WO2014010968A1 - 연성 금속 적층체 - Google Patents
연성 금속 적층체 Download PDFInfo
- Publication number
- WO2014010968A1 WO2014010968A1 PCT/KR2013/006214 KR2013006214W WO2014010968A1 WO 2014010968 A1 WO2014010968 A1 WO 2014010968A1 KR 2013006214 W KR2013006214 W KR 2013006214W WO 2014010968 A1 WO2014010968 A1 WO 2014010968A1
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- WIPO (PCT)
- Prior art keywords
- formula
- resin layer
- polymer resin
- flexible metal
- fluorine
- Prior art date
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Classifications
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
-
- 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
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
Definitions
- the present invention relates to a flexible metal laminate, and more particularly, to a flexible metal laminate having a low dielectric constant and a low water absorption rate and having a high elasticity and an optimized coefficient of thermal expansion.
- IXP Liquid Crystalline Polymer
- 7026032 discloses a method of lowering the dielectric constant of a product produced by dispersing a fine powder of a fluorine-based polymer in a polyimide.
- the U.S. Patent discloses that the bloso-based polymer fine powder is more distributed on the outer surface than the inner core of the insulator.
- the content of the fluorine-based polymer in the outermost layer of the insulator has a high water permeation and absorption is lowered by the fluorine-based polymer on the outer surface, but the overall water absorption rate can be lowered, the ductility of the existing polyimide Problems that copper foil laminates do not have may occur.
- the polyimide resin described in the US patent may have a weak adhesion to the coverlay or prepreg and a low ACF, and the coefficient of thermal expansion (CTE) of the polyimide resin described in the US patent may be soft.
- the surface of the polyimide resin has an excessive amount of fluorine resin on the outside, so that the fluorine resin may be melted at a temperature of about 380 ° C that is applied to the storage process during the PCB manufacturing process. There is a risk of the copper foil circuit peeling off the insulator. Accordingly, in order to make low dielectric constant printed circuit boards, polyimide including fluorine resin has low dielectric constant and low coefficient of thermal expansion, and it is necessary to develop polyimide material having high elastic modulus and low moisture absorption. to be.
- Patent Document 1 (Preceding Document 001) US Patent No. 4816516
- Patent Document 2 (Prior Document 002) United States Patent No. 7026032
- the present invention is to provide a flexible metal laminate having a low dielectric constant and a low water absorption, while ensuring an optimized coefficient of thermal expansion with high elasticity. [Measures of problem]
- the present invention includes a polymer resin layer including a polyimide resin and a fluorine-based resin including a repeating unit represented by Formula 1 below, and the fluorine-based resin is distributed more in the polymer resin layer than in the surface of the polymer resin layer. It provides a flexible metal laminate.
- ⁇ is a tetravalent aromatic organic functional group
- X is a divalent aromatic organic functional group
- n is an integer of 1 to 300.
- a polyimide resin comprising a repeating unit of Formula 1 and a polymer resin layer comprising a fluorine-based resin, wherein the fluorine-based resin than the surface of the polymer resin layer inside the polymer resin layer More ductile metal laminates can be provided.
- a method of adding a fluorine-based polymer resin in order to lower the dielectric constant of a polymer resin such as plyimide applied to a flexible metal laminate is known, but polytetrafluoroethylene (PTFE) and tetrafluoroethylene-nucleus, which are representative fluorine-based resins, are known.
- PTFE polytetrafluoroethylene
- FEP fluoropropylene copolymer
- PFA perfluoroalkoxy
- the present inventors conducted a related research, wherein the flexible metal laminate of the embodiment includes a polymer resin layer containing a polyimide resin and a fluorine resin having the specific chemical structure, and the fluorine resin is outside the polymer resin layer.
- the flexible metal laminate of the embodiment includes a polymer resin layer containing a polyimide resin and a fluorine resin having the specific chemical structure, and the fluorine resin is outside the polymer resin layer.
- the fluorine resin may be more dispersed in the polymer resin layer than the outer surface of the polymer resin layer, and the content of the fluorine resin may be It may become larger toward the inside of the polymer resin layer.
- the flexible metal laminated in the body up to 20% of the thickness from the surface of the polymer resin, the amount of the fluorine-based resin per unit volume of the polymer resin can be "increases with depth.
- the content of the fluorine resin per unit volume of the polymer resin layer may be minimum on the surface of the polymer resin layer.
- the content of the fluorine resin contained in a unit volume (for example, a cube having a depth at one corner) from a surface of the polymer resin layer to a depth of 1% of the total thickness is 1 of the total thickness. It may be smaller than the amount of fluorine resin per unit volume in the interior deeper than% depth.
- the content of the fluorine-based resin per unit volume on the surface of the polymer resin layer is minimal, and the content of the fluorine-based resin per unit volume may be increased up to 20% of the total thickness from the surface of the polymer resin layer.
- the fluorine resin content may increase from the surface of the polymer resin layer to 20% of the total thickness, and the fluorine resin content may increase toward the inside from 20% to 50> of the total thickness from the polymer layer resin surface. It may be maintained at the same level as the content of the fluorine resin at a depth point of 20% of the total thickness.
- the total content of the fluorine-based resin in the polymer resin layer As the thickness increases to 20%, the weight ratio of the polyimide resin and the fluorine resin per unit volume of the polymer resin layer may vary depending on the depth.
- the weight ratio of the polyimide resin: fluorine-based resin per unit volume of the polymer resin layer may be 100: 0 to 60:40.
- the weight ratio of the plyimide resin: the fluorine-based resin per unit volume of the polymer resin layer may be 80:20 to 30:70.
- the fluorine-based resin is more distributed in the polymer resin than the outer surface of the polymer resin layer, or the content of the fluorine-based resin is increased toward the inside of the polymer resin, or the content of the fluorine-based resin per unit volume of the polymer resin.
- the effect of the fluorine-based resin contained in the polymer resin layer for example, the effect of significantly lowering the dielectric constant and moisture absorption rate can be expressed fully, while the fluorine-based resin Due to this, it is possible to minimize the phenomenon that the thermal expansion coefficient of the polymer resin layer is increased or the elasticity is lowered.
- the polymer resin layer may be more firmly bonded to the metal thin film included in the flexible metal laminate, and may be further bonded to at least one surface of the polymer resin layer.
- the difference in the coefficient of thermal expansion of the polymer resin layer (for example, the second or crab polyimide layer) can be greatly reduced.
- the fluorine-based resin is more distributed in the polymer resin layer than the surface of the polymer resin layer, the high temperature that can be applied in the manufacturing process of the flexible metal laminate or printed circuit board, for example, application
- the phenomenon that the fluorine resin melts or the copper foil circuit peels from the insulator can be prevented at a temperature of about 380 ° C.
- the characteristics of the flexible metal laminate of one embodiment described above In addition to the distribution properties of the fluorine-based resin in the polymer layer seems to be due to using a polyimide resin having a specific chemical structure.
- the polyimide resin including the repeating unit of Formula 1 may include a tetravalent functional group selected from the group consisting of the following Formulas 21 to 27.
- ⁇ is a single bond, -0-, -CO-, -S-, -S0 2- , -C (C3 ⁇ 4) 2- , -C (CF 3 ) 2- , -C0NH-, -C00 -, - (CH 2) n ⁇ , - 0 (CH 2) n2 0-, or - 0C0 (C3 ⁇ 4) 0C0- and n3, wherein nl, n2 and n3 is an integer of 1 to 10, respectively.
- ⁇ 2 and ⁇ 3 may be the same as or different from each other, a single bond, ⁇ 0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH ⁇ , -C00-,-
- nl, n2 and ⁇ 3 are each an integer from 1 to 10.
- Y 4 , ⁇ 5 and ⁇ 6 may be the same as or different from each other, each of a single bond, -0-, -CO-, -S-, -S0 2- , — C (C3 ⁇ 4) 2- , -C (CF 3) 2 -, -C0NH-, - C00-, - (CH 2) nl -, -0 (CH 2) n2 is 0-, or -0C0 (CH 2) n3 0C0-, wherein nl, n2 and n3 are the integers of 1-10, respectively.
- Chemical Formulas 21 to 27 means a bonding point (bonding point).
- tetravalent selected from the group consisting of the following Chemical Formulas 28 to 30 It is preferably a functional group. ⁇ May be the same as or different from each repeating unit of Formula 1.
- X may be a divalent functional group selected from the group consisting of Chemical Formulas 31 to 34.
- 3 ⁇ 4 is hydrogen, -CH 3 , -C3 ⁇ 4CH 3 , -CH 2 CH 2 CH 2 CH 3 , -CF 3 ,-CF 2 CF 3) -CF2CF2CF3, or -CF 2 CF 2 CF 2 CF 3 Can be.
- Chemical Formula 32 is a single bond, -0-, -C0-, —S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2 —, -C0NH-, -C00 -, - (CH 2) nl -, -0 (C3 ⁇ 4) n2 0-, -0CH 2 -C (CH 3) 2 - CH2O- or
- nl, n2 and n3 is an integer of 1 to 10, respectively, 3 ⁇ 4 and 3 ⁇ 4 may be the same or different from each other, and hydrogen, -CH 3 , -CH 2 C3 ⁇ 4, -CH 2 CH 2 C3 ⁇ 4CH 3 , -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , or -CF 2 CF 2 CF 2 CF 3 .
- L 2 and L 3 may be the same as or different from each other, and each single bond, -0—, -CO—, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH-, -C00-,-(CH 2 ) n ⁇ , -0 (C3 ⁇ 4) n2 0—, -0CH 2 -C (CH 3 ) 2 -CH 2 0- or -0C0 (CH 2 ) n3 0C ()-, nl, n2 and n3 are each an integer of 1 to 10, R 2 and 3 ⁇ 4 may be the same or different from each other, hydrogen,-(3 ⁇ 4, -CH 2 CH 3 ) -CH 2 CH 2 CH 2 CH 3> _CF 3 , -CF 2 CF 3> -CF 2 CF 2 CF 3 , or -CF 2 CF 2 CF 2 CF 3 .
- L 4 , L 5, and L 6 may be the same as or different from each other, and each single bond, -0-, -CO-, -S-, -S0 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -C0NH ⁇ , -C00-,-(CH 2 ) n ⁇ , -0 (CH 2 ) n2 0—, -0CH 2 -C (CH 3 ) 2 -CH 2 0 Or -0C0 (C3 ⁇ 4) n3 0C0-, nl, n2 and n3 are each an integer of 1 to 10, 3 ⁇ 4 and R4 may be the same or different from each other, hydrogen, -CH 3 , -CH 2 CH 3 ,- It may be CF 2 CF 3, -CF 2 CF 2 CF 3, or -CF 2 CF 2 CF 2 CF 3 - CH 2 CH 2 CH 3, -CF 3,.
- the flexible metal laminate of the embodiment may have a lower dielectric constant and a lower water absorption rate, and may also secure an optimized coefficient of thermal expansion with high elasticity.
- X may be the same as or different from each repeating unit of Formula 1.
- R 2 may be the same as or different from each other, and-CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 ( -CF 3) — CF 2 CF 3 , -CF 2 CF 2 CF 3) or —CF 2 CF 2 CF 2 CF 3 .
- the polymer resin layer may include a polyimide resin 20 to 95 weight 3 ⁇ 4> or 40 to 90 weight and the remaining amount of the fluorine-based resin comprising a repeating unit of the formula (1). If the content of the fluorine-based resin is too small, the resulting soft metal laminate may not be able to secure a sufficiently low dielectric constant or moisture absorption rate. In addition, if the content of the fluorine-based resin is too large, the mechanical properties of the flexible metal laminate is lowered and easily torn or broken The thermal expansion coefficient of the polymer resin layer included in the flexible metal laminate may be greatly increased.
- the fluororesin is polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), tetrafluoroethylene-nuclear fluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer It includes a fluoropolymer containing at least one selected from the group consisting of a polymer resin (ETFE), tetrafluoroethylene- chlorotrifluoroethylene copolymer (TFE / CTFE) and ethylene- chlorotrifluoroethylene resin (ECTFE) can do.
- PTFE polytetrafluoroethylene
- PFA tetrafluoroethylene-perfluoroalkylvinylether copolymer
- FEP tetrafluoroethylene-nuclear fluoropropylene copolymer
- ETFE polymer resin
- TFE / CTFE tetrafluor
- the fluorine-based resin may include particles having a longest diameter of 0.05 Urn to 20, or 0.1 to 10 to 10. If the longest diameter of the fluorine-based resin is too small, the surface area of the fluorine-based resin may increase to decrease the physical properties of the polymer resin layer or increase the amount of the dispersant to be described later. In addition, when the longest diameter of the fluorine-based resin is too large, the surface properties of the polymer resin layer to be produced may be lowered or the dispersibility of the polymer composition solution for producing the polymer resin layer may be lowered.
- the flexible metal laminate of the embodiment may further include a dispersant dispersed in the polymer resin layer.
- the polymer resin layer may be formed from a resin composition comprising a polyamic acid, a fluorine resin, and a predetermined dispersant, and as the dispersant is used, the fluorine resin is more distributed in the polymer resin than the outer surface of the polymer resin layer.
- the content of the fluorine resin may be increased toward the inside of the polymer resin layer, or the content of the fluorine resin per unit volume of the polymer resin layer may be minimum on the surface of the polymer layer resin.
- the dispersant include polyester-based polymers, polyether-modified polydimethylsiloxanes, polyester / polyamine condensation polymers or two or more kinds thereof.
- the 'according to the use of such compounds, may be a fluorine-based resin is the above-described distribution pattern in the number of the polymer resin contained in the flexible laminated body, whereby the depending Flexible metal laminates or printed circuit boards may have an optimized coefficient of thermal expansion with high elasticity while having low dielectric constant and low moisture absorption.
- a method of using a fluorine-based dispersant or a fluorine-based surfactant in order to disperse the fluorine-based resin in polyamic acid or polyimide is known, but according to the conventional method, the dielectric constant of the polymer resin layer manufactured may be somewhat lowered. The coefficient of thermal expansion of the polymer resin layer prepared according to the use of the agent or the fluorine-based surfactant may be greatly increased.
- the fluorine-based dispersant or the fluorine-based surfactant when used, a phenomenon in which the fluorine-based resin is concentrated on the surface of the polymer resin layer, such as a polyimide resin, to be produced, may occur. Exposure to high temperatures that may be applied in the manufacture of sieves or printed circuit boards, for example around 380 o C, may cause the fluorine resin to melt or to exfoliate portions of the flexible metal laminate or printed circuit board. have.
- a method of adding a fluorine-based polymer resin in order to lower the dielectric constant of a polymer resin such as polyimide applied to a flexible metal laminate is known.
- polytetrafluoroethylene (PTFE) and tetrafluoroethylene-nucleofluoride which are representative fluorine resins
- the thermal expansion coefficients of propylene copolymer (FEP) and perfluoroalkoxy (PFA) are 135ppm, 150ppm and 230ppm, respectively, which are considerably larger than those of 10 to 30ppm, which is the coefficient of thermal expansion of conventional polyimides.
- FEP propylene copolymer
- PFA perfluoroalkoxy
- the overall coefficient of thermal expansion is bound to increase.
- the dispersant is 0.92 g / ml to 1.2 g / ml, or 0.95 g / ml at 20 o C
- the dispersant may have an acid value (Ac id value) of 20 to 30 mg KOH / g.
- the dispersant has a base equivalent of 1000 to 1700 Can have.
- the polymer resin layer may include 0.1 parts by weight to 25 parts by weight or 0.5 parts by weight to 10 parts by weight of the dispersant relative to 100 parts by weight of the fluorine resin.
- the fluorine-based resin agglomeration may occur to reduce the appearance characteristics or uniformity of the polymer resin layer, uniformity of the polymer resin composition solution for the production of the polymer resin layer Can be lowered.
- the content of the dispersant is too large, the elasticity or mechanical properties of the polymer resin layer may be lowered.
- the polymer resin layer included in the flexible metal laminate may have a thickness of 0.1zm to 100 / ⁇ , or 1 / ⁇ to 50.
- the flexible metal laminate may exhibit a dielectric constant (Dk) of 2.2 to 2.8, or 2.3 to 2.7 in a dry state at 5 GHz.
- Dk dielectric constant
- the polyimide resin has a dielectric constant of 3.0 or more in a dry state at 5 GHz
- the flexible laminated metal laminate of the embodiment may have a relatively low dielectric constant as described above with the polymer resin layer.
- the flexible laminated body may have a coefficient of thermal expansion of lppm to 28ppm at 100 ° C to 200 o C.
- the polymer resin layer described above may have a relatively low coefficient of thermal expansion, for example, lppm to 20 ppm, and a flexible metal including the polymer resin layer or an additional polyimide layer on at least one surface of the polymer resin layer.
- the laminate may also have a coefficient of thermal expansion of lppm to 28 ppm, or 15 ppm to 25 ppm.
- the thermal expansion coefficient of copper foil which is a commonly used metal foil
- the thermal expansion coefficient of the flexible metal laminate should be within the above-described range, so that warpage phenomenon resulting from the difference in thermal expansion coefficient with the metal foil can be minimized. Minimize the difference in expansion and contraction with other materials forming the printed circuit board.
- the flexible metal laminate is copper, iron, nickel, titanium, aluminum, At least one metal thin film including at least one selected from the group consisting of silver, gold and two or more alloys thereof may be included.
- the flexible metal laminate may include one metal thin film, and the flexible metal laminate may include two metal thin films that face each other, and in this case, the polymer resin layer may face each other. It may be located between two metal thin film.
- Ten-point average roughness (R Z ) of the surface of the metal thin film may be 0. 3 to 2.5 ⁇ . If the ten point average roughness of the metal thin film surface is too small, the adhesive strength with the polymer resin layer may be low, and if the ten point average roughness of the metal thin film surface is too large, the surface roughness may increase to increase the transmission loss in the high frequency region.
- the metal thin film may have a thickness of 0.1 to.
- the flexible metal laminate described above may further include a polyimide resin layer formed on at least one surface of the polymer resin layer.
- the flexible metal laminate may further include second and third polyimide resins bonded to both sides of the polymer resin layer.
- the second and third polyimide resins may each have the same or different composition as the above-described polyimide resin.
- the second and third polyimide resin may have the same or different thickness as the polymer resin layer, and may have a thickness in the range of 0.1 to 100 / ⁇ , or to 50 / ⁇ .
- the manufacturing method of the above-mentioned flexible metal laminated body is not restrict
- the polyimide resin included in the polymer resin layer may be obtained by heat treatment at a high temperature of 250 ° C. to 400 ° C. after coating and drying a polymer resin solution including a polyamic acid as a precursor.
- the polyamic acid as a precursor of the polyimide resin reacts with tetracarboxylic acid or its anhydride and diamine compound.
- a diamine comprising a tetracarboxylic acid or an anhydride thereof including a tetravalent functional group selected from the group consisting of Formula 21 to Formula 27 and a divalent functional group selected from the group consisting of Formulas 31 to 34, for example.
- the resin composition including a polyamic acid, a fluorine resin, and a dispersant, which is a precursor of the polyimide may include an organic solvent, and examples of the organic solvent that can be used are not particularly limited.
- the organic solvent that can be used are not particularly limited.
- N, N′-dimethylformamide, N, N'-dimethylacetamide, N, N'-diethylacetamide, N, N'-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, 1, 3- Dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxydi, dimethulfone, m-cresol, P- Chlorophenol, anisol, etc. may be used, and may be used alone or in combination of two or more.
- the usable amount of the organic solvent may
- a flexible metal laminate having a low dielectric constant and a low water absorption rate, while ensuring an optimized coefficient of thermal expansion with high elasticity.
- the present invention is a solution to the increase in the data loss rate, the thickening of the printed circuit board, the narrowing of the circuit on the printed circuit board caused by the recent increase in data transmission speed of devices such as laptops, computers, mobile phones
- a method capable of producing a low dielectric constant polyimide having a low dielectric constant and having characteristics such as high heat resistance chemical resistance and dimensional stability of an existing polyimide insulator.
- the present invention provides a method capable of producing a low dielectric constant copper foil laminate using a low dielectric constant polyimide prepared according to the above method.
- the printed circuit board can be made thinner while matching impedance, thereby making the portable electronic device thinner, and the line width of the printed circuit board can be widened, thereby significantly reducing the defect rate of the PCB manufacturing company. It can greatly contribute to cost reduction.
- Figure 1 shows a cross-sectional SEM photograph and EDS results of the copper foil laminate obtained in Example 8.
- FIG. 2 is an enlarged cross-sectional SEM photograph of the laminate of FIG. 1.
- Nitrogen was charged in a 1 L PE bottle, 765 g of dimethylacetamide (DMAc), 219 g polytetra pulluloethylene micro powder (PTFE micro powder, particle size: 0.1 to 2.0 um), and poly with dispersant. 10.95 g of ester polymer [acid value 26 mg KOH / g, base value 1200] and 765 g of beads having a diameter of 2 mm were added thereto, and PTFE was dispersed while stirring in a high speed ball milling machine. .
- DMAc dimethylacetamide
- PTFE micro powder polytetra pulluloethylene micro powder
- the PTFE was dispersed in a 500 mL back bottom flask. 73 g of solution 73 g dimethylacetamide, 11.609 g pyromellitic dianhydride, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl 17.391g, at 50 ° C
- 1 L of PE bottle was filled with nitrogen, 765 g of dimethylacetamide (DMAc), 219 g of polytetrafluoroethylene micro powder (particle size: 0.1 to 2.0 um), polyester with dispersant 10.95 g of a system polymer (density (20): 1.13 g / ml) and 765 g of beads having a diameter of 2 mm were added thereto, and PTFE was dispersed while stirring in a high speed ball milling machine.
- DMAc dimethylacetamide
- polytetrafluoroethylene micro powder particle size: 0.1 to 2.0 um
- polyester with dispersant 10.95 g of a system polymer (density (20): 1.13 g / ml) and 765 g of beads having a diameter of 2 mm were added thereto, and PTFE was dispersed while stirring in a high speed ball milling machine.
- DMAc dimethylacetamide
- PMDA pyromellitic di anhydride
- BPDA pyromellitic di anhydride
- DMAc dimethylacetamide
- PMDA pyromellitic di anhydride
- 1 L of PE bottle was filled with nitrogen, 765 g of dimethylacetamide (DMAc), 219 g of polytetrafluoroethylene micro powder (PTFE micro powder, particle size: 0.1 to 2.0 um), polyester with dispersant Type Polymer [acid value 26 mg K0H / g, base value 10.95 g and 765 g of beads having a diameter of 2 mm were added, and PTFE was dispersed while stirring in a high speed ball milling machine.
- DMAc dimethylacetamide
- PTFE micro powder polytetrafluoroethylene micro powder
- polyester with dispersant Type Polymer [acid value 26 mg K0H / g, base value 10.95 g and 765 g of beads having a diameter of 2 mm were added, and PTFE was dispersed while stirring in a high speed ball milling machine.
- the polyamic acid solutions prepared in Preparation Examples 1 to 3 were coated on a Matte surface of copper foil (thickness: 12) so that the final thickness was 25 ⁇ m, and then dried at 80 ° C. for 10 minutes. The dried product was started at room temperature in a nitrogen oven to proceed with curing at 350 ° C. for 30 minutes. After the curing was completed, the copper foil was etched to prepare a polyimide film having a thickness of 25 ⁇ m.
- a film was prepared.
- the polyamic acid solution (P5) prepared in Preparation Example 5 was coated on a Matte surface of a copper foil (thickness: i / m) so that the final thickness is 2um and dried at 80 ° C for 10 minutes.
- the polyamic acid solution (P1) prepared in Preparation Example 1 thereon was coated to a final thickness of 20um and then dried at 80 ° C for 10 minutes.
- the polyamic acid solution (P1) on the surface of the dried product, the polyamic acid solution (P5) prepared in Preparation Example 5 was coated to a final thickness of 3um and then dried at 80 ° C. for 10 minutes to prepare a laminate. .
- the dried laminate was heated at room temperature in a nitrogen oven, and cured at 350 ° C. for 30 minutes to produce a flexible copper foil laminate having one surface of the copper foil. Examples 6-7
- Example 8 The surface was the same as in Example 5 except for using the polyamic acid solutions (P2 and P3) prepared in Preparation Example 2 and Preparation Example 3 instead of the polyamic acid solution (P1) prepared in Preparation Example 1.
- the flexible copper foil laminated board which one side is made of copper foil was manufactured.
- the polyamic acid solution (P5) prepared in Preparation Example 5 was coated on a Matte surface of copper foil (thickness: 12zm) so that the final thickness is 2um, and dried at 80 ° C for 10 minutes.
- the polyamic acid solution (P1) prepared in Preparation Example 1 was coated thereon to have a final thickness of 20 ⁇ m, and then dried at 80 ° C. for 10 minutes.
- the polyamic acid solution (P5) was coated to a final thickness of 3 ⁇ m and then at 80 o C
- the copper foil (thickness: 1 ⁇ ) on the other side of the cured product so as to face the copper foil at a temperature of 400 ° C. It bonded by and manufactured the flexible copper foil laminated board which copper foil was bonded to both surfaces. Examples 9-10
- the cross section of the copper foil crushing plate obtained in the said Example 8 was confirmed through the SEM photograph.
- the polyimide film laminate obtained by etching the copper foil in the polyimide film obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the flexible copper foil laminate obtained in Examples 4 to 11 was dried at 150 ° C. for 30 minutes, and The dielectric constant of the polyimide film or the polyimide film laminate was measured using a split post dielectric resonance (SPDR) method at 25 ° C. and 50% RH.
- SPDR split post dielectric resonance
- the measurement was performed using a Resonator using an E5071B ENA apparatus.
- the linear thermal expansion coefficients of the polyimide films obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the linear thermal expansion coefficients of the polyimide film laminates obtained by etching copper foil from the flexible copper foil laminates obtained in Examples 4 to 11 were obtained from IPC TM-.
- the absorption rate of the polyimide film obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the absorption rate of the polyimide film laminate obtained by etching copper foil from the flexible copper foil laminates obtained in Examples 4 to 11 were IPC TM-650 2.6.2C It was immersed in distilled water of 23 0 C for 24 hours based on the criterion of, and the water absorption was calculated by measuring the mass of the measurement object before and after the deposition.
- the composition of the polyamic acid of Examples 5 to 11 relates to the precursor of the polyimide film located in the middle layer of the polyimide films of the flexible copper foil laminate.
- the polyimide film obtained in Examples 1 to 3 has a low dielectric constant and low water absorption, but also in a suitable range (for example, lppm to 20 ppm) as compared to the polyimide films of Comparative Examples 1 to 3. It was confirmed that it has a coefficient of thermal expansion of.
- the polyimide films of Comparative Examples 1 to 3 had relatively high dielectric constants (for example, 2.8 or more or 3.0 or more) and high absorption rates (for example, 1.5% or more).
- the dielectric constant of 2.80 or less and the absorption rate of 1.2 or less can be secured, while the thermal expansion coefficient of the laminated structure excluding copper foil can be adjusted in the range of 18 ppm to 28 ppm. Confirmed.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
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CN201380006267.5A CN104220251B (zh) | 2012-07-11 | 2013-07-11 | 柔性金属层压板 |
JP2015506920A JP5997830B2 (ja) | 2012-07-11 | 2013-07-11 | 軟性金属積層体 |
US14/357,855 US9307638B2 (en) | 2012-07-11 | 2013-07-11 | Flexible metal laminate |
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KR1020130081375A KR101344006B1 (ko) | 2012-07-11 | 2013-07-11 | 연성 금속 적층체 |
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Cited By (2)
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JP2016020488A (ja) * | 2014-06-17 | 2016-02-04 | 東邦化成株式会社 | フッ素樹脂含有水性ポリイミド前駆体組成物及びそれを用いた積層体とプリント配線基板、並びにその積層体の製造方法 |
WO2022050253A1 (ja) | 2020-09-03 | 2022-03-10 | Agc株式会社 | パウダー分散液および複合体の製造方法 |
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US5011727A (en) * | 1988-09-09 | 1991-04-30 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Polyimide resin laminate improved in slidability |
JP2003227467A (ja) * | 2002-01-31 | 2003-08-15 | Yodogawa Kasei Kk | フッ素系樹脂多層積層ポリイミドフィルムを用いた小型定量ポンプ用ダイヤフラム |
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US20050096429A1 (en) * | 2003-11-05 | 2005-05-05 | Yueh-Ling Lee | Polyimide based compositions useful as electronic substrates, derived in part from (micro-powder) fluoropolymer, and methods and compositions relating thereto |
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US5011727A (en) * | 1988-09-09 | 1991-04-30 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Polyimide resin laminate improved in slidability |
JP2003227467A (ja) * | 2002-01-31 | 2003-08-15 | Yodogawa Kasei Kk | フッ素系樹脂多層積層ポリイミドフィルムを用いた小型定量ポンプ用ダイヤフラム |
JP2004195776A (ja) * | 2002-12-18 | 2004-07-15 | Asahi Glass Co Ltd | ビルドアップ配線板用積層フィルム及びビルドアップ配線板 |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2016020488A (ja) * | 2014-06-17 | 2016-02-04 | 東邦化成株式会社 | フッ素樹脂含有水性ポリイミド前駆体組成物及びそれを用いた積層体とプリント配線基板、並びにその積層体の製造方法 |
WO2022050253A1 (ja) | 2020-09-03 | 2022-03-10 | Agc株式会社 | パウダー分散液および複合体の製造方法 |
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