WO2022061971A1 - 绝缘板及其制备方法、层压板及其制备方法、和应用 - Google Patents

绝缘板及其制备方法、层压板及其制备方法、和应用 Download PDF

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Publication number
WO2022061971A1
WO2022061971A1 PCT/CN2020/120365 CN2020120365W WO2022061971A1 WO 2022061971 A1 WO2022061971 A1 WO 2022061971A1 CN 2020120365 W CN2020120365 W CN 2020120365W WO 2022061971 A1 WO2022061971 A1 WO 2022061971A1
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Prior art keywords
resin
resin layer
layer
pfa
ptfe
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PCT/CN2020/120365
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English (en)
French (fr)
Inventor
王宏远
张翼蓝
王和志
Original Assignee
瑞声声学科技(深圳)有限公司
瑞声精密制造科技(常州)有限公司
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Publication of WO2022061971A1 publication Critical patent/WO2022061971A1/zh

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    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific 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
    • B32B27/06—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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • 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
    • 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
    • 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
    • B32B2307/206—Insulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present application relates to the field of circuit board preparation, in particular to an insulating board and a preparation method thereof, a laminate and a preparation method thereof, and applications.
  • the flexible insulating board made of fiber-reinforced polytetrafluoroethylene (PTFE) resin has many characteristics such as low water absorption, good bending resistance, excellent dielectric properties and low price. It shows great potential for application in other fields.
  • PTFE polytetrafluoroethylene
  • the preparation of the flexible insulating board is made of PTFE resin emulsion
  • the PTFE resin emulsion is an aqueous dispersion
  • the surface of the PTFE resin particles is coated with a hydrophilic surfactant.
  • the surfactant is decomposed and volatilized, while the PTFE
  • the resin has high melting temperature and high melt viscosity, and it is difficult for the surfactant gas to escape, which leads to the easy generation of holes in the flexible insulating board during the high temperature pressing and sintering process, resulting in high porosity and reducing the performance of the flexible insulating board.
  • One of the objectives of the present application is to provide an insulating plate with low porosity, and the insulating plate also has many advantages such as low water absorption, excellent bending resistance and low cost, which can meet the requirements of printing electronic components in the high frequency field in the future. circuit board requirements.
  • An insulating board comprising a fiber layer, a first resin layer covering the fiber layer, a second resin layer covering the first resin layer, and a third resin layer covering the second resin layer;
  • the material of the first resin layer is PFA resin or a mixture of PFA resin and PTFE resin with a mass ratio of 1/9-6/4;
  • the material of the second resin layer is a mixture of PFA resin and PTFE resin with a mass ratio of 1/9-6/4;
  • the material of the third resin layer is a mixture of PFA resin and PTFE resin whose mass ratio is 1/9-6/4;
  • the mass fraction of the fiber layer is 5 parts to 50 parts, and the total mass fraction of the first resin layer, the second resin layer and the third resin layer is 50 parts to 95 parts.
  • the second purpose of the present application is to provide a method for preparing the above-mentioned insulating plate.
  • a preparation method of an insulating board comprising the following processes:
  • a first resin emulsion layer is respectively formed on both sides of the fiber layer, and after drying, a first resin layer covering the fiber layer is formed to obtain a first semi-finished product;
  • a second resin emulsion layer is respectively formed on both sides of the first semi-finished product, and after drying, a second resin layer covering the first semi-finished product is formed to obtain a second semi-finished product;
  • a third resin emulsion layer is respectively formed on both sides of the second semi-finished product, and after drying, a third resin layer covering the second semi-finished product is formed to obtain a third semi-finished product;
  • the third semi-finished product is heat-treated to remove the surfactant in the first resin layer, the second resin layer and the third resin layer to obtain the insulating plate.
  • the third object of the present application is to provide a laminate.
  • a laminated board includes the above-mentioned insulating board and conductive metal sheets stacked on both sides of the above-mentioned insulating board.
  • the fourth purpose of the present application is to provide a method for preparing the above-mentioned laminate.
  • a preparation method of a laminate comprising the following processes:
  • Both sides of the above-mentioned insulating plate are covered with conductive metal sheets, and pressed into shape to form the laminated plate.
  • the fifth purpose of the present application is to provide the application of the above-mentioned insulating board or the above-mentioned laminated board in the field of circuit board preparation.
  • the thickness of each drying resin layer is reduced, which is conducive to the volatilization of the solvent inside each resin layer, and improves the The density of each resin layer; by increasing the PFA resin with lower melt viscosity than PTFE resin in the first resin layer, the second resin layer and the third resin layer, the first resin layer, the second resin layer and the third resin layer are reduced
  • the melt viscosity of the resin layer is beneficial to the overflow of the surfactant gas, reducing the porosity of the insulating plate during the high temperature pressing and sintering process, and improving the performance of the insulating plate.
  • the present application discloses an insulating board, comprising a fiber layer, a first resin layer covering the fiber layer, a second resin layer covering the first resin layer, and a third resin layer covering the second resin layer,
  • the material of the first resin layer is PFA resin or a mixture of PFA resin and PTFE resin with a mass ratio of 1/9-6/4;
  • the material of the second resin layer is PFA resin with a mass ratio of 1/9-6/4 and The mixture of PTFE resin;
  • the material of the third resin layer is a mixture of PFA resin and PTFE resin whose mass ratio is 1/9-6/4;
  • the total mass fraction of the second resin layer and the third resin layer is 50 parts to 95 parts, and the total mass fraction of the insulating plate is 100 parts.
  • the resin layer of the insulating board is divided into a first resin layer, a second resin layer and a third resin layer, which are respectively formed by drying, thereby reducing the thickness of each drying resin layer, which is beneficial to each layer of resin.
  • the solvent inside the layer volatilizes, improving the compactness of each resin layer.
  • the PFA resin having a lower melt viscosity than the PTFE resin in the first resin layer, the second resin layer and the third resin layer respectively, the reduction of the first resin layer, the second resin layer and the third resin layer.
  • the melt viscosity is beneficial to the overflow of surfactant gas, reducing the porosity of the insulating board during the high temperature pressing and sintering process, and improving the performance of the insulating board.
  • the compatibility of PFA resin and PTFE resin is due to the high price of PFA resin.
  • the materials of the first resin layer, the second resin layer, and the third resin layer may be the same or different.
  • the materials of the first resin layer, the second resin layer and the third resin layer are all the same, and in the first resin layer, the mass ratio of the PFA resin and the PTFE resin is 1/9-6/4, and each The mass percentage content of the PFA resin in the resin layer is not less than 10%, and when it is less than 10%, the effect of the PFA resin on improving the melt viscosity of each resin layer is not obvious, and the effect on improving the porosity is not obvious. And the anti-peeling strength of the conductive metal layer of the laminate is low, which cannot meet the demand. When the mass percentage of the PFA resin is higher than 60%, the cost is likely to be too high.
  • the materials of the first resin layer, the second resin layer and the third resin layer are all the same, and in the first resin layer, the mass ratio of PFA resin and PTFE resin is 4/6-6/4 , at this time, the porosity of the insulating plate is lower, the cost is more reasonable, and the performance parameters such as dielectric constant Dk, low loss Changshu Df, and peel strength are all better.
  • the materials of the first resin layer, the second resin layer and the third resin layer are all the same, and the mass ratio of PFA resin and PTFE resin in the first resin layer is 1.
  • the mass percentage content of the PFA resin contained in the first resin layer is greater than that of the PFA resin contained in the second resin layer and is greater than the mass percentage of the PFA resin contained in the third resin layer.
  • the mass percentage content of the PFA resin contained in the first resin layer can be 50 %-100%, so that most of the PFA resin is added to the first resin layer, so that the surfactant gas in the deepest first resin layer can be completely discharged and avoid causing high porosity.
  • the mass percentage content of the PFA resin contained in the second resin layer is 10%-50%
  • the mass percentage content of the PFA resin contained in the third resin layer is 10%-50%
  • the material of the second resin layer and the material of the third resin layer may be the same or different. When they are different, the mass percentage content of the PFA resin contained in the second resin layer may be greater than that of the third resin layer. The mass percentage content of the PFA resin contained may also be less than the mass percentage content of the PFA resin contained in the third resin layer.
  • the mass percentage content of the PFA resin contained in the second resin layer is greater than the mass percentage content of the PFA resin contained in the third resin layer, namely the first resin layer.
  • the mass percentage content of the PFA resin contained in the first resin layer, the second resin layer and the third resin layer decreases in turn, and the performance parameters such as porosity, cost, dielectric constant Dk, loss Changshu Df, peel strength and other performance parameters can be obtained. Excellent insulation board.
  • the thickness of the insulating plate is 20 ⁇ m-150 ⁇ m.
  • the thickness of the fiber layer is 15 ⁇ m-60 ⁇ m.
  • the material of the fiber layer is selected from one or more of glass fibers, quartz fibers and organic fibers.
  • the present application also discloses a method for preparing the above-mentioned insulating plate, including the following processes:
  • PFA resin was purchased from Daikin Fluoride Chemical's AD-2CRER product
  • PTFE resin was purchased from Daikin Fluoride Chemical's D-210 product
  • the purchased PFA resin and PTFE resin included surfactants.
  • the solvent can be water or any other solvent in the prior art.
  • the solid mass percentage content contained in the first resin emulsion is 20%-68%, the solid content is too low, and the thickness of the resin layer formed each time is too thin, resulting in the formation of the target thickness of the insulating plate.
  • the curing times of the thickness increase and prolong the production cycle. Too high a solids content and the resin cannot fully soak into the fiber layer, resulting in voids.
  • the average particle size of the solid particles in the first resin emulsion is 0.1 ⁇ m-1 ⁇ m, more preferably 0.1 ⁇ m-0.5 ⁇ m. If the average particle size is too small, agglomeration may occur, and if the average particle size is too large, the dispersion may be uneven.
  • a first resin emulsion layer is formed on both sides of the fiber layer, the first resin emulsion layer is dried, the solvent in the first resin emulsion layer is removed, and the first resin emulsion layer is cured on both sides of the fiber layer to form a coated fiber layer of the first resin layer to obtain the first semi-finished product.
  • the first resin emulsion layer may be formed by means of dipping, coating, spraying or the like.
  • the fiber layer is immersed in the first resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 70 °C-150 °C to remove the solvent. If the temperature is lower than 70 °C, the water in the fiber layer cannot be completely dried.
  • the temperature is higher than 150°C, part of the surfactant in the first resin emulsion layer decomposes or volatilizes, and the surface energy decreases, making it difficult for the subsequent immersion liquid to adhere.
  • the average particle diameter of the solid particles in the second resin emulsion is 0.1 ⁇ m-1 ⁇ m, more preferably 0.1 ⁇ m-0.5 ⁇ m.
  • the solid mass percentage content contained in the second resin emulsion is 20%-68%.
  • a second resin emulsion layer is formed on both sides of the first semi-finished product, the second resin emulsion layer is dried, the solvent in the second resin emulsion layer is removed, and the second resin emulsion layer is cured on both sides of the first semi-finished product to form a coating
  • the second resin layer of the first semi-finished product is obtained to obtain a second semi-finished product.
  • the second resin emulsion layer may be formed by means of dipping, coating, spraying or the like.
  • the first semi-finished product is immersed in the second resin emulsion and then dried in an oven through a roller, and the drying temperature can also be 70°C-150°C to remove the solvent.
  • the temperature of heat treatment is 180 °C-270 °C. If the temperature is lower than 180 °C, the surfactant is difficult to remove cleanly, and if the temperature is higher than 270 °C, the active agent is easily decomposed and carbonized in the resin, which affects the dielectric properties of the material.
  • the present application also discloses a laminated board, comprising the above-mentioned insulating board and conductive metal sheets stacked on both sides of the insulating board.
  • the conductive metal sheet is copper foil.
  • the number of insulating plates can be 1 or greater than or equal to 2.
  • the insulating plates are stacked in sequence, and the conductive metal sheets are stacked on both sides of the stacked insulating plates.
  • the present application also discloses a method for preparing a laminate, comprising the following processes:
  • the two sides of the above insulating plate are covered with conductive metal sheets, and pressed and sintered at high temperature to form a laminate.
  • the laminates are processed into corresponding circuits or laminated structures to obtain flexible circuit boards.
  • Insulation plate 1 is prepared.
  • the first resin emulsion includes PFA resin, surfactant and water.
  • the fiber layer in the first resin emulsion After immersing the fiber layer in the first resin emulsion, it is dried in an oven through a roller, the drying temperature is 70 °C, and the drying time is 5 minutes, and the water is removed to obtain the first semi-finished product.
  • the first resin emulsion includes PFA resin, PTFE resin, surfactant and water, and the mass ratio of PFA resin and PTFE resin is 1:9.
  • the first semi-finished product is immersed in the second resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 70 °C, and the drying time is 8 min. After removing water, the second semi-finished product is obtained.
  • the third resin emulsion includes PFA resin, PTFE resin, surfactant and water, and the mass ratio of PFA resin and PTFE resin is 1:9.
  • the second semi-finished product is immersed in the third resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 70 °C and the drying time is 10 min. After removing the water, the third semi-finished product is obtained.
  • the insulating board 1 includes a fiber layer, a first resin layer covering the fiber layer, a second resin layer covering the first resin layer, and a third resin layer covering the second resin layer;
  • the material of the first resin layer is PFA resin
  • the material of the second resin layer is a mixture of PFA resin and PTFE resin, and the mass ratio of PFA resin and PTFE resin is 1:9;
  • the material of the third resin layer is a mixture of PFA resin and PTFE resin, and the mass ratio of PFA resin and PTFE resin is 1:9;
  • the total mass of the first resin layer, the second resin layer and the third resin layer accounts for 76% of the total mass of the insulating board 1, that is, the mass percentage of the resin in the insulating board 1 is 76%.
  • the laminated board 1 is formed by covering both surfaces of the insulating board 1 with copper foil.
  • the first resin emulsion includes PFA resin, surfactant and water.
  • the fiber layer in the first resin emulsion After immersing the fiber layer in the first resin emulsion, it is dried in an oven through a roller, the drying temperature is 90 °C, and the drying time is 3 minutes, and the water is removed to obtain the first semi-finished product.
  • the first resin emulsion includes PFA resin, PTFE resin, surfactant and water, and the mass ratio of PFA resin and PTFE resin is 3:7.
  • the first semi-finished product is immersed in the second resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 90 °C, and the drying time is 5 minutes. After removing water, the second semi-finished product is obtained.
  • the third resin emulsion includes PFA resin, PTFE resin, surfactant and water, and the mass ratio of PFA resin and PTFE resin is 5:5.
  • the second semi-finished product is immersed in the third resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 90 °C, and the drying time is 8 minutes.
  • the water is removed to obtain the third semi-finished product.
  • the insulating board 2 includes a fiber layer, a first resin layer covering the fiber layer, a second resin layer covering the first resin layer, and a third resin layer covering the second resin layer;
  • the material of the first resin layer is PFA resin
  • the material of the second resin layer is a mixture of PFA resin and PTFE resin, and the mass ratio of PFA resin and PTFE resin is 3:7;
  • the material of the third resin layer is a mixture of PFA resin and PTFE resin, and the mass ratio of PFA resin and PTFE resin is 5:5;
  • the total mass of the first resin layer, the second resin layer and the third resin layer accounts for 76% of the total mass of the insulating board 2, that is, the mass percentage of the resin in the insulating board 2 is 76%.
  • the laminated board 2 is formed by covering both surfaces of the insulating board 2 with copper foil.
  • the first resin emulsion includes PFA resin, PTFE resin, surfactant and water, and the mass ratio of PFA resin and PTFE resin is 1:9.
  • the fiber layer in the first resin emulsion After immersing the fiber layer in the first resin emulsion, it is dried in an oven through a roller, the drying temperature is 110 °C, the drying time is 1 min, and the water is removed to obtain the first semi-finished product.
  • the first semi-finished product is immersed in the first resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 110 °C, and the drying time is 2 minutes. After removing water, the second semi-finished product is obtained.
  • the second semi-finished product is immersed in the first resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 110 °C, and the drying time is 4 minutes.
  • the water is removed to obtain the third semi-finished product.
  • the insulating board 3 includes a fiber layer, a first resin layer covering the fiber layer, a second resin layer covering the first resin layer, and a third resin layer covering the second resin layer;
  • the material of the first resin layer is a mixture of PFA resin and PTFE resin, and the mass ratio of PFA resin and PTFE resin is 1:9;
  • the material of the second resin layer and the material of the third resin layer are the same as those of the first resin layer.
  • the total mass of the first resin layer, the second resin layer and the third resin layer accounts for 75% of the total mass of the insulating board 3, that is, the mass percentage of the resin in the insulating board 3 is 75%.
  • the laminated board 3 is formed by covering both surfaces of the insulating board 3 with copper foil.
  • the first resin emulsion includes PFA resin, PTFE resin, surfactant and water, and the mass ratio of PFA resin and PTFE resin is 5:5.
  • the fiber layer in the first resin emulsion After immersing the fiber layer in the first resin emulsion, it is dried in an oven through a roller, the drying temperature is 130 °C, the drying time is 2 minutes, and the water is removed to obtain the first semi-finished product.
  • the first resin emulsion includes PFA resin, PTFE resin, surfactant and water, and the mass ratio of PFA resin and PTFE resin is 3:7.
  • the first semi-finished product is immersed in the second resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 90 °C, and the drying time is 2 min. After removing water, the second semi-finished product is obtained.
  • the third resin emulsion includes PFA resin, PTFE resin, surfactant and water, and the mass ratio of PFA resin and PTFE resin is 1:9.
  • the second semi-finished product is immersed in the third resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 90 °C, and the drying time is 2 minutes. After removing water, the third semi-finished product is obtained.
  • the insulating board 4 includes a fiber layer, a first resin layer covering the fiber layer, a second resin layer covering the first resin layer, and a third resin layer covering the second resin layer;
  • the material of the first resin layer is a mixture of PFA resin and PTFE resin, and the mass ratio of PFA resin and PTFE resin is 5:5;
  • the material of the second resin layer is a mixture of PFA resin and PTFE resin, and the mass ratio of PFA resin and PTFE resin is 3:7;
  • the material of the third resin layer is a mixture of PFA resin and PTFE resin, and the mass ratio of PFA resin and PTFE resin is 1:9;
  • the total mass of the first resin layer, the second resin layer and the third resin layer accounts for 77% of the total mass of the insulating board 4 , that is, the mass percentage of the resin in the insulating board 2 is 77%.
  • the laminated board 4 is formed by covering both surfaces of the insulating board 4 with copper foil.
  • the first resin emulsion includes PFA resin, PTFE resin, surfactant and water, and the mass ratio of PFA resin and PTFE resin is 5:5.
  • the fiber layer in the first resin emulsion After immersing the fiber layer in the first resin emulsion, it is dried in an oven through a roller, the drying temperature is 110 °C, and the drying time is 2 minutes, and the water is removed to obtain the first semi-finished product.
  • the first semi-finished product is immersed in the first resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 110 °C, and the drying time is 3 min. After removing water, the second semi-finished product is obtained.
  • the second semi-finished product is immersed in the first resin emulsion and then dried in an oven through a roller.
  • the drying temperature is 110 °C, and the drying time is 5 min. After removing water, the third semi-finished product is obtained.
  • the insulating board 5 includes a fiber layer, a first resin layer covering the fiber layer, a second resin layer covering the first resin layer, and a third resin layer covering the second resin layer;
  • the material of the first resin layer is a mixture of PFA resin and PTFE resin, and the mass ratio of PFA resin and PTFE resin is 5:5;
  • the material of the second resin layer and the material of the third resin layer are the same as those of the first resin layer.
  • the total mass of the first resin layer, the second resin layer and the third resin layer accounts for 76% of the total mass of the insulating board 5, that is, the resin mass percentage in the insulating board 5 is 76%.
  • the laminated board 5 is formed by covering both surfaces of the insulating board 5 with copper foil.
  • Comparative Example 1 adopts the same method as Example 5 to prepare insulating boards and laminates, except that the first resin emulsion is an emulsion of pure PTFE resin, and the second resin emulsion, the third resin emulsion and the first resin emulsion same.
  • Comparative Example 2 adopts the same method as Example 5 to prepare insulating boards and laminates, except that the first resin emulsion is an emulsion of pure PFA resin, and the second resin emulsion, the third resin emulsion and the first resin emulsion same.
  • Comparative example 2 adopts the same method as Example 5 to prepare insulating boards and laminates, except that the first resin emulsion is an emulsion of pure PTFE resin, and the second resin emulsion includes PFA resin, PTFE resin, surfactant and The mass ratio of water, PFA resin and PTFE resin is 9:1, the second resin emulsion includes PFA resin, PTFE resin, surfactant and water, and the mass ratio of PFA resin and PTFE resin is 9:1.
  • Table 1 shows the performance parameters of the laminates of Examples 1-5 and Comparative Examples 1-3, which can be seen from Table 1: 1) Referring to Comparative Example 1, when the first, second and third resin layers When both are PTFE resins, the porosity of the laminate is the largest, and the copper peel strength is low, which cannot meet the demand. 2) Referring to Comparative Example 2, when the first, second and third resin layers are all PFA resins, each performance index is better, but when all PFA resins are used, the production cost is too high. The purpose of this application is to provide An insulating board with low cost, low porosity, high copper peel strength, and excellent Dk, Df, and water absorption resistance.
  • Comparative Example 1 when the first resin layer is PTFE resin, even if the mass percentage of PFA resin in the second resin layer and the third resin layer is as high as 90%, the problem of high porosity cannot be overcome. 4) Comparing Examples 1-5 with Comparative Example 1, Examples 1-5 all have lower porosity, because each resin layer has introduced PFA resin with lower melt viscosity.
  • Examples 1-5 all have higher copper peel strength, this is because the viscosity of the PFA resin is higher, and the adhesion between the copper foil and the copper foil is enhanced, Furthermore, since each resin layer contains PFA resin, the compatibility between the resin layers is improved, the phase separation between the layers is reduced, and the copper peel strength of the laminate as a whole is improved.

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Abstract

一种绝缘板及其制备方法、层压板及其制备方法、和应用，绝缘板包括纤维层、包覆所述纤维层的第一树脂层、包覆所述第一树脂层的第二树脂层和包覆所述第二树脂层的第三树脂层；所述第一树脂层的材料为PFA树脂或质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；所述第二树脂层的材料为质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；所述第三树脂层的材料为质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；所述纤维层的质量份数为5份-50份，所述第一树脂层、所述第二树脂层和所述第三树脂层的总质量份数为50份-95份。该绝缘板具有低孔隙率、低吸水率、低成本、耐弯折性能优异的特点，能够满足未来高频领域电子元器件对印制电路板的要求。

Description

绝缘板及其制备方法、层压板及其制备方法、和应用 技术领域
本申请涉及线路板制备领域，具体涉及一种绝缘板及其制备方法、层压板及其制备方法、和应用。
 背景技术
采用纤维增强聚四氟乙烯（PTFE）树脂制备的挠性绝缘板具有吸水率低、耐弯折性能佳、介电性能优异以及价格低等诸多特点，因而，在高频、高速、大容量存储等领域展现出巨大的应用潜质。
 技术问题
由于制备挠性绝缘板采用的是PTFE树脂乳液，PTFE树脂乳液为水性分散液，PTFE树脂颗粒表面被亲水性的表面活性剂所包覆，经过烘烤，表面活性剂分解，挥发，而PTFE树脂熔融温度高，熔融粘度大，表面活性剂气体溢出困难，导致挠性绝缘板在高温压合烧结过程中易产生孔洞，导致高孔隙率，降低挠性绝缘板的性能。
 技术解决方案
本申请的目的之一在于提供一种低孔隙率的绝缘板，且该绝缘板还具有吸水率低、耐弯折性能优异及低成本等诸多优点，能够满足未来高频领域电子元器件对印制电路板的要求。
本申请的技术方案如下：
一种绝缘板，包括纤维层、包覆所述纤维层的第一树脂层、包覆所述第一树脂层的第二树脂层和包覆所述第二树脂层的第三树脂层；
所述第一树脂层的材料为PFA树脂或质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；
所述第二树脂层的材料为质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；
所述第三树脂层的材料为质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；
所述纤维层的质量份数为5份-50份，所述第一树脂层、所述第二树脂层和所述第三树脂层的总质量份数为50份-95份。
本申请的目的之二在于提供上述绝缘板的制备方法。
本申请的技术方案如下：
一种绝缘板的制备方法，包括以下过程：
将PFA树脂和表面活性剂分散在溶剂中形成第一树脂乳液，或者将表面活性剂以及质量比为1/9-6/4的PFA树脂和PTFE树脂分散在溶剂中形成第一树脂乳液；
在纤维层的双面分别形成第一树脂乳液层，干燥后形成包覆所述纤维层的第一树脂层，得到第一半成品；
将所述表面活性剂以及质量比为1/9-6/4的PFA树脂和PTFE树脂分散在所述溶剂中形成第二树脂乳液；
在所述第一半成品的双面分别形成第二树脂乳液层，干燥后形成包覆所述第一半成品的第二树脂层，得到第二半成品；
将所述表面活性剂以及质量比为1/9-6/4的PFA树脂和PTFE树脂分散在所述溶剂中形成第二树脂乳液；
在所述第二半成品的双面分别形成第三树脂乳液层，干燥后形成包覆所述第二半成品的第三树脂层，得到第三半成品；
对所述第三半成品进行热处理，去除所述第一树脂层、所述第二树脂层和所述第三树脂层中的所述表面活性剂，得到所述绝缘板。
本申请的目的之三在于提供一种层压板。
本申请的技术方案如下：
一种层压板，包括上述的绝缘板和叠加在上述绝缘板的双面的导电金属片。
本申请的目的之四在于提供上述层压板的制备方法。
本申请的技术方案如下：
一种层压板的制备方法，包括以下过程：
将上述的绝缘板的双面覆上导电金属片，压合成型，形成所述层压板。
本申请的目的之五在于提供上述绝缘板或上述层压板在线路板制备领域的应用。
 有益效果
本申请的有益效果在于：
通过将绝缘板的树脂层分成第一树脂层、第二树脂层和第三树脂层，分别干燥形成，降低了每次干燥的树脂层的厚度，有利于每层树脂层内部的溶剂挥发，提高每层树脂层的密实度；通过在第一树脂层、第二树脂层和第三树脂层中增加熔融粘度比PTFE树脂低的PFA树脂，降低了第一树脂层、第二树脂层和第三树脂层的熔融粘度，有益于表面活性剂气体的溢出，降低绝缘板在高温压合烧结过程中产生的孔隙率，提高绝缘板的性能。
 本发明的实施方式
下面结合具体实施方式对本申请作进一步说明。
参考图1本申请公开了一种绝缘板，包括纤维层、包覆纤维层的第一树脂层、包覆第一树脂层的第二树脂层和包覆第二树脂层的第三树脂层，第一树脂层的材料为PFA树脂或质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；第二树脂层的材料为质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；第三树脂层的材料为质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；纤维层的质量份数为5份-50份，第一树脂层、第二树脂层和第三树脂层的总质量份数为50份-95份，绝缘板的总质量份数为100份。
上述技术方案，一方面，通过将绝缘板的树脂层分成第一树脂层、第二树脂层和第三树脂层，分别干燥形成，降低了每次干燥的树脂层的厚度，有利于每层树脂层内部的溶剂挥发，提高每层树脂层的密实度。另一方面，通过在第一树脂层、第二树脂层和第三树脂层中分别增加熔融粘度比PTFE树脂低的PFA树脂，降低了第一树脂层、第二树脂层和第三树脂层的熔融粘度，有益于表面活性剂气体的溢出，降低绝缘板在高温压合烧结过程中产生的孔隙率，提高绝缘板的性能，再者，将PFA树脂和PTFE树脂配伍，由于PFA树脂的价格远大于PTFE树脂的价格，因此，也避免仅使用PFA树脂制备绝缘板带来的高造价，在保证低孔隙率、低吸水率低、低介电常数Dk、低损耗常熟Df、高抗剥离强度的条件下，大大降低了绝缘板的生产成本。
第一树脂层、第二树脂层和第三树脂层的材料可以相同，也可以不同。在一具体实施例中，第一树脂层、第二树脂层和第三树脂层的材料均相同，第一树脂层中，PFA树脂和PTFE树脂的质量比为1/9-6/4，每层树脂层中的PFA树脂的质量百分含量不低于10 %，低于10 %时，PFA树脂对改善每层树脂层的熔融粘度的作用不明显，对改善孔隙率的效果也不明显，且层压板的导电金属层的抗剥离强度低，无法满足需求，当PFA树脂的质量百分数高于60 %时，易造成成本过高。
在一较优具体实施例中，第一树脂层、第二树脂层和第三树脂层的材料均相同，第一树脂层中，PFA树脂和PTFE树脂的质量比为4/6-6/4，此时，绝缘板的孔隙率更低，成本更合理，且介电常数Dk、低损耗常熟Df、抗剥离强度等性能参数均较优。
在最佳实施例中，第一树脂层、第二树脂层和第三树脂层的材料均相同，第一树脂层中，PFA树脂和PTFE树脂的质量比为1。
当第一树脂层、第二树脂层和第三树脂层的材料不相同时，在一具体实施例中，第一树脂层含有的PFA树脂的质量百分含量大于第二树脂层含有的PFA树脂的质量百分含量，且大于第三树脂层含有的PFA树脂的质量百分含量。当第一树脂层、第二树脂层和第三树脂层均加工完成时，对形成第一树脂层、第二树脂层和第三树脂层的半成品进行加热去除表面活性剂时，第一树脂层的深度最深，使第一树脂层内的表面活性剂气体更易排出，保证绝缘板整体的低孔隙率。
进一步的，可以使第一树脂层含有的PFA树脂的质量百分含量为50 %-100 %，使大部分的PFA树脂均增加到第一树脂层，便于位于最深的第一树脂层的表面活性剂气体完全排出，避免造成高孔隙率。
进一步的，使第二树脂层含有的PFA树脂的质量百分含量为10 %-50 %，以及使第三树脂层含有的PFA树脂的质量百分含量为10 %-50 %。在本具体实施例中，第二树脂层的材料和第三树脂层的材料可以相同，也可以不同，当不同时，第二树脂层含有的PFA树脂的质量百分含量可以大于第三树脂层含有的PFA树脂的质量百分含量，也可以小于第三树脂层含有的PFA树脂的质量百分含量。
进一步的，当第二树脂层的材料和第三树脂层的材料不同时，第二树脂层含有的PFA树脂的质量百分含量大于第三树脂层含有的PFA树脂的质量百分含量，即第一树脂层、第二树脂层和第三树脂层含有的PFA树脂的质量百分含量依次减小，可以获得孔隙率、成本、介电常数Dk、损耗常熟Df、抗剥离强度等性能参数均较优的绝缘板。
在一具体实施例中，绝缘板的厚度为20 μm-150 μm。
在一具体实施例中，纤维层的厚度为15 μm-60 μm。纤维层的材质选自玻璃纤维、石英纤维和有机纤维中的一种或两种以上。
本申请还公开了上述绝缘板的制备方法，包括以下过程：
1）制备第一树脂乳液，将PFA树脂和表面活性剂分散在溶剂中形成第一树脂乳液，或者将PFA树脂、PTFE树脂和表面活性剂分散在溶剂中形成第一树脂乳液，当第一树脂乳液包括PFA树脂和PTFE树脂时，PFA树脂和PTFE树脂的质量比为1/9-6/4。
在本过程中，PFA树脂购买自大金氟化工的AD-2CRER产品，PTFE树脂购买自大金氟化工的D-210产品，购买的PFA树脂和PTFE树脂包括表面活性剂。
在本过程中，溶剂可以为水，也可以为现有技术的任何其它溶剂。
在本过程中，第一树脂乳液中含有的固体质量百分含量为20 %-68 %，固体含量过低，每次形成的树脂层的厚度过薄，导致形成目标厚度的绝缘板的固化次数增多，延长生产周期。固体含量过高，树脂无法完全浸入纤维层，从而产生孔洞。
优选的，第一树脂乳液中的固体颗粒的平均粒径为0.1 μm-1 μm，更优选为0.1 μm-0.5 μm，平均粒径过小易发生团聚，平均粒径过大易分散不均匀。
2）在纤维层的双面分别形成第一树脂乳液层，干燥第一树脂乳液层，去除第一树脂乳液层中的溶剂，第一树脂乳液层固化在纤维层的双面形成包覆纤维层的第一树脂层，得到第一半成品。
在本过程中，可以采用浸渍、涂覆、喷淋等方式形成第一树脂乳液层。在本具体实施例中，将纤维层浸入第一树脂乳液后经滚轴进入烘箱中干燥，干燥温度为70 ℃-150 ℃，以去除溶剂，温度低于70 ℃，纤维层中的水无法完全去除，高于150 ℃，第一树脂乳液层的部分表面活性剂分解或挥发，表面能下降，使后续浸渍液难以附着。
3）将PFA树脂、PTFE树脂和表面活性剂分散在溶剂中形成第二树脂乳液，其中，PFA树脂和PTFE树脂的质量比为1/9-6/4。
在本过程中，第二树脂乳液中的固体颗粒的平均粒径为0.1 μm-1 μm，更优选为0.1 μm-0.5 μm。
在本过程中，第二树脂乳液中含有的固体质量百分含量为20 %-68 %。
4）在第一半成品的双面分别形成第二树脂乳液层，干燥第二树脂乳液层，去除第二树脂乳液层中的溶剂，第二树脂乳液层固化在第一半成品的双面形成包覆第一半成品的第二树脂层，得到第二半成品。
在本过程中，可以采用浸渍、涂覆、喷淋等方式形成第二树脂乳液层。在本具体实施例中，将第一半成品浸入第二树脂乳液后经滚轴进入烘箱中干燥，干燥温度也可以为70 ℃-150 ℃，以去除溶剂。
5）将PFA树脂、PTFE树脂和表面活性剂分散在溶剂中形成第三树脂乳液，其中，PFA树脂和PTFE树脂的质量比为1/9-6/4；
6）在第二半成品的双面分别形成第三树脂乳液层，干燥第三树脂乳液层，去除第三树脂乳液层中的溶剂，第三树脂乳液层固化在第二半成品的双面形成包覆第二半成品的第三树脂层，得到第三半成品；
7）对第三半成品进行热处理，去除第一树脂层、第二树脂层和第三树脂层中的表面活性剂，得到绝缘板。
在本过程中，热处理的温度为180 ℃-270 ℃。温度低于180 ℃，表面活性剂难以去除干净，大于270 ℃，活性剂易在树脂中分解碳化，影响材料介电性能。
本申请还公开了一种层压板，包括上述的绝缘板和叠加在绝缘板的双面的导电金属片。
在一具体实施例中，导电金属片为铜箔。
绝缘板的数量可以为1个，也可以大于或等于2，当绝缘板的数量大于或等于2时，各绝缘板依次层叠，导电金属片叠加在层叠后的绝缘板的双面。
本申请还公开了一种层压板的制备方法，包括以下过程：
将上述绝缘板的双面覆上导电金属片，经高温压合烧结成型，形成层压板。
将层压板加工成相应的线路或叠层结构制得柔性电路板。
以下为具体实施例。
实施例1
制备绝缘板1。
1）配制第一树脂乳液，第一树脂乳液包括PFA树脂、表面活性剂和水。
2）将纤维层浸入第一树脂乳液后经滚轴进入烘箱中干燥，干燥温度为70 ℃，干燥时间为5min，去除水，得到第一半成品。
3）配制第二树脂乳液，第一树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为1:9。
4）将第一半成品浸入第二树脂乳液后经滚轴进入烘箱中干燥，干燥温度为70 ℃，干燥时间为8min，去除水，得到第二半成品。
5）配制第三树脂乳液，第三树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为1:9。
6）将第二半成品浸入第三树脂乳液后经滚轴进入烘箱中干燥，干燥温度为70 ℃，干燥时间为10min，去除水，得到第三半成品。
7）将第三半成品转入烘箱中进行热处理，热处理温度为180 ℃，热处理时间为180min，得绝缘板1。
绝缘板1包括纤维层、包覆所述纤维层的第一树脂层、包覆所述第一树脂层的第二树脂层和包覆所述第二树脂层的第三树脂层；
第一树脂层的材料为PFA树脂；
第二树脂层的材料为PFA树脂和PTFE树脂的混合物，PFA树脂和PTFE树脂的质量比为1:9；
第三树脂层的材料为PFA树脂和PTFE树脂的混合物，PFA树脂和PTFE树脂的质量比为1:9；
第一树脂层、第二树脂层和第三树脂层的总质量占绝缘板1总质量的76 %，即绝缘板1中的树脂质量百分含量为76 %。
在绝缘板1的双面覆盖铜箔形成层压板1。
实施例2
制备绝缘板2
1）配制第一树脂乳液，第一树脂乳液包括PFA树脂、表面活性剂和水。
2）将纤维层浸入第一树脂乳液后经滚轴进入烘箱中干燥，干燥温度为90 ℃，干燥时间为3min，去除水，得到第一半成品。
3）配制第二树脂乳液，第一树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为3:7。
4）将第一半成品浸入第二树脂乳液后经滚轴进入烘箱中干燥，干燥温度为90 ℃，干燥时间5min，去除水，得到第二半成品。
5）配制第三树脂乳液，第三树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为5:5。
6）将第二半成品浸入第三树脂乳液后经滚轴进入烘箱中干燥，干燥温度为90 ℃，干燥时间8min，去除水，得到第三半成品。
7）将第三半成品转入烘箱中进行热处理，热处理温度为200 ℃，热处理时间为120min，得绝缘板2。
绝缘板2包括纤维层、包覆所述纤维层的第一树脂层、包覆所述第一树脂层的第二树脂层和包覆所述第二树脂层的第三树脂层；
第一树脂层的材料为PFA树脂；
第二树脂层的材料为PFA树脂和PTFE树脂的混合物，PFA树脂和PTFE树脂的质量比为3:7；
第三树脂层的材料为PFA树脂和PTFE树脂的混合物，PFA树脂和PTFE树脂的质量比为5:5；
第一树脂层、第二树脂层和第三树脂层的总质量占绝缘板2总质量的76 %，即绝缘板2中的树脂质量百分含量为76 %。
在绝缘板2的双面覆盖铜箔形成层压板2。
实施例3
制备绝缘板3
1）配制第一树脂乳液，第一树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为1:9。
2）将纤维层浸入第一树脂乳液后经滚轴进入烘箱中干燥，干燥温度为110 ℃，干燥时间1min，去除水，得到第一半成品。
3）将第一半成品浸入第一树脂乳液后经滚轴进入烘箱中干燥，干燥温度为110 ℃，干燥时间2min，去除水，得到第二半成品。
4）将第二半成品浸入第一树脂乳液后经滚轴进入烘箱中干燥，干燥温度为110 ℃，干燥时间4min，去除水，得到第三半成品。
5）将第三半成品转入烘箱中进行热处理，热处理温度为230 ℃，热处理时间为90min，得绝缘板3。
绝缘板3包括纤维层、包覆所述纤维层的第一树脂层、包覆所述第一树脂层的第二树脂层和包覆所述第二树脂层的第三树脂层；
第一树脂层的材料为PFA树脂和PTFE树脂的混合物，PFA树脂和PTFE树脂的质量比为1:9；
第二树脂层的材料和第三树脂层的材料与第一树脂层的材料相同。
第一树脂层、第二树脂层和第三树脂层的总质量占绝缘板3总质量的75%，即绝缘板3中的树脂质量百分含量为75 %。
在绝缘板3的双面覆盖铜箔形成层压板3。
实施例4
制备绝缘板4
1）配制第一树脂乳液，第一树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为5:5。
2）将纤维层浸入第一树脂乳液后经滚轴进入烘箱中干燥，干燥温度为130 ℃，干燥时间2min，去除水，得到第一半成品。
3）配制第二树脂乳液，第一树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为3:7。
4）将第一半成品浸入第二树脂乳液后经滚轴进入烘箱中干燥，干燥温度为90 ℃，干燥时间2min，去除水，得到第二半成品。
5）配制第三树脂乳液，第三树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为1:9。
6）将第二半成品浸入第三树脂乳液后经滚轴进入烘箱中干燥，干燥温度为90 ℃，干燥时间2min，去除水，得到第三半成品。
7）将第三半成品转入烘箱中进行热处理，热处理温度为270 ℃，热处理时间为60min，得绝缘板4。
绝缘板4包括纤维层、包覆所述纤维层的第一树脂层、包覆所述第一树脂层的第二树脂层和包覆所述第二树脂层的第三树脂层；
第一树脂层的材料为PFA树脂和PTFE树脂的混合物，PFA树脂和PTFE树脂的质量比为5:5；
第二树脂层的材料为PFA树脂和PTFE树脂的混合物，PFA树脂和PTFE树脂的质量比为3:7；
第三树脂层的材料为PFA树脂和PTFE树脂的混合物，PFA树脂和PTFE树脂的质量比为1:9；
第一树脂层、第二树脂层和第三树脂层的总质量占绝缘板4总质量的77%，即绝缘板2中的树脂质量百分含量为77%。
在绝缘板4的双面覆盖铜箔形成层压板4。
实施例5
制备绝缘板5
1）配制第一树脂乳液，第一树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为5:5。
2）将纤维层浸入第一树脂乳液后经滚轴进入烘箱中干燥，干燥温度为110 ℃，干燥时间为2min，去除水，得到第一半成品。
3）将第一半成品浸入第一树脂乳液后经滚轴进入烘箱中干燥，干燥温度为110 ℃，干燥时间为3min，去除水，得到第二半成品。
4）将第二半成品浸入第一树脂乳液后经滚轴进入烘箱中干燥，干燥温度为110 ℃，干燥时间为5min，去除水，得到第三半成品。
5）将第三半成品转入烘箱中进行热处理，热处理温度为230 ℃，热处理时间为90min，得绝缘板5。
绝缘板5包括纤维层、包覆所述纤维层的第一树脂层、包覆所述第一树脂层的第二树脂层和包覆所述第二树脂层的第三树脂层；
第一树脂层的材料为PFA树脂和PTFE树脂的混合物，PFA树脂和PTFE树脂的质量比为5:5；
第二树脂层的材料和第三树脂层的材料与第一树脂层的材料相同。
第一树脂层、第二树脂层和第三树脂层的总质量占绝缘板5总质量的76%，即绝缘板5中的树脂质量百分含量为76 %。
在绝缘板5的双面覆盖铜箔形成层压板5。
对比例1
对比例1采用和实施例5相同的方法制备绝缘板和层压板，不同之处，在于，第一树脂乳液为纯PTFE树脂的乳液，且第二树脂乳液和第三树脂乳液和第一树脂乳液相同。
对比例2
对比例2采用和实施例5相同的方法制备绝缘板和层压板，不同之处，在于，第一树脂乳液为纯PFA树脂的乳液，且第二树脂乳液和第三树脂乳液和第一树脂乳液相同。
对比例3
对比例2采用和实施例5相同的方法制备绝缘板和层压板，不同之处，在于，第一树脂乳液为纯PTFE树脂的乳液，第二树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为9:1, 第二树脂乳液包括PFA树脂、PTFE树脂、表面活性剂和水，PFA树脂和PTFE树脂的质量比为9:1。
表1给出了上述实施例1-5和对比例1-3的各层压板的性能参数，从表1可以看到：1）参考对比例1，当第一、第二和第三树脂层均为PTFE树脂时，层压板的孔隙率最大，铜剥离强度较低，无法满足需求。2）参考对比例2，当第一、第二和第三树脂层均为PFA树脂时，各项性能指数均较优，但是全部使用PFA树脂时，生产成本过高，本申请的目的在于提供一种低成本、低孔隙率、高铜剥离强度以及优异的Dk、Df、抗吸水性能的绝缘板。3）参考对比例1，当第一树脂层为PTFE树脂时，第二树脂层和第三树脂层中即使PFA树脂的质量百分含量高达90%，也无法克服高孔隙率的问题。4）将实施例1-5和对比例1相比，实施例1-5均具有较低的孔隙率，这是因为每层树脂层均引入了熔融粘度较低的PFA树脂。5）将实施例1-5和对比例1相比，实施例1-5均具有较高的铜剥离强度，这是因为PFA树脂的粘度较大，与铜箔之间的粘结力增强，再者，由于每层树脂层均含有PFA树脂，各层树脂之间的兼容能力被提高，减少了层与层之间的相分离，从而提高了层压板整体的铜剥离强度。
Figure dest_path_image001
以上所述的仅是本申请的实施方式，在此应当指出，对于本领域的普通技术人员来说，在不脱离本申请创造构思的前提下，还可以做出改进，但这些均属于本申请的保护范围。

Claims (15)

  1. 一种绝缘板，其特征在于，包括纤维层、包覆所述纤维层的第一树脂层、包覆所述第一树脂层的第二树脂层和包覆所述第二树脂层的第三树脂层；
    所述第一树脂层的材料为PFA树脂或质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；
    所述第二树脂层的材料为质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；
    所述第三树脂层的材料为质量比为1/9-6/4的PFA树脂和PTFE树脂的混合物；
    所述纤维层的质量份数为5份-50份，所述第一树脂层、所述第二树脂层和所述第三树脂层的总质量份数为50份-95份。
  2. 根据权利要求1所述的绝缘板，其特征在于，所述第一树脂层中， PFA树脂和PTFE树脂的质量比为1/9-6/4，所述第二树脂层和所述第三树脂层的材料均与所述第一树脂层的材料相同。
  3. 根据权利要求1所述的绝缘板，其特征在于，所述第一树脂层中， PFA树脂和PTFE树脂的质量比为4/6-6/4，所述第二树脂层和所述第三树脂层的材料均与所述第一树脂层的材料相同。
  4. 根据权利要求1所述的绝缘板，其特征在于，所述第一树脂层中的PFA树脂的质量百分含量大于所述第二树脂层中的PFA树脂的质量百分含量，且大于所述第三树脂层中的PFA树脂的质量百分含量。
  5. 根据权利要求4所述的绝缘板，其特征在于，所述第一树脂层中，PFA树脂的质量百分含量为50 %-100 %。
  6. 根据权利要求5所述的绝缘板，其特征在于，所述第二树脂层中，PFA树脂的质量百分含量为10 %-50 %；
    所述第三树脂层中，PFA树脂的质量百分含量为10 %-50 %。
  7. 根据权利要求6所述的绝缘板，其特征在于，所述第二树脂层中的PFA树脂的质量百分含量大于所述第三树脂层中的PFA树脂的质量百分含量。
  8. 根据权利要求1所述的绝缘板，其特征在于，
    所述绝缘板的厚度为20 μm-150 μm；
    所述纤维层的厚度为15 μm-60 μm。
  9. 根据权利要求1所述的绝缘板，其特征在于，所述纤维层的材质选自玻璃纤维、石英纤维和有机纤维中的一种或两种以上。
  10. 一种权利要求9任意一项所述的绝缘板的制备方法，其特征在于，包括以下过程：
    将PFA树脂和表面活性剂分散在溶剂中形成第一树脂乳液，或者将表面活性剂以及质量比为1/9-6/4的PFA树脂和PTFE树脂分散在溶剂中形成第一树脂乳液；
    在纤维层的双面分别形成第一树脂乳液层，干燥后形成包覆所述纤维层的第一树脂层，得到第一半成品；
    将所述表面活性剂以及质量比为1/9-6/4的PFA树脂和PTFE树脂分散在所述溶剂中形成第二树脂乳液；
    在所述第一半成品的双面分别形成第二树脂乳液层，干燥后形成包覆所述第一半成品的第二树脂层，得到第二半成品；
    将所述表面活性剂和质量比为1/9-6/4的PFA树脂和PTFE树脂分散在所述溶剂中形成第二树脂乳液；
    在所述第二半成品的双面分别形成第三树脂乳液层，干燥后形成包覆所述第二半成品的第三树脂层，得到第三半成品；
    对所述第三半成品进行热处理，去除所述第一树脂层、所述第二树脂层和所述第三树脂层中的所述表面活性剂，得到所述绝缘板。
  11. 根据权利要求10所述的制备方法，其特征在于，干燥所述第一树脂乳液层的温度为70 ℃-150 ℃；
    干燥所述第二树脂乳液层的温度为70 ℃-150 ℃；
    干燥所述第三树脂乳液层的温度为70 ℃-150 ℃；
    所述热处理的温度为180 ℃-270 ℃。
  12. 一种层压板，其特征在于，包括如权利要求1-9任意一项所述的绝缘板和叠加在所述绝缘板的双面的导电金属片。
  13. 根据权利要求12所述的层压板，其特征在于，所述绝缘板的数量大于或等于2，所述绝缘板依次层叠，所述导电金属片叠加在层叠后的所述绝缘板的双面。
  14. 一种层压板的制备方法，其特征在于，包括以下过程：
    将如权利要求1-9任意一项所述的绝缘板的双面覆上导电金属片，压合成型，形成所述层压板。
  15. 权利要求1-9任意一项所述的绝缘板或权利要求12-13任意一项所述的层压板在线路板制备领域的应用。
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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113119546A (zh) * 2021-04-20 2021-07-16 华南理工大学 一种聚四氟乙烯印刷电路基板及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008129784A1 (ja) * 2007-03-20 2008-10-30 Sumitomo Bakelite Co., Ltd. 積層板の製造方法および積層板
CN102114453A (zh) * 2011-03-03 2011-07-06 吴江市东风电子有限公司 一种制备覆铜板用介质布的制备方法
CN102173175A (zh) * 2011-02-24 2011-09-07 禹胜林 一种改性聚四氟乙烯覆铜板制备方法
CN105862421A (zh) * 2016-04-11 2016-08-17 浙江科力新材料科技有限公司 一种含铜基的聚四氟乙烯/玻璃纤维布膜状复合材料及其制作方法
CN106633785A (zh) * 2016-12-30 2017-05-10 广东生益科技股份有限公司 用于电路基板的预浸渍料、层压板、制备方法及包含其的印制电路板

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100797691B1 (ko) * 2005-12-19 2008-01-23 삼성전기주식회사 인쇄회로기판 및 그 제조방법
CN102166852A (zh) * 2010-12-31 2011-08-31 广东生益科技股份有限公司 一种高弹性模量的ptfe覆铜板的制备方法
CN102514353B (zh) * 2011-12-13 2014-11-26 广东生益科技股份有限公司 覆铜板的生产方法及该覆铜板
CN104553224B (zh) * 2014-12-30 2017-05-24 广东生益科技股份有限公司 粘性漆布制作方法、应用该方法制成的粘性漆布和覆铜板
CN105153451A (zh) * 2015-09-22 2015-12-16 广东生益科技股份有限公司 一种浸渍方法、浸渍片及层压板
CN111251676A (zh) * 2020-02-25 2020-06-09 无锡睿龙新材料科技有限公司 一种高导热改性聚四氟乙烯覆铜板及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008129784A1 (ja) * 2007-03-20 2008-10-30 Sumitomo Bakelite Co., Ltd. 積層板の製造方法および積層板
CN102173175A (zh) * 2011-02-24 2011-09-07 禹胜林 一种改性聚四氟乙烯覆铜板制备方法
CN102114453A (zh) * 2011-03-03 2011-07-06 吴江市东风电子有限公司 一种制备覆铜板用介质布的制备方法
CN105862421A (zh) * 2016-04-11 2016-08-17 浙江科力新材料科技有限公司 一种含铜基的聚四氟乙烯/玻璃纤维布膜状复合材料及其制作方法
CN106633785A (zh) * 2016-12-30 2017-05-10 广东生益科技股份有限公司 用于电路基板的预浸渍料、层压板、制备方法及包含其的印制电路板

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