or at least two combination.
Preferably, the wire feeding be functional filler, preferably dielectric ceramics filler, heat-resistant filler, fire-retardant filler, In heat filling, conductive filler, fluorescer, UV absorbent, magnetic fillers or reactive filler etc. any one or at least Two kinds of combination.
Preferably, the conductive filler is one of the carbon fiber of metal powder, draw ratio less than 20 or at least two Combination.
In the present invention, the composite material can also include other components in addition to space network material and filler, But it does not contain other thermoplastic resins and/or thermosetting resin, including for example in addition to other of thermoplastic fibre form The substance of any existence of thermoplastic resin, such as thermoplastic resin membrane, thermoplastic resin dispersion emulsion etc., Yi Jiqi His thermoplasticity and/or thermosetting resin.For example, the thermoplastic fibre is polytetrafluoroethylene fibre, it is described " not contain other Thermoplastic resin and/or thermosetting resin " refers to, i.e., without containing including for example in addition to other of polytetrafluoroethylene fibre form Polytetrafluoroethylene (PTFE) any existence substance, such as polytetrafluoroethylene film, polytetrafluoroethylene (PTFE) dispersion emulsion etc., and Other thermoplasticity and/or thermosetting resin.
Preferably, filler is pre-dispersed in mounting medium, then is introduced into the hole of space network material In.
Preferably, the mounting medium is liquid solvent and optionally auxiliary agent.
Preferably, the liquid solvent is water, halogenated hydrocarbon solvent, halogenated phenols solvent, ether solvents, ketone solvent, ester solvent, carbon Acid esters solvent, amine solvent, nitrogenous heterocyclic aromatic compounds solvent, nitrile solvent, amide solvent, carbamide compound solvent, nitration Close in object solvent, sulphur compound solvent or phosphorus compound solvent etc. any one or at least two combination.
Preferably, the auxiliary agent includes coupling agent, dispersing agent or surface tension processing for dispersing and stablizing filler, auxiliary agent In agent etc. any one or at least two combination.
Preferably, the mounting medium may be gas.
Preferably, the gas includes air, nitrogen, carbon dioxide or inert gas etc..
Preferably, the space network material for mainly mutually being overlapped or being bonded by thermoplastic fibre and formed is incorporated fillers into Method in the hole of material includes: in extrusion, infusion process, ultrasonic method, vacuum decompression method, gunite or dynamic negative-pressure method etc. Any one or at least two combination.Various action intensities are so that space network material fracture or damaged for the upper limit.
Preferably, the extrusion, refer to space network material some tension effect under with roll shaft or other objects Body contact or space network material cause solid netted between the object of the mutual extrusion of two or more quantity Structural material is squeezed power, make wherein hole in extrusion process with the external world generate pressure difference, pressure difference promotes solid netted Filler near structural material enters in hole.
In the present invention, the infusion process refers to filler being pre-dispersed in formation filler dispersion liquid, institute in mounting medium Stating mounting medium is liquid solvent and optionally auxiliary agent, then impregnates space network material in filler dispersion liquid, with Filler is set to be introduced into hole in the diffusion process of mounting medium.
In the present invention, the ultrasonic method refers to and impregnates space network material in filler dispersion liquid, and is aided with super Sound further promotes filler to be introduced into hole in the diffusion process of mounting medium.
In the present invention, the vacuum decompression method refers to and places point of filler or filler in the side of stereo net material Dispersion liquid applies vacuum decompression in the other side, so that the two sides of material is generated pressure difference, filler or filler dispersion liquid is promoted to be moved by side The other side is moved on to, so that filler be made to enter in hole.
In the present invention, the gunite, be directed to space network material one or both sides injection filler or Filler dispersion liquid enters filler in material hole.
In the present invention, the dynamic negative-pressure method refers to and applies certain frequency in the one or both sides of stereo net material The hydraulic or air pressure change of variation promotes filler or filler point to make to generate dynamic pressure difference with extraneous in material hole Dispersion liquid enters in hole.
Preferably, when mounting medium is liquid solvent and optionally auxiliary agent, the method also includes going before hot pressing The step of except liquid solvent.
For the removal liquid solvent generally by the way of heat treatment, the temperature of heat treatment is preferably greater than the boiling of liquid solvent Point；When heat treatment temperature is less than 220 DEG C, convection oven or heat radiation baking oven can be used, when heat treatment temperature is greater than 220 DEG C When, vacuum drying oven need to be used, or heat in the inert gas environments such as nitrogen.Heat treatment time need to meet the following conditions: Material after heat treatment dries 1h in the temperature greater than 20 DEG C of liquid adjuvants boiling point or more, and weightlessness is less than 3%.In order to further It avoids will volatilize part and be introduced into sheet material or circuit substrate, preferably weightlessness is less than 1%.
Preferably, the method also includes the filler of space network material surface is removed before hot pressing.
The processing of the present invention for removing surface filler can be before or after removing liquid solvent.Removing liquid solvent Before, scraper can be used or press from both sides the filler dispersion liquid that axis scrapes off space network material surface.After removing liquid solvent, it can adopt The filler on surface is removed with the mode patted or struck off.The filler on removing surface is the fiber in order to make space network material It exposes, there is between lamination better bonding force when guaranteeing hot pressing.
In the present invention, the purpose of hot pressing be make thermoplastic fibre melt or semi-molten so that thermoplastic fibre melting or It is sticked together.In hot pressing, the filler in hole can be melted or the thermoplastic of adhesion during forming sheet material Property fiber cladding, block or be adhered in resin.
The mode of hot pressing of the present invention refers to and is placed on the lamination of individual or multiple composite materials for containing filler Hot pressing obtains sheet material in hot press.Hot pressing temperature can be carried out according to the fusing point of the thermoplastic fibre in space network material Adjustment, generally takes the slightly below temperature of thermoplastic fibre fusing point or the temperature of slightly above thermoplastic fibre fusing point, pressure is so that heat Can be subject to adhesion after Plasitc fibers melting, generally 2MPa to 20MPa, preferably 4MPa to 10MPa.
Hot pressing of the present invention can also refer to the composite lay that individual or multiple are contained filler in high temperature roll-in Hot-pressing processing is carried out on machine, obtains sheet material.Hot pressing temperature can be according to the molten of the thermoplastic fibre in space network material Point is adjusted, and generally takes the slightly below temperature of thermoplastic fibre fusing point or the temperature of slightly above thermoplastic fibre fusing point.Pressure So that can be subject to adhesion after thermoplastic fibre melting, generally 8-18kN, preferably 10-15kN.High temperature roll squeezer hot-pressing processing Before can be to lamination embryo material preheating, to guarantee hot pressing effect, preheating temperature is slightly below or close to hot pressing temperature, after hot-pressing processing It can further be heat-treated.
Can be used in hot pressing and front and back treatment process heat-resisting organic film, metallic film or inert gas to material into Row protection, prevents material oxidation.
Release film need to be used in hot pressing, the use temperature of the release film should be greater than practical hot pressing temperature, to prevent from containing It is bonded between the space network material of filler, polluted product.The release film can be melting temperature greater than practical hot pressing The smooth metallic film etc. of organic film or surface of the surface of temperature with mould release.
The fourth object of the present invention is to provide a kind of circuit substrate, i.e., at least one composite material or piece containing filler Conductive film is covered in the one or both sides of the lamination of material composition, and then hot pressing obtains together.
Conductive film of the present invention, including copper foil, aluminium foil, silver foil, goldleaf or electrically conductive macromolecule membrane etc..
When only covering conductive film on one side in lamination, another side needs to cover release film.The use temperature of release film should be big In practical hot pressing temperature.
In the hot pressing of circuit substrate of the present invention, according to actual needs, enhancement layer can be inserted among lamination And/or adhesive layer.
The enhancement layer includes inorfil cloth, inorganic fibre paper, is prepared by inorfil cloth impregnating resin composition Prepreg, prepreg, ceramic wafer, the film of metal plate or thin plate for being prepared by inorganic fibre paper impregnating resin composition etc. One or more of combination.
The adhesive layer include the thermosetting resin film not being fully cured, melting temperature be less than hot pressing temperature thermoplastic resin Membrane of lipoprotein or toner etc..
Compared with the prior art, the invention has the following beneficial effects:
The present invention by using filler is dispersed in mainly mutually overlapped or bonded as thermoplastic fibre made of stereoscopic graticule In shape structural material, without the use of braided material (woven cloths), the composite material containing filler is made to assign the sheet material obtained using it And circuit substrate has the further advantage that in addition to isotropism
(1) it assigns the space network material excellent mechanical property since fiber orientation crystallizes, makes the strong of sheet material Spend relative in prior art film or die casting film strength and toughness it is higher, can reach 60MPa or more；
(2) since space network material has a flourishing pore structure, filler can uniformly respectively in hole, Being uniformly distributed for filler is realized, sheet material specific function is imparted；
(3) since uniform filling is dispersed in hole, sheet material will not generate gap, avoid and directly adopt thermoplastic The sheet material that property fiber hot pressing obtains stronger disadvantage of hygroscopicity there are gap；
(4) and thermoplastic resin and filler mixed phase ratio are directlyed adopt, it is meltable since thermoplastic fibre heating surface area is big Melt, makes sheet material be easier to bond with metal foil such as copper foil, improve the binding force of circuit substrate, peel strength can reach 0.6N/ Mm or more；
(5) compared with traditional circuit board use bonding sheet manufacture, filler is introduced directly into space network material, It is remarkably improved the content of filler, can reach 60% or more.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Preparation example 1
Liquid crystal polymer non-woven fabrics is prepared using meltblown.Use single axle extruding machine (bore 30mm, L/D=24) by liquid Importing after polycrystalline macromolecule resin (Polyplastics Co., Ltd., LAPREOS) melting, there is flow adjustment structure and heating air to lead Enter the special dies of structure, then (there are 10 circular molten resin discharge hole (400 μ of internal diameter from the spinning-nozzle on mold M) with the gas discharge hole (wide 1mm) of slit-shaped, these molten resin discharge holes are formed a line with the effective width of 5cm, described The gas discharge Kong Nengyu orientation sprays heating air in parallel, to apply tensile stress to molten resin.) in spray Out, it stretches and forms fiber.And collect the fiber on the surface of film-like substrate, formation width is about 5cm to dressed nonwoven fabrics. Then this is waited for into dressed nonwoven fabrics by between a pair of of heating roller for being made of metallic roll and rubber rollers, to make it by hot pressing And become the non-woven fabrics of specific thicknesses.
The fineness that fiber is adjusted by the flow of the heating air in regulating gas discharge hole collects fiber by adjusting The movement speed of film-like substrate adjusts the substance of non-woven fabrics, and temperature, pressure and two roller gaps when by adjusting hot pressing is adjusted The thickness of whole non-woven fabrics.To obtain the non-woven fabrics of following corresponding index.
(avarage fiber diameter is 2.6 μm to liquid crystal polymer fabric nonwoven cloth, substance 22g/m2, 50 μm of thickness, porosity About 75%, interfiber pore diameter is about 15 μm)
(avarage fiber diameter is 7 μm to liquid crystal polymer fabric nonwoven cloth, substance 22g/m2, 75 μm of thickness, porosity is about It is 83%, interfiber pore diameter is about 25 μm)
(avarage fiber diameter is 2.6 μm to liquid crystal polymer fabric nonwoven cloth, substance 10g/m2, 75 μm of thickness, porosity About 92%, interfiber pore diameter is about 55 μm)
(avarage fiber diameter is 2.6 μm to liquid crystal polymer fabric nonwoven cloth, substance 22g/m2, 18 μm of thickness, porosity About 28%, interfiber pore diameter is about 0.01 μm)
(avarage fiber diameter is 45 μm to liquid crystal polymer fabric nonwoven cloth, substance 155g/m2, 220 μm of thickness, hole Rate is about 60%, and interfiber pore diameter is about 50 μm)；
(avarage fiber diameter is 0.5 μm to liquid crystal polymer fabric nonwoven cloth, substance 10g/m2, 25 μm of thickness, porosity About 75%, interfiber pore diameter is about 8 μm)；
Preparation example 2
Polyflon non-woven fabrics is prepared using meltblown.Specific preparation method and preparation example 1 are similar, use poly- four Fluoroethylene resin is polytetrafluoroethylene (PTFE) compound resin (C-88AXP, Japan AGC system).Prepare polyflon non-woven fabrics It is as follows.
(avarage fiber diameter is 7 μm to polytetrafluoroethylene (PTFE) non-woven fabrics, substance 40g/m2, 100 μm of thickness, porosity is about 82%, interfiber pore diameter is about 20 μm)
Embodiment 1
By the liquid crystal polymer non-woven fabrics of sheet, (avarage fiber diameter is 2.6 μm, substance 22g/m2, 50 μm of thickness, hole Gap rate is about 75%, and interfiber pore diameter is about 15 μm), ball-shaped silicon micro powder slurry (ball-type silicon powder partial size D90 be 3 μm, D50 is about 1 μm, slurry be 70% butanone suspension) in dipping, then by the gap of 0.1mm, scrape off surface size, dry Except solvent, then infiltrates again, solvent is removed by gap and baking, repeatedly for three times.The non-woven fabrics for being impregnated with slurry is dried in air blast In 155 DEG C of baking 5min in case, the non-woven fabrics of drying is patted, the filler on surface is removed.Then 3 non-woven fabrics containing filler are folded Polytetrafluoroethylene film is covered as release film in layer, two sides, in 350 DEG C, under vacuum environment, and hot pressing 1h, pressure in electric heating press For 6MPa, the liquid crystal polymer sheet material containing filler is obtained.
Comparative example 1
With extruder by liquid crystalline polymer resin (Polyplastics Co., Ltd., LAPREOS) and ball-shaped silicon micro powder (ball-type silicon Grain size of micropowder D90 is 3 μm, and D50 is about 1 μm, powder) it is uniformly mixed, mixed proportion 4:6.Then mixture tiling is put into In hot press, the thin plate that surrounding places 0.1mm thickness is used to limit thickness, and upper and lower surface covers polytetrafluoroethylene film as release film, in 350 DEG C, under vacuum environment, the hot pressing 1h in electric heating press, pressure 6MPa obtain the liquid crystal polymer membrane containing filler.
Comparative example 2
By the liquid crystal polymer non-woven fabrics of 3 sheets, (avarage fiber diameter is 2.6 μm, substance 22g/m2, 50 μ of thickness M, porosity are about 75%, and interfiber pore diameter is about 15 μm) lamination, upper and lower surface covers polytetrafluoroethylene film as release Film, in 350 DEG C, under vacuum environment, the hot pressing 1h in electric heating press, pressure 6MPa obtain the liquid crystal polymer without filler Film.
Embodiment 2
By the liquid crystal polymer non-woven fabrics of sheet, (avarage fiber diameter is 2.6 μm, substance 22g/m2, 50 μm of thickness, hole Gap rate is about 75%, and interfiber pore diameter is about 15 μm), ball-shaped silicon micro powder slurry (ball-type silicon powder partial size D90 be 3 μm, D50 is about 1 μm, slurry be 70% butanone suspension) in dipping, then by the gap of 0.1mm, scrape off surface size, dry Except solvent, then infiltrates again, solvent is removed by gap and baking, repeatedly for three times.The non-woven fabrics for being impregnated with slurry is dried in air blast In 155 DEG C of baking 5min in case, the non-woven fabrics of drying is patted, the filler on surface is removed.Then by 3 nonwoven fabric laminates, two sides 18 μm of copper foils are covered, in 350 DEG C, under vacuum environment, the hot pressing 1h in electric heating press, pressure 6MPa obtain the liquid crystal containing filler Polymeric circuit substrate.
Embodiment 3
A square box is made, is opened wide above box, connects a suction pipe in side, suction pipe connects vacuum pump.By piece (avarage fiber diameter is 2.6 μm to the liquid crystal polymer non-woven fabrics of shape, substance 22g/m2, 50 μm of thickness, porosity is about 75%, interfiber pore diameter is about 15 μm) it is placed on above box, and the edge that non-woven fabrics is open with box is come into full contact with, Then by carbon fiber, short fine (carbon fiber, 7 μm of diameter, draw ratio is about that aqueous dispersions 10) drench on non-woven fabrics, opens vacuum Pump, and persistently spread the short fine dispersion liquid of carbon fiber.After spreading 1min, vacuum pump is closed, the short fibre of nonwoven surface is scraped off, in 160 DEG C of drying 30min, then by non-woven fabrics it is another up, repeat it is above-mentioned spread dispersion liquid and drying operation, repeatedly three It is secondary.The non-woven fabrics of drying is patted, the filler on surface is removed.Then by 3 treated nonwoven fabric laminates, polytetrafluoro is covered on two sides Vinyl film is as release film, and in 350 DEG C, under vacuum environment, the hot pressing 1h in electric heating press, pressure 6MPa are obtained carbon containing The liquid crystal polymer sheet material of the short fibre of fiber.
Embodiment 4
By the polytetrafluoroethylene (PTFE) non-woven fabrics of sheet, (avarage fiber diameter is 7 μm, substance 40g/m2, 100 μm of thickness, hole Gap rate is about 82%, and interfiber pore diameter is about 20 μm), in dispersion liquid (barium titanate D90 of the barium titanate in ethylene glycol monomethyl ether About 3.5 μm, D50 is about 2 μm, solid content 80%) in dipping, then by the gap of 0.15mm, scrape off surface size, dry Except solvent, then infiltrates again, solvent is removed by gap and baking, repeatedly for three times.The non-woven fabrics for being impregnated with slurry is dried in air blast In 155 DEG C of baking 5min in case, the non-woven fabrics of drying is patted, the filler on surface is removed.Then by 2 nonwoven fabric laminates, two sides 18 μm of copper foils are covered, in 380 DEG C, under vacuum environment, the hot pressing 2h in electric heating press obtains the polyflon electricity containing filler Base board.
Embodiment 5
By the liquid crystal polymer non-woven fabrics of sheet, (avarage fiber diameter is 7 μm, substance 22g/m2, 75 μm of thickness, hole Rate is about 83%, and interfiber pore diameter is about 25 μm) it evens up, and be horizontally arranged.By barium titanate powder, (barium titanate D50 is about 2 μm) be uniformly sprinkled upon on non-woven fabrics, and ceaselessly shake non-woven fabrics.Then non-woven fabrics top and bottom are exchanged, and are uniformly sprinkled with metatitanic acid again Barium dust, and shake non-woven fabrics.It claps except after surface filler powder, by 3 nonwoven fabric laminates, 18 μm of copper foils are covered on two sides, in 350 DEG C, under vacuum environment, the hot pressing 1h in electric heating press obtains the liquid crystal polymer circuit substrate containing filler.
Embodiment 6
Liquid crystal polymer sheet material containing filler, production method is same as Example 1, but by the sheet liquid crystal in embodiment 1 Macromolecule non-woven fabrics replaces with the higher non-woven fabrics of porosity, and (avarage fiber diameter is 2.6 μm, substance 10g/m2, 75 μ of thickness M, porosity are about 92%, and interfiber pore diameter is about 55 μm).
Embodiment 7
Liquid crystal polymer sheet material containing filler, production method is same as Example 1, but by the sheet liquid crystal in embodiment 1 Macromolecule non-woven fabrics replaces with the lower non-woven fabrics of porosity, and (avarage fiber diameter is 2.6 μm, substance 22g/m2, 18 μ of thickness M, porosity are about 28%, and interfiber pore diameter is about 0.01 μm).Non-woven fabrics used is by the liquid crystal high score in embodiment 1 The appropriate hot pressing in electric heating press of sub- non-woven fabrics obtains.
Embodiment 8
Liquid crystal polymer sheet material containing filler, production method is same as Example 1, but by the sheet liquid crystal in embodiment 1 Macromolecular fibre non-woven fabrics replaces with liquid crystal polymer fabric nonwoven cloth, and (avarage fiber diameter is 45 μm, substance 155g/m2, 220 μm of thickness, porosity is about 60%, and interfiber pore diameter is about 50 μm)；Ball-shaped silicon micro powder slurry is replaced with into molten silicon The slurry of micro mist (molten silicon grain size of micropowder D90 is about 20 μm, and D50 is about 5 μm, the butanone suspension that slurry is 75%)；It will be hot Lamination when pressure is changed to 2 layers of liquid crystal polymer composite containing filler.
Embodiment 9
Liquid crystal polymer sheet material containing filler, production method is same as Example 1, but by the sheet liquid crystal in embodiment 1 Macromolecular fibre non-woven fabrics replaces with liquid crystal polymer fabric nonwoven cloth, and (avarage fiber diameter is 0.5 μm, substance 10g/m2, 25 μm of thickness, porosity is about 75%, and interfiber pore diameter is about 8 μm)；Ball-shaped silicon micro powder slurry is replaced with into solid content more Low slurry (ball-type silicon powder partial size D90 is about 3 μm, and D50 is about 1 μm, the butanone suspension that slurry is 45%)；When by hot pressing Lamination be changed to 7 layers of liquid crystal polymer composite containing filler.
Embodiment 10
Liquid crystal polymer sheet material containing filler, production method is same as Example 1, but by the sheet liquid crystal in embodiment 1 Macromolecular fibre non-woven fabrics replaces with liquid crystal polymer fabric nonwoven cloth, and (Kuraray Co., Ltd., KURAFLEX-MBBK22 are put down Equal fibre diameter is 2.8 μm, substance 22g/m2, 50 μm of thickness, porosity is about 75%, and interfiber pore diameter is about 14 μ m)。
The performance of each Examples and Comparative Examples see the table below shown.
Table 1
Continued 1
It can be seen from the above result that: resin is used in comparative example 1 and the method for the direct mixed pressuring plate of filler prepares composite wood Material, tensile strength are very poor relative to the present invention；
Filler is not added in non-woven fabrics in comparative example 2, after hot pressing, is still observed that in sample sections Gap causes its sample water absorption rate higher, and secondary apparent colour is uneven；
The porosity of non-woven fabrics used is excessively high in embodiment 6 (being greater than 90%), so that filler is excessively loose in sample, sample Product intensity is extremely low, frangible, easily loses powder；
Hole is too small (less than 30%) in non-woven fabrics in embodiment 7, and filler is unable to fully enter in material, so that filler Content is too low, there is a small amount of filler at its edge to slice as the result is shown, and gap is more, and water absorption rate is higher, therefore can from embodiment 6 and 7 To find out that the porosity of the non-woven fabrics of thermoplastic material preparation is preferably 30% to 90%.
Filler is the short fibre of carbon fiber in embodiment 3, conductive, dielectric properties is not measured, as a kind of preparation method Example；
Dielectric ceramics filler barium titanate is used in embodiment 4 and 5, the dielectric constant of gained sample is significantly higher, but Its dielectric loss is still lower, can satisfy the demand to high dielectric constant material such as capacitor.
Sheet structure prepared by embodiment 8, embodiment 9 and embodiment 10 is complete, and defect is less, and dielectric properties and stretching are strong It spends.
The test method of the above characteristic is as follows:
(1) thickness of dielectric layers: with the thickness (if it is circuit substrate, copper foil is etched away) of miking insulating layer.
(2) it peel strength: is tested referring to IPC-TM-650 2.4.8 test method, test condition is normality.
(3) dielectric constant of 5GHz, dielectric loss angle tangent: flat referring to the test of IPC-TM-650 2.5.5.9 test method Plate capacitance method.
(4) it is sliced gap: observing plate cross-sectional slices using scanning electron microscope, observe in sample with the presence or absence of sky Gap.
(5) picking rate: taking the composite sample (no copper foil, or copper foil is etched after) having a size of 100mm*100mm, On a piece of smooth A4 paper, above-mentioned composite sample is cut out as the strip of size 10mm*100mm, then picks up strip sample Product, measurement fall the quality of powder or disintegrating slag on A4 paper and the mass ratio of former composite sample.
(6) secondary apparent: apparent after visually observing copper foil etching.
(7) filer content: by mass change of the space network material before and after adding filler, filler is calculated compound Quality specific gravity in material, as filer content.
(8) tensile strength test, Sample Width 15mm, collet distance tensile strength: are carried out using Material Testing Machine 50.8mm, speed of experiment 12.5mm/min.
(9) composite sample of 100mm*100mm (no copper foil, or copper foil is etched after) water absorption rate: is immersed in 25 DEG C water in for 24 hours, then take out the water stain of wipe samples surface, then measure sample impregnate front and back quality difference and proper mass Between ratio.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.

Claims (54)

1. a kind of composite material containing filler for circuit substrate, the composite material include space network material and The filler being dispersed in space network material hole, wherein the space network material is mainly by thermoplastic fibre It mutually overlaps or bonds；
In space network material, the hole for being 0.1-60 μm with diameter between thermoplastic fibre, in space network In material, pore diameter size is 0.1~30 times of thermoplastic fibre diameter, the space network material between thermoplastic fibre The porosity of material is 30% to 90%；The partial size of filler is less than the pore diameter between thermoplastic fibre.
2. composite material as described in claim 1, which is characterized in that the hole for being 0.1-50 μm with diameter between the fiber Gap.
3. composite material as described in claim 1, which is characterized in that the partial size D90 of filler is 30 μm or less.
4. composite material as claimed in claim 3, which is characterized in that the partial size D50 of filler is 0.1-5 μm.
5. composite material as described in claim 1, which is characterized in that the porosity of the space network material is 50% To 85%.
6. composite material as described in claim 1, which is characterized in that the thermoplastic fibre refers to mainly by thermoplastic resin Manufactured fiber.
7. composite material as claimed in claim 6, which is characterized in that the thermoplastic fibre refers to and mainly existed by melting temperature Thermoplastic fibre made of 100~600 DEG C of thermoplastic resin.
8. composite material as claimed in claim 7, which is characterized in that the thermoplastic fibre refers to and mainly existed by melting temperature Thermoplastic fibre made of 200~500 DEG C of thermoplastic resin.
9. composite material as claimed in claim 7, which is characterized in that the thermoplastic fibre refers to and mainly existed by melting temperature Thermoplastic fibre made of 260-360 DEG C of thermoplastic resin.
10. composite material as described in claim 1, which is characterized in that the thermoplastic fibre is selected from liquid crystal polymer, polyamides Imines, polytetrafluoroethylene (PTFE), polyphenylene oxide, polyphenylene sulfide, polysulfones, polytrifluorochloroethylene, polyether-ether-ketone, polyester, polyacrylonitrile, polyphenyl Thermoplasticity made of any one or at least two combination in ethylene, polycarbonate, polyethylene, polypropylene or polyamide is fine Dimension.
11. composite material as described in claim 1, which is characterized in that further include glass in the space network material In glass fiber, quartz fibre, carbon fiber, basalt fibre, boron fibre, metallic fiber or ceramic fibre any one or extremely Few two kinds of combination.
12. composite material as described in claim 1, which is characterized in that the filler is inorganic filler and/or organic filler.
13. composite material as claimed in claim 12, which is characterized in that the inorganic filler is selected from carbon black, silicon powder, three oxygen It is short to change the quartz of two aluminium, titanate, metatianate, titanium dioxide, draw ratio less than 20 staple glass fibre, draw ratio less than 20 In fiber or metal powder any one or at least two combination.
14. composite material as claimed in claim 12, which is characterized in that the organic filler is selected from polyphenylene ether powder, polyphenyl Any one in thioether powder, teflon resin powder, polyimide resin powder end or rubber particle or at least two Combination.
15. composite material as described in claim 1, which is characterized in that the wire feeding is functional filler.
16. composite material as claimed in claim 15, which is characterized in that the functional filler be dielectric ceramics filler, In heat-resistant filler, fire-retardant filler, heat filling, conductive filler, fluorescer, UV absorbent, magnetic fillers or reactive filler Any one or at least two combination.
17. a kind of sheet material, the sheet material is the containing for circuit substrate as at least one as described in one of claim 1-16 The resin film that the composite material hot pressing of filler obtains.
18. a kind of preparation method of sheet material as claimed in claim 17, the described method comprises the following steps:
(1) hole for mainly mutually overlapping or bonding the space network material formed by thermoplastic fibre is incorporated fillers into In, form the composite material containing filler；
(2) sheet material will be obtained by way of hot pressing by the lamination that at least a composite material containing filler is formed.
19. method as claimed in claim 18, which is characterized in that in space network material, have between thermoplastic fibre Having diameter is 0.1-60 μm of hole.
20. method as claimed in claim 19, which is characterized in that the hole for being 0.1-50 μm with diameter between the fiber.
21. method as claimed in claim 18, which is characterized in that in space network material, hole between thermoplastic fibre Gap diameter is 0.1~30 times of thermoplastic fibre diameter.
22. method as claimed in claim 18, which is characterized in that the hole that the partial size of filler is less than between thermoplastic fibre is straight Diameter.
23. method as claimed in claim 18, which is characterized in that the partial size D90 of filler is 30 μm or less.
24. method as claimed in claim 23, which is characterized in that the D50 of filler is 0.1-5 μm.
25. method as claimed in claim 18, which is characterized in that the porosity of the space network material be 30% to 90%.
26. method as claimed in claim 25, which is characterized in that the porosity is 50% to 85%.
27. method as claimed in claim 18, which is characterized in that the thermoplastic fibre refers to mainly by thermoplastic resin system At fiber.
28. method as claimed in claim 27, which is characterized in that the thermoplastic fibre refers to and mainly existed by melting temperature Thermoplastic fibre made of 100~600 DEG C of thermoplastic resin.
29. method as claimed in claim 28, which is characterized in that the thermoplastic fibre refers to and mainly existed by melting temperature Thermoplastic fibre made of 200~500 DEG C of thermoplastic resin.
30. method as claimed in claim 28, which is characterized in that the thermoplastic fibre refers to and mainly existed by melting temperature Thermoplastic fibre made of 260-360 DEG C of thermoplastic resin.
31. method as claimed in claim 18, which is characterized in that the thermoplastic fibre mainly by selected from liquid crystal polymer, Polyimides, polytetrafluoroethylene (PTFE), polyphenylene oxide, polyphenylene sulfide, polysulfones, polytrifluorochloroethylene, polyether-ether-ketone, polyester, polyacrylonitrile, Thermoplastic made of any one or at least two combination in polystyrene, polycarbonate, polyethylene, polypropylene or polyamide Property fiber.
32. method as claimed in claim 18, which is characterized in that further include glass in the space network material In fiber, quartz fibre, carbon fiber, basalt fibre, boron fibre, metallic fiber or ceramic fibre any one or at least Two kinds of combination.
33. method as claimed in claim 18, which is characterized in that the filler is inorganic filler and/or organic filler.
34. method as claimed in claim 33, which is characterized in that the inorganic filler is selected from carbon black, silicon powder, three oxidations two The quartzy staple fiber of aluminium, titanate, metatianate, titanium dioxide, draw ratio less than 20 staple glass fibre, draw ratio less than 20 In metal powder any one or at least two combination.
35. method as claimed in claim 33, which is characterized in that the organic filler is selected from polyphenylene ether powder, polyphenylene sulfide Powder, teflon resin powder, polyimide resin powder end or rubber particle in any one or at least two group It closes.
36. method as claimed in claim 18, which is characterized in that the wire feeding is functional filler.
37. method as claimed in claim 36, which is characterized in that the functional filler is dielectric ceramics filler, heat-resisting It is any in filler, fire-retardant filler, heat filling, conductive filler, fluorescer, UV absorbent, magnetic fillers or reactive filler It is a kind of or at least two combination.
38. method as claimed in claim 18, which is characterized in that filler is pre-dispersed in mounting medium, then is drawn Enter into the hole of space network material.
39. method as claimed in claim 38, which is characterized in that the mounting medium is liquid solvent and optionally helps Agent.
40. method as claimed in claim 39, which is characterized in that the liquid solvent is that water, halogenated hydrocarbon solvent, halogenated phenols are molten Agent, ether solvents, ketone solvent, ester solvent, amine solvent, nitrogenous heterocyclic aromatic compounds solvent, nitrile solvent, amide solvent, urea Close object solvent, nitro compound solvent, in sulphur compound solvent or phosphorus compound solvent any one or at least two Combination.
41. method as claimed in claim 39, which is characterized in that the auxiliary agent includes coupling agent, any one in dispersing agent Kind or at least two combination.
42. method as claimed in claim 38, which is characterized in that the mounting medium is gas.
43. method as claimed in claim 42, which is characterized in that the gas includes air, nitrogen, carbon dioxide or inertia Gas.
44. method as claimed in claim 18, which is characterized in that incorporate fillers into and mainly mutually overlapped by thermoplastic fibre Method in the hole of the space network material of composition includes: extrusion, infusion process, ultrasonic method, vacuum decompression method, injection In method or dynamic negative-pressure method any one or at least two combination, intensity is so that the fracture or broken of space network material Damage is the upper limit.
45. method as claimed in claim 39, which is characterized in that when mounting medium is liquid solvent and optionally auxiliary agent When, the method also includes removing liquid solvent before hot pressing.
46. method as claimed in claim 18, which is characterized in that the method also includes removing solid netted knot before hot pressing The step of filler of structure material surface.
47. method as claimed in claim 18, which is characterized in that the mode of the hot pressing refers at least one containing filler Composite material formed lamination be placed on hot pressing in the hot press heated up and down.
48. method as claimed in claim 47, which is characterized in that the pressure of hot pressing is 2MPa~20MPa.
49. method as claimed in claim 48, which is characterized in that pressure 4MPa~10MPa of hot pressing.
50. method as claimed in claim 18, which is characterized in that the mode of the hot pressing refers at least one containing filler Composite material formed be stacked on high temperature roll squeezer and carry out hot-pressing processing.
51. method as claimed in claim 50, which is characterized in that the pressure of the hot pressing is 8~18kN.
52. method as claimed in claim 51, which is characterized in that the pressure of the hot pressing is 10~15kN.
53. a kind of circuit substrate, by by least one mainly as described in one of claim 1-16 containing the compound of filler Conductive film is covered in the one or both sides for the lamination that sheet material described in material or at least a claim 17 is formed, and then hot pressing obtains It arrives.
54. circuit substrate according to claim 53, which is characterized in that have enhancement layer and/or adhesive layer in the lamination.
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CN107501609B (en) * 2017-07-26 2019-07-05 兰州蓝星纤维有限公司 A kind of thermoplastic fibre composite material sheet and its preparation method and application product
CN110092854B (en) * 2019-04-30 2021-08-10 安徽中科元贞科技有限责任公司 Polymer composite material embedded with three-dimensional inorganic framework and preparation method thereof
JP7238648B2 (en) * 2019-07-08 2023-03-14 Tdk株式会社 Printed wiring board, multilayer printed wiring board, and printed wiring board manufacturing method
TW202206286A (en) 2020-07-28 2022-02-16 美商聖高拜塑膠製品公司 Dielectric substrate and method of forming the same
US20230191750A1 (en) * 2021-12-17 2023-06-22 Saint-Gobain Performance Plastics Corporation Dielectric substrate and method of forming the same
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JP4260789B2 (en) * 2005-10-31 2009-04-30 日本ピラー工業株式会社 Method of using printed circuit board for millimeter wave band communication
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