WO2022141662A1 - 一种覆不对称金属箔的层压板和包含其的印刷线路板 - Google Patents

一种覆不对称金属箔的层压板和包含其的印刷线路板 Download PDF

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Publication number
WO2022141662A1
WO2022141662A1 PCT/CN2021/070942 CN2021070942W WO2022141662A1 WO 2022141662 A1 WO2022141662 A1 WO 2022141662A1 CN 2021070942 W CN2021070942 W CN 2021070942W WO 2022141662 A1 WO2022141662 A1 WO 2022141662A1
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Prior art keywords
modulus
metal foil
low
prepreg
asymmetric
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PCT/CN2021/070942
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English (en)
French (fr)
Inventor
唐军旗
李志光
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广东生益科技股份有限公司
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Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to US18/270,038 priority Critical patent/US20240064910A1/en
Priority to KR1020227025954A priority patent/KR20220123044A/ko
Priority to JP2023514778A priority patent/JP2023540509A/ja
Publication of WO2022141662A1 publication Critical patent/WO2022141662A1/zh

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0271—Arrangements for reducing stress or warp in rigid printed circuit boards, e.g. caused by loads, vibrations or differences in thermal expansion
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • 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
    • B32B17/061—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 metal
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • H05K3/4632—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating thermoplastic or uncured resin sheets comprising printed circuits without added adhesive materials between the 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0263—High current adaptations, e.g. printed high current conductors or using auxiliary non-printed means; Fine and coarse circuit patterns on one circuit board
    • H05K1/0265—High current adaptations, e.g. printed high current conductors or using auxiliary non-printed means; Fine and coarse circuit patterns on one circuit board characterized by the lay-out of or details of the printed conductors, e.g. reinforced conductors, redundant conductors, conductors having different cross-sections
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0133—Elastomeric or compliant polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0275—Fibers and reinforcement materials
    • H05K2201/0278—Polymeric fibers

Definitions

  • the invention belongs to the technical field of circuit boards, and in particular relates to a laminated board covered with asymmetric metal foil and a printed circuit board containing the same.
  • the printed circuit board is the support of electronic components and the provider of electrical connection of electronic components. It is widely used in various electronic equipment, communication equipment, computers, automobiles, household appliances and other equipment. With the development of electronic information technology and the multi-functionalization and miniaturization of electronic products, the core skeleton integrated circuit board tends to be multi-layered and multi-functional.
  • Metal-clad laminates are the basic materials for making printed circuit boards.
  • Conventional double-sided metal foil clad laminates are covered with metal foils with the same thickness and the same characteristics on both sides. Even if the metal foils on both sides are different, their thickness and characteristics will not be too different. This is to make double-sided metal foil clad laminates. In state A and after reflow soldering, the amount of warpage is small, or even no warpage occurs, so as to ensure that the printed circuit board has a good bearing capacity for electronic components.
  • the metal foils on both sides of the double-sided metal-clad laminates need to be designed with different thicknesses, which can not only meet the performance and It can meet the requirements of reducing costs and meet the heat dissipation requirements of lines under high current.
  • the asymmetric structure of this metal foil will lead to uneven internal stress generated during the processing of the asymmetric metal foil laminate, such as lamination, solder mask and hot air leveling, resulting in the laminate and its use.
  • the printed circuit board is warped, which in turn causes the failure of electronic component installation, circuit short circuit and other problems of reliability reduction.
  • the purpose of the present invention is to provide an asymmetric metal foil-clad laminate and a printed circuit board including the same.
  • the asymmetric metal foil-clad laminate has lower A-state warpage and warpage after reflow soldering, which helps to improve the safety and reliability of the printed circuit board.
  • the present invention provides an asymmetric metal foil-clad laminate, the asymmetric metal foil-clad laminate comprising one or at least two laminated low-modulus prepregs, and an asymmetric metal foil-clad laminate. sheet or at least two laminated low modulus prepregs with metal foils on one side or metal foils with different thicknesses on both sides;
  • the elastic modulus of the low-modulus prepreg after curing is below 22GPa (for example, it can be 22GPa, 21.5GPa, 21GPa, 20.5GPa, 20GPa, 19.5GPa, 19GPa, 18.5GPa, 18GPa, 17.5GPa, 17GPa, 16.5GPa , 16GPa, 15.5GPa, 15GPa, 14GPa, 13GPa, 12GPa, 11GPa, 10GPa, 8GPa, 6GPa or 5GPa, etc.).
  • the inventor found through research that by selecting a low-modulus prepreg with an elastic modulus below 22 GPa after curing as an insulating material for a laminate covered with asymmetric metal foil, the laminate can be guaranteed to have a lower amount of warpage. If the elastic modulus of the cured prepreg is higher than 22GPa, the rigidity of the laminate is too large, and the buffering ability to stress is weak, which cannot effectively buffer the stress caused by the asymmetric structure of the laminate covered with asymmetric metal foil, resulting in Laminates covered with asymmetric metal foils are prone to warping.
  • one side or both sides of the low-modulus prepreg refers to one side or one side of the sheet of low-modulus prepreg. Both sides; when the laminate includes at least two laminated low modulus prepregs, "one or both sides of the low modulus prepreg” means one side of the laminated low modulus prepreg composite or sides.
  • the present invention does not limit the thickness of the prepreg.
  • the "asymmetric" in the present invention mainly means that the thickness of the metal foil on both sides of the low-modulus prepreg is not equal, including the case where the low-modulus prepreg is only covered with metal foil on one side, that is, one side is covered with metal foil, A single panel without metal foil on one side, including the case where metal foils of different thicknesses are covered on both sides.
  • Low modulus prepregs include a substrate and a resin composition attached to the substrate by impregnation or coating.
  • the present invention does not have special restrictions on the type of resin composition, and those skilled in the art can select it according to actual needs, as long as the elastic modulus of the low-modulus prepreg after curing is 22 GPa or less.
  • the present invention has no particular limitation on the substrate. Exemplarily, textiles, non-woven fabrics, rovings, short fibers, fiber paper, etc.
  • the materials can be selected, and the materials can be inorganic fibers (such as E glass, D glass, L glass, M glass, etc.) , S glass, T glass, NE glass, Q glass, quartz and other glass fibers) or organic fibers (such as polyimide, polyamide, polyester, polyphenylene ether, liquid crystal polymer, etc.), preferably glass fiber cloth.
  • inorganic fibers such as E glass, D glass, L glass, M glass, etc.
  • organic fibers such as polyimide, polyamide, polyester, polyphenylene ether, liquid crystal polymer, etc.
  • the preparation method of the asymmetric metal foil-clad laminate according to the present invention is not specifically limited, and can be prepared by a known method.
  • the lamination conditions can be selected from general lamination conditions for metal foil-clad laminates, laminates for printed wiring boards, and multilayer boards.
  • the elastic modulus of the low-modulus prepreg after curing is 20 GPa or less.
  • the elastic modulus of the low-modulus prepreg after curing is 18 GPa or less.
  • the elastic modulus of the low-modulus prepreg after curing is 16 GPa or less.
  • the elastic modulus of the low-modulus prepreg after curing is 5 GPa or more. If the elastic modulus of the cured prepreg is too low, the rigidity of the laminate is too small. When the external force is too large, the laminate covered with asymmetric metal foil may be deformed, and the bearing capacity of the printed circuit board for electronic components In addition, when the modulus is too low, it also brings operational difficulties to the manufacture of printed circuit boards. Appropriate modulus should be selected according to application requirements to avoid large deformation of laminates or printed circuit boards covered with asymmetric metal foils during use.
  • the XY-CTE (coefficient of thermal expansion in the plane direction) of the low-modulus prepreg after curing is below 18ppm/°C; 16.5ppm/°C, 16ppm/°C, 15.5ppm/°C, 15ppm/°C, 14.5ppm/°C, 14ppm/°C, 13.5ppm/°C, 13ppm/°C, 12.5ppm/°C, 12ppm/°C, 11.5ppm/°C, 11ppm/°C, 10ppm/°C, 9ppm/°C, 8ppm/°C, 7ppm/°C, 6ppm/°C, 5ppm/°C, 3ppm/°C or 1.5ppm/°C, etc.
  • the XY-CTE of the low-modulus prepreg after curing is 16 ppm/°C or less.
  • the XY-CTE of the low-modulus prepreg after curing is 14 ppm/°C or less.
  • the deformation of the laminate will be larger when the laminate is heated and subjected to stress, and the laminate covered with asymmetric metal foil will And the warpage of the printed circuit board made by using it increases, which leads to a decrease in reliability; the use of a low-modulus prepreg with a cured XY-CTE below 18ppm/°C can ensure the layer covered with asymmetric metal foil.
  • the deformation amount of the pressing plate and the printed circuit board produced by using the same is not enough to affect the normal use thereof, and has lower warpage and better reliability.
  • the present invention has no particular limitation on the type of the metal foil, which can be selected from metal foils used for printed wiring board materials.
  • the present invention has no particular limitation on the thickness of the metal foil, which can be selected from metal foils of any thickness used for printed circuit board materials.
  • the thickness of the metal foil covered on one side of the low-modulus prepreg is 1.5-700 ⁇ m; for example, it can be 1.5 ⁇ m. ⁇ m, 3 ⁇ m, 5 ⁇ m, 9 ⁇ m, 12 ⁇ m, 18 ⁇ m, 35 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 105 ⁇ m, 120 ⁇ m, 140 ⁇ m, 175 ⁇ m, 200 ⁇ m, 210 ⁇ m, 245 ⁇ m, 280 ⁇ m, 300 ⁇ m, 315 ⁇ m, 350 ⁇ m, 385 ⁇ m, 490 ⁇ m, 420 ⁇ m 525 ⁇ m or 700 ⁇ m etc.
  • the thickness difference between the metal foils on both sides is ⁇ 5 ⁇ m, for example, the thickness difference may be 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 18 ⁇ m, 20 ⁇ m, 22 ⁇ m, 25 ⁇ m, 28 ⁇ m, 30 ⁇ m, 32 ⁇ m, 35 ⁇ m, 38 ⁇ m, 40 ⁇ m, 42 ⁇ m, 45 ⁇ m, 48 ⁇ m, 50 ⁇ m, 52 ⁇ m, 55 ⁇ m, 58 ⁇ m, 60 ⁇ m, 65 ⁇ m, 70 ⁇ m, 75 ⁇ m, 80 ⁇ m, 85 ⁇ m, 90 ⁇ m, 95 ⁇ m, 100 ⁇ m, 110 ⁇ m, 130 ⁇ m, 150 ⁇ m, 170 ⁇ m, 190 ⁇ m, 200 ⁇ m, 210 ⁇ m, 230 ⁇ m, 250 ⁇ m, 270 ⁇ m, 290 ⁇ m, 300 ⁇ m, 310 ⁇ m, 330 ⁇ m, 350
  • the thickness difference between the metal foils on both sides is greater than or equal to 5 ⁇ m, the metal foil-clad laminate will warp, and the use of the low-modulus prepreg of the present invention can effectively improve or even completely eliminate the warpage.
  • the thickness difference of the metal foils on both sides is larger, the internal stress difference caused by the structural asymmetry is larger, the metal foil-clad laminate is more likely to warp, and the low-modulus prepreg of the present invention can be more manifested. Compared with conventional prepregs, it plays an obvious role in improving or even completely eliminating warpage.
  • the thickness of the metal foil on one side of the one or at least two laminated low-modulus prepregs is less than or equal to 35 ⁇ m (for example, it can be 35 ⁇ m, 33 ⁇ m, 30 ⁇ m, 28 ⁇ m, 25 ⁇ m, 22 ⁇ m, 20 ⁇ m, 18 ⁇ m, 15 ⁇ m, 12 ⁇ m, 9 ⁇ m, 6 ⁇ m, 5 ⁇ m, 3 ⁇ m or 1.5 ⁇ m, etc.); from the perspective of current transmission and heat dissipation capability, the thickness of the metal foil covering the other side of the one or at least two laminated low-modulus prepregs is ⁇ 70 ⁇ m ( For example, it can be 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 105 ⁇ m, 120 ⁇ m, 140 ⁇ m, 175 ⁇ m, 200 ⁇ m, 210 ⁇ m, 245 ⁇ m, 280 ⁇ m, 300 ⁇ m, 315 ⁇ m, 350 ⁇ m, 385 ⁇ m
  • the T g of the low-modulus prepreg after curing is 150°C or higher, such as 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C, 255°C, 260°C, 265°C, 270°C , 275°C, 280°C, 290°C or 300°C, etc.; preferably 170°C or higher, more preferably 200°C or higher, still more preferably 230°C or higher, most preferably 250°C or higher.
  • the choice of the cured T g of the low modulus prepreg according to the present invention is related to the operating temperature of the asymmetric metal foil clad laminate and the printed wiring board made therefrom.
  • the operating temperature is higher than T g , the cured prepreg is in a rubbery state, and the asymmetric metal foil-coated laminate and the printed circuit board made with it have a large amount of deformation under stress, which affects its reliability.
  • the operating temperature of the laminate covered with asymmetric metal foil and the printed circuit board made by using it generally exceeds 150°C, so the T g of the low-modulus prepreg of the present invention after curing is 150°C or higher, preferably 170°C or higher, It is more preferably 200°C or higher, still more preferably 230°C or higher, and most preferably 250°C or higher, in order to improve the modulus retention rate of the cured prepreg at high temperature.
  • the present invention provides a printed circuit board, the printed circuit board comprising at least one asymmetric metal foil-clad laminate according to the first aspect.
  • the present invention has the following beneficial effects:
  • the elastic modulus after curing of the prepreg is adjusted and controlled below 22GPa, so that the obtained laminate covered with asymmetric metal foil has a lower warpage, and the printed circuit board prepared therefrom is guaranteed. reliability.
  • Prepreg A The elastic modulus after curing is 17GPa, the XY-CTE is 13ppm/°C, and the T g is 270°C;
  • Prepreg B The elastic modulus after curing is 21GPa, the XY-CTE is 10ppm/°C, and the T g is 270°C;
  • Prepreg C The elastic modulus after curing is 10GPa, the XY-CTE is 10ppm/°C, and the T g is 170°C;
  • Prepreg D The elastic modulus after curing is 18GPa, the XY-CTE is 20ppm/°C, and the T g is 150°C;
  • Prepreg E The elastic modulus after curing is 17GPa, the XY-CTE is 20ppm/°C, and the T g is 270°C;
  • Prepreg F The elastic modulus after curing is 28GPa, the XY-CTE is 10ppm/°C, and the T g is 270°C;
  • Prepreg G The elastic modulus after curing is 23GPa, the XY-CTE is 15ppm/°C, and the T g is 270°C;
  • Prepreg H The elastic modulus after curing is 28GPa, the XY-CTE is 20ppm/°C, and the T g is 270°C;
  • Prepreg I The elastic modulus after curing was 17 GPa, the XY-CTE was 15 ppm/°C, and the T g was 270°C.
  • the present invention does not limit the thickness of the prepreg and the thickness of the glass fiber cloth.
  • the thickness of the above single prepreg is uniformly selected to be 125 ⁇ m.
  • the performance test method of the cured prepreg is as follows:
  • Sample preparation 12 ⁇ m copper foil was coated on both sides of 8 laminated prepregs and 1 prepreg respectively, and then placed in a hot press to cure at a temperature of 200 °C and a pressure of 30 kg/cm 2 Under the condition of curing for 90min, the prepreg is completely cured, and the copper foil can be etched to obtain laminates with thicknesses of 1.0mm and 0.125mm, respectively.
  • Copper foil thickness test method refer to GB/T 29847-2013 copper foil test method 6.3 for printed boards.
  • Elastic modulus test method Take a laminate with a length of 76.2mm, a width of 25.4mm and a thickness of 1.0mm as a sample, and use a material testing machine to measure it. The span is 25.4mm, the test speed is 0.76mm/min, and the maximum bending strength The flexural modulus can be converted according to the formula, which is the elastic modulus, and the unit is GPa.
  • XY-CTE test method Take a laminate with a length of 60mm, a width of 4mm and a thickness of 0.125mm as a sample, the glass fiber weft direction is X direction, the glass fiber warp direction is Y direction, and the sample is dried in an oven at 105 ° C for 1 hour Then cool to room temperature in a desiccator.
  • the thermal analysis mechanical method (TMA) was used for measurement, the heating rate was 10 °C/min, the temperature was raised from room temperature to 260 °C, and the temperature was increased twice. Coefficient of thermal expansion in the plane direction at a secondary temperature rise of 50°C to 130°C, in ppm/°C.
  • Glass transition temperature (T g ) test method Take a laminate with a length of 60mm, a width of 10mm and a thickness of 1.0mm as a sample, and use a dynamic mechanical thermal analyzer (DMA) to measure it. The heating rate is 10°C/min. The results Take the transition peak temperature of tan ⁇ , and the unit is °C.
  • DMA dynamic mechanical thermal analyzer
  • Copper foil A thickness 12 ⁇ m
  • Copper foil B thickness 35 ⁇ m
  • Copper foil C thickness 105 ⁇ m
  • Copper foil D thickness 210 ⁇ m
  • Examples 1-11 and Comparative Examples 1-4 respectively provide a laminate covered with asymmetric metal foil, which is composed of the low-modulus prepreg and a metal foil covered on one side of the low-modulus prepreg or metal foils with different thicknesses on both sides. Its preparation method is as follows:
  • Two copper foils with different thicknesses are respectively covered on both sides of the prepreg, or one copper foil is covered on one side of the prepreg, and then placed in a hot press at a temperature of 200°C and a pressure of Under the condition of 30kg/ cm2 , curing for 90min, the prepreg is completely cured to obtain a laminate covered with asymmetric metal foil;
  • warpage types of asymmetric metal foil clad laminates are divided into bow and twist, and their definitions and test methods refer to the IPC-TM-650 standard.
  • the bow is defined as a deformation of the plate similar to a cylindrical or curved shape.
  • a copper-clad plate with a rectangular shape its four corners are on the same plane.
  • the bow test method is: the convex side of the sample is placed on the test platform, and the maximum vertical distance between the sample and the platform is measured.
  • Distortion is defined as a deformation of a rectangular sheet in a direction parallel to the diagonal, where one corner is not contained in the plane of the other three corners.
  • the twist test method is: place the sample on the test platform, make any three corners contact the platform, and measure the maximum vertical distance between the corners that do not touch the platform and the platform.
  • the amount of warpage in state A refers to the amount of warpage in state A, which means that the sample is directly tested without treatment, and the maximum value of bow or twist obtained is the amount of warpage in state A.
  • the warpage amount after reflow soldering treatment refers to the reflow soldering parameters after reflow soldering treatment: heating from 30°C to 260°C, and then cooling from 260°C to 30°C at a rate of 3°C/min.
  • the maximum value of the bow or twist is the amount of warpage after the reflow process.
  • the dimensions of the asymmetric metal foil clad laminate samples were 250 mm (warp) x 300 mm (wrap).
  • Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Prepreg 1 x Prepreg F 1 x Prepreg G 1 x Prepreg F 1 x Prepreg H upper copper foil Copper foil A Copper foil A Copper foil B Copper foil A Lower copper foil copper foil D copper foil D copper foil D Warp Amount/mm 10 6 7 15 Warpage after reflow soldering/mm 15 12 13 20

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Abstract

本发明提供一种覆不对称金属箔的层压板和包含其的印刷线路板。所述覆不对称金属箔的层压板包括一张或至少两张层叠的低模量预浸料，和覆于所述一张或至少两张层叠的低模量预浸料一侧的金属箔或两侧的厚度不同的金属箔；所述低模量预浸料固化后的弹性模量为22GPa以下。本发明通过选择固化后弹性模量在22GPa以下的低模量预浸料作为覆不对称金属箔的层压板的绝缘材料，从而使得到的覆不对称金属箔的层压板和由其制备的印刷线路板具有较低的A态翘曲量和回流焊处理后的翘曲量，保证印刷线路板的可靠性。

Description

一种覆不对称金属箔的层压板和包含其的印刷线路板 技术领域
本发明属于电路板技术领域，具体涉及一种覆不对称金属箔的层压板和包含其的印刷线路板。
背景技术
印刷线路板是电子元器件的支撑体，是电子元器件电气连接的提供者，其广泛应用于各种电子装备、通信设备、电脑、汽车、家用电器等设备中。随着电子信息技术的发展，电子产品的多功能化和微型化，其核心骨架集成电路板越来越趋向于多层化和多功能化。
覆金属箔层压板是制作印刷线路板的基础材料。常规的双面覆金属箔层压板两面都是覆厚度相同、特性一致的金属箔，即使两面金属箔不同，其厚度、特性也不会相差太远，这样是为了使双面覆金属箔层压板在A态及回流焊处理后的翘曲量较少，甚至不发生翘曲，以保证印刷线路板对电子元器件具有良好的承载能力。
对于单面线路板，则需要单面覆铜板；对于单面线路要求能通过大电流的情况，则需要将双面覆金属箔层压板两面的金属箔设计成不同厚度，这样既能满足性能和降低成本的要求，又能满足大电流下线路的散热要求。但是这种金属箔不对称的结构会导致覆不对称金属箔层压板在加工过程，如层压、阻焊以及热风平整等工序中，产生的内应力不均，导致层压板和使用其制得的印刷线路板翘曲，进而引起电子元器件安装失效、线路短路等可靠性降低的问题。
因此，有必要开发出一种具有较低翘曲量的覆不对称金属箔的层压板，以提高使用其制得的印刷线路板的可靠性。
发明内容
针对现有技术存在的不足，本发明的目的在于提供一种覆不对称金属箔的层压板和包含其的印刷线路板。该覆不对称金属箔的层压板具有较低的A态翘曲量和回流焊处理后的翘曲量，有助于提高印刷线路板的安全可靠性。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供一种覆不对称金属箔的层压板，所述覆不对称金属箔的层压板包括一张或至少两张层叠的低模量预浸料，和覆于所述一张或至少两张层叠的低模量预浸料一侧的金属箔或两侧的厚度不同的金属箔；
所述低模量预浸料固化后的弹性模量为22GPa以下(例如可以是22GPa、21.5GPa、21GPa、20.5GPa、20GPa、19.5GPa、19GPa、18.5GPa、18GPa、17.5GPa、17GPa、16.5GPa、16GPa、15.5GPa、15GPa、14GPa、13GPa、12GPa、11GPa、10GPa、8GPa、6GPa或5GPa等)。
发明人通过研究发现，通过选择固化后弹性模量在22GPa以下的低模量预浸料作为覆不对称金属箔的层压板的绝缘材料，能够保证层压板具有较低的翘曲量。若预浸料固化后的弹性模量高于22GPa，则层压板的刚性过大，对应力的缓冲能力较弱，不能有效缓冲因覆不对称金属箔的层压板结构不对称引起的应力，导致覆不对称金属箔的层压板容易发生翘曲。
需要说明的是，本发明中当层压板包括一张低模量预浸料时，“低模量预浸料一侧或两侧”是指该一张低模量预浸料的一侧或两侧；当层压板包括至少两张层叠的低模量预浸料时，“低模量预浸料一侧或两侧”是指层叠后的低模量预浸料复合材料的一侧或两侧。本发明对预浸料的厚度不做限制。本发明中所述“不对称”主要是指低模量预浸料两侧的金属箔厚度不相等，包括低模量预浸料仅一侧覆金属箔的情况，即一侧覆金属箔，一侧没有金属箔的单面板，也包括两侧覆不同厚度的金属箔的情况。
低模量预浸料包括基材及通过浸渍或涂覆而附着于基材上的树脂组合物。本发明对树脂组合物的种类没有特殊限制，本领域技术人员可根据实际需要进行选择，其满足使低模量预浸料固化后的弹性模量为22GPa以下即可。本发明对基材没有特别的限制，示例性的，可以选择纺织物、无纺布、粗纱、短纤维、纤维纸等，材质可以是无机纤维(例如E玻璃、D玻璃、L玻璃、M玻璃、S玻璃、T玻璃、NE玻璃、Q玻璃、石英等玻璃纤维)或有机纤维(例如聚酰亚胺、聚酰胺、聚酯、聚苯醚、液晶聚合物等)，优选玻璃纤维布。
本发明所述的覆不对称金属箔的层压板的制备方式没有具体的限制，可以通过公知的方法来制备。层压条件可以选用覆金属箔层压板、印刷线路板用的层压板和多层板的通用层压条件。
以下作为本发明的优选技术方案，但不作为对本发明提供的技术方案的限制，通过以下优选的技术方案，可以更好地达到和实现本发明的目的和有益效果。
作为本发明的优选技术方案，所述低模量预浸料固化后的弹性模量为20GPa以下。
作为本发明的优选技术方案，所述低模量预浸料固化后的弹性模量为18GPa以下。
作为本发明的优选技术方案，所述低模量预浸料固化后的弹性模量为16GPa以下。
作为本发明的优选技术方案，所述低模量预浸料固化后的弹性模量为5GPa以上。若预浸料固化后的弹性模量过低，则层压板的刚性过小，当外力过大时，覆不对称金属箔的层压板有变形的可能，印刷线路板对电子元器件的承载能力变差，另外当模量太低时，也为印刷线路板的制造带来了操作难度。应根据应 用需求，选择合适的模量，避免覆不对称金属箔的层压板或印刷线路板在使用过程中折弯从而产生较大的形变。
作为本发明的优选技术方案，所述低模量预浸料固化后的XY-CTE(平面方向热膨胀系数)为18ppm/℃以下；例如可以是18ppm/℃、17.5ppm/℃、17ppm/℃、16.5ppm/℃、16ppm/℃、15.5ppm/℃、15ppm/℃、14.5ppm/℃、14ppm/℃、13.5ppm/℃、13ppm/℃、12.5ppm/℃、12ppm/℃、11.5ppm/℃、11ppm/℃、10ppm/℃、9ppm/℃、8ppm/℃、7ppm/℃、6ppm/℃、5ppm/℃、3ppm/℃或1.5ppm/℃等。
作为本发明的优选技术方案，所述低模量预浸料固化后的XY-CTE为16ppm/℃以下。
作为本发明的优选技术方案，所述低模量预浸料固化后的XY-CTE为14ppm/℃以下。
本发明中，若所述低模量预浸料固化后的XY-CTE过高，高于18ppm/℃，则层压板受热后受到应力作用时形变量较大，覆不对称金属箔的层压板及使用其制得的印刷线路板的翘曲变大，进而造成可靠性下降；采用固化后的XY-CTE在18ppm/℃以下的低模量预浸料，可以保证覆不对称金属箔的层压板及使用其制得的印刷线路板在使用过程中产生的形变量不足以影响其正常使用，具备较低的翘曲量和较好的可靠性。
本发明对所述金属箔的种类没有特别的限制，其可选自用于印刷线路板材料的金属箔。
本发明对所述金属箔的厚度没有特别的限制，其可选自用于印刷线路板材料的任意厚度的金属箔。
作为本发明的优选技术方案，当覆不对称金属箔的层压板为单面覆金属箔 时，所述覆于低模量预浸料一侧的金属箔厚度为1.5-700μm；例如可以为1.5μm、3μm、5μm、9μm、12μm、18μm、35μm、70μm、80μm、90μm、105μm、120μm、140μm、175μm、200μm、210μm、245μm、280μm、300μm、315μm、350μm、385μm、400μm、420μm、490μm、525μm或700μm等。
作为本发明的优选技术方案，当所述一张或至少两张层叠的低模量预浸料两侧均覆有金属箔时，两侧的金属箔的厚度差≥5μm，例如厚度差可以为5μm、8μm、10μm、12μm、15μm、18μm、20μm、22μm、25μm、28μm、30μm、32μm、35μm、38μm、40μm、42μm、45μm、48μm、50μm、52μm、55μm、58μm、60μm、65μm、70μm、75μm、80μm、85μm、90μm、95μm、100μm、110μm、130μm、150μm、170μm、190μm、200μm、210μm、230μm、250μm、270μm、290μm、300μm、310μm、330μm、350μm、370μm、390μm、400μm或410μm等，优选≥10μm，更优选≥18μm，进一步优选≥35μm。当两侧的金属箔的厚度差≥5μm，覆金属箔层压板就会发生翘曲，选用本发明所述的低模量预浸料能有效改善甚至完全消除翘曲。随着两侧的金属箔的厚度差越大，结构不对称性产生的内应力差越大，覆金属箔层压板越容易发生翘曲，越能显现本发明所述的低模量预浸料相比于常规预浸料在改善甚至完全消除翘曲所发挥的明显作用。
作为本发明的优选技术方案，从信号传输损耗及细线路加工能力的角度考虑，当所述一张或至少两张层叠的低模量预浸料两侧均覆有金属箔时，优选覆于所述一张或至少两张层叠的低模量预浸料一侧的金属箔厚度≤35μm(例如可以是35μm、33μm、30μm、28μm、25μm、22μm、20μm、18μm、15μm、12μm、9μm、6μm、5μm、3μm或1.5μm等)；从电流传输及散热能力的角度考虑，覆于所述一张或至少两张层叠的低模量预浸料另一侧的金属箔厚度≥70 μm(例如可以是70μm、80μm、90μm、105μm、120μm、140μm、175μm、200μm、210μm、245μm、280μm、300μm、315μm、350μm、385μm、400μm、420μm、490μm、525μm或700μm等)，从覆金属箔层压板和印刷线路板加工能力的角度考虑，进一步优选覆于所述一张或至少两张层叠的低模量预浸料另一侧的金属箔厚度为70-420μm，进一步综合考虑电流传输及散热能力、覆金属箔层压板和印刷线路板加工能力，更优选覆于所述一张或至少两张层叠的低模量预浸料另一侧的金属箔厚度为140-420μm。
作为本发明的优选技术方案，所述低模量预浸料固化后的T g为150℃以上，例如可以是150℃、155℃、160℃、165℃、170℃、175℃、180℃、185℃、190℃、195℃、200℃、205℃、210℃、220℃、225℃、230℃、235℃、240℃、245℃、250℃、255℃、260℃、265℃、270℃、275℃、280℃、290℃或300℃等；优选170℃以上，进一步优选200℃以上，更进一步优选230℃以上，最优选250℃以上。
本发明对低模量预浸料固化后的T g的选择与覆不对称金属箔的层压板及使用其制得的印刷线路板的操作温度有关。操作温度高于T g时，固化后的预浸料为橡胶态，覆不对称金属箔的层压板及使用其制得的印刷线路板受应力后的形变量大，影响其可靠性。覆不对称金属箔的层压板及使用其制得的印刷线路板的操作温度一般超过150℃，因此本发明中低模量预浸料固化后的T g为150℃以上，优选170℃以上，进一步优选200℃以上，更进一步优选230℃以上，最优选250℃以上，这样是为了提高固化后的预浸料在高温下的模量保持率。
第二方面，本发明提供一种印刷线路板，所述印刷线路板包括至少一张第一方面所述的覆不对称金属箔的层压板。
与现有技术相比，本发明具有以下有益效果：
本发明通过调节预浸料固化后的弹性模量并将其控制在22GPa以下，从而使得到的覆不对称金属箔的层压板具有较低的翘曲量，保证了由其制备的印刷线路板的可靠性。
具体实施方式
下面通过具体实施例来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
本发明实施例中采用的预浸料的规格如下：
预浸料A：固化后弹性模量为17GPa，XY-CTE为13ppm/℃，T g为270℃；
预浸料B：固化后弹性模量为21GPa，XY-CTE为10ppm/℃，T g为270℃；
预浸料C：固化后弹性模量为10GPa，XY-CTE为10ppm/℃，T g为170℃；
预浸料D：固化后弹性模量为18GPa，XY-CTE为20ppm/℃，T g为150℃；
预浸料E：固化后弹性模量为17GPa，XY-CTE为20ppm/℃，T g为270℃；
预浸料F：固化后弹性模量为28GPa，XY-CTE为10ppm/℃，T g为270℃；
预浸料G：固化后弹性模量为23GPa，XY-CTE为15ppm/℃，T g为270℃；
预浸料H：固化后弹性模量为28GPa，XY-CTE为20ppm/℃，T g为270℃；
预浸料I：固化后弹性模量为17GPa，XY-CTE为15ppm/℃，T g为270℃。
本发明对预浸料厚度和玻璃纤维布的厚度不做限制，为了便于比较，统一选取以上单张预浸料的厚度均为125μm。
固化后预浸料的性能测试方法如下：
样品制备：将12μm的铜箔分别覆于8张层叠的预浸料两侧和1张预浸料两侧，然后置于热压机中固化，在温度为200℃，压力为30kg/cm 2的条件下固化90min，使预浸料完全固化，把铜箔蚀刻后可以得到厚度分别为1.0mm和0.125mm的层压板。
铜箔厚度测试方法：参照GB/T 29847-2013印制板用铜箔试验方法6.3。
弹性模量测试方法：取长为76.2mm、宽为25.4mm、厚为1.0mm的层压板作为样品，采用材料试验机进行测量，跨距为25.4mm，试验速度0.76mm/min，最大弯曲强度按公式可换算得到弯曲模量，即为弹性模量，单位为GPa。
XY-CTE测试方法：取长为60mm、宽为4mm、厚为0.125mm的层压板作为样品，玻纤纬纱方向为X向，玻纤经纱方向为Y向，样品在105℃烘箱中烘1小时后在干燥器中冷却至室温。使用热分析机械法(TMA)进行测量，升温速率10℃/min，从室温升温至260℃，进行两次升温，第一次升温结束冷却至室温后重新放样进行第二次升温，结果取第二次升温50℃到130℃下的平面方向热膨胀系数，单位为ppm/℃。
玻璃化转变温度(T g)测试方法：取长为60mm、宽为10mm、厚为1.0mm的层压板作为样品，使用动态机械热分析仪(DMA)进行测量，升温速率10℃/min，结果取tanδ的转变峰温度，单位为℃。
本发明实施例中采用的铜箔的规格如下：
铜箔A：厚度12μm；
铜箔B：厚度35μm；
铜箔C：厚度105μm；
铜箔D：厚度210μm；
实施例1-11和对比例1-4
实施例1-11和对比例1-4分别提供一种覆不对称金属箔的层压板，由所述低模量预浸料，和覆于所述低模量预浸料一侧的金属箔或两侧的厚度不同的金属箔构成。其制备方法如下：
将两张厚度不同的铜箔分别覆于所述预浸料两侧，或一张铜箔覆于所述预 浸料一侧，然后置于热压机中，在温度为200℃，压力为30kg/cm 2的条件下固化90min，使预浸料完全固化，得到覆不对称金属箔的层压板；
其中预浸料和铜箔的种类如下表1和表2所示。
对上述实施例1-11和对比例1-4提供的覆不对称金属箔层压板的翘曲性进行测试：
覆不对称金属箔层压板的翘曲类型分为弓曲和扭曲，其定义和测试方法参照IPC-TM-650标准。
弓曲的定义为：板材类似于柱形或曲球形的一种变形，对于形状为矩形的覆铜箔板材，它的四个角位于同一平面。
弓曲测试方法为：样品凸面向上置于测试平台上，测量样品与平台最大垂直距离。
扭曲的定义为：矩形的板材在平行于对角线方向的一种变形，其中一个角不包含在另外三个角的平面上。
扭曲测试方法为：样品置于测试平台上，使任意三个角接触到平台，测量不接触平台的角与平台最大垂直距离。
A态翘曲量是指未经过处理，直接测试样品，得到的弓曲或扭曲的最大值即为A态翘曲量。
回流焊处理后的翘曲量是指经过回流焊处理后，回流焊参数设置为：从30℃升温至260℃，再从260℃降温至30℃，速率为3℃/min，测试样品，得到的弓曲或扭曲的最大值即为回流焊处理后的翘曲量。
覆不对称金属箔层压板样品的尺寸为250mm(经向)×300mm(纬向)。
上述测试的结果如下表1、表2和表3所示：
表1
Figure PCTCN2021070942-appb-000001
表2
Figure PCTCN2021070942-appb-000002
表3
  对比例1 对比例2 对比例3 对比例4
预浸料 1×预浸料F 1×预浸料G 1×预浸料F 1×预浸料H
上层铜箔 铜箔A 铜箔A 铜箔B 铜箔A
下层铜箔 铜箔D 铜箔D 铜箔D 铜箔D
A态翘曲量/mm 10 6 7 15
回流焊处理后翘曲量/mm 15 12 13 20
由表1和表2的测试结果可以看出，采用固化后弹性模量在22GPa以下的低模量预浸料的覆不对称金属箔的层压板具有较低的翘曲量，A态翘曲量和回 流焊处理后的翘曲量均在5mm以下。
从表3的测试数据可知，当预浸料固化后的模量过高时(对比例1-4)，覆不对称金属箔层压板在A态及回流焊处理后的翘曲量均明显增大，超过5mm，其中，回流焊处理后的翘曲量远超过A态翘曲量。
比较实施例1和实施例5、对比例1和对比例4可以看出，预浸料模量和T g相近时，XY-CTE越小，抵抗形变的能力越大，因此对减低翘曲量有帮助，尤其是降低回流焊处理后的翘曲量有帮助，但预浸料弹性模量降低对降低翘曲量有更明显的影响。
申请人声明，以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种覆不对称金属箔的层压板，其特征在于，所述覆不对称金属箔的层压板包括一张或至少两张层叠的低模量预浸料，和覆于所述一张或至少两张层叠的低模量预浸料一侧的金属箔或两侧的厚度不同的金属箔；
    所述低模量预浸料固化后的弹性模量为22GPa以下。
  2. 根据权利要求1所述的覆不对称金属箔的层压板，其特征在于，所述低模量预浸料固化后的弹性模量为20GPa以下，优选为18GPa以下。
  3. 根据权利要求1或2所述的覆不对称金属箔的层压板，其特征在于，所述低模量预浸料固化后的弹性模量为5GPa以上。
  4. 根据权利要求1-3任一项所述的覆不对称金属箔的层压板，其特征在于，所述低模量预浸料固化后的XY-CTE为18ppm/℃以下，优选为16ppm/℃以下，进一步优选为14ppm/℃以下。
  5. 根据权利要求1-4任一项所述的覆不对称金属箔的层压板，其特征在于，所述一张或至少两张层叠的低模量预浸料两侧均覆有金属箔，所述一张或至少两张层叠的低模量预浸料两侧的金属箔的厚度差≥35μm。
  6. 根据权利要求1-5任一项所述的覆不对称金属箔的层压板，其特征在于，所述一张或至少两张层叠的低模量预浸料两侧均覆有金属箔，所述一张或至少两张层叠的低模量预浸料一侧的金属箔厚度为≤35μm，另一侧的金属箔厚度为≥70μm。
  7. 根据权利要求1-6任一项所述的覆不对称金属箔的层压板，其特征在于，所述覆于低模量预浸料一侧的金属箔厚度为≤35μm，另一侧的金属箔厚度为70-420μm，优选为140-420μm。
  8. 根据权利要求1-7任一项所述的覆不对称金属箔的层压板，其特征在于，所述一张或至少两张层叠的低模量预浸料一侧覆有金属箔，所述金属箔的厚度 为1.5-700μm。
  9. 根据权利要求1-8任一项所述的覆不对称金属箔的层压板，其特征在于，所述低模量预浸料固化后的T g为150℃以上，优选170℃以上，进一步优选200℃以上，更进一步优选230℃以上，最优选250℃以上。
  10. 一种印刷线路板，其特征在于，所述印刷线路板包括至少一张如权利要求1-9任一项所述的覆不对称金属箔的层压板。
PCT/CN2021/070942 2020-12-29 2021-01-08 一种覆不对称金属箔的层压板和包含其的印刷线路板 WO2022141662A1 (zh)

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