CN102939671A - Heat dissipation substrate for led - Google Patents
Heat dissipation substrate for led Download PDFInfo
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- CN102939671A CN102939671A CN2011800268541A CN201180026854A CN102939671A CN 102939671 A CN102939671 A CN 102939671A CN 2011800268541 A CN2011800268541 A CN 2011800268541A CN 201180026854 A CN201180026854 A CN 201180026854A CN 102939671 A CN102939671 A CN 102939671A
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- Prior art keywords
- foil
- polyimide film
- polyimide
- heat
- hot press
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/089—Coatings, claddings or bonding layers made from metals or metal alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/64—Heat extraction or cooling elements
- H01L33/641—Heat extraction or cooling elements characterized by the materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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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
- H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
- H05K1/0203—Cooling of mounted components
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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
- H05K1/18—Printed circuits structurally associated with non-printed electric components
- H05K1/189—Printed circuits structurally associated with non-printed electric components characterised by the use of a flexible or folded printed circuit
-
- 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
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10007—Types of components
- H05K2201/10106—Light emitting diode [LED]
Abstract
A heat dissipation substrate for an LED has copper foil or copper alloy foil layered on one side of a polyimide film and also has aluminum foil or aluminum alloy foil layered on the other side thereof. The thermal resistance between the surface of the copper foil or the copper alloy foil and the surface of the aluminum foil or the aluminum alloy foil is 1.8 DEG C/W or less.
Description
Technical field
The present invention relates to a kind of LED heat-radiating substrate.More specifically, but the present invention relates to a kind of LED heat-radiating substrate of thin, flexible and three-dimensional process.
Background technology
In recent years, it is low in energy consumption because of it as the LED lighting device of light source to contain LED (light-emitting diode), and the life-span is long, and demand increases rapidly.Yet, when LED lights, can produce heat.When the heat that produces was heated to high temperature to LED, the luminous efficiency of LED may significantly reduce, and the life-span of LED may be affected.Particularly high power, high-brightness LED can produce a large amount of heats when it is lighted, thereby for fear of the rising of LED temperature, it is particularly important that the heat radiation of LED becomes.
Therefore, has the heat-radiating substrate of good heat dispersion as the substrate of LED installation.Heat-radiating substrate commonly used comprises the epoxy resin film as insulating barrier, is laminated to the Copper Foil of epoxy resin film one side, and the aluminium foil that is laminated to the epoxy resin film opposite side.Yet, aspect proof voltage, if epoxy resin film must be about 1mm by used thickness, at least about 100 μ m or larger epoxy resin film as insulating barrier.Simultaneously, because the epoxy resin film of this thickness has higher thermal resistance, in order to realize enough heat radiations, must in epoxy resin film, add a large amount of inorganic fillers with high heat conductance, such as aluminium oxide, to reduce thermal resistance.Yet, this LED heat-radiating substrate that contains a large amount of inorganic fillers, it is low to have low machinability, and in processing (machining) process, around this filler may be scattered in, may throw into question like this.In addition, this LED heat-radiating substrate can not be crooked, can not three-dimensional process (or manufacturing).When the LED heat-radiating substrate is three-dimensional when accessible, the design freedom of circuit increases.The LED heat-radiating substrate that therefore, need to have good bending property.
Patent document 1 discloses a kind of LED lighting device, comprising:
Substrate body, described substrate body is formed by the thermoplasticity heat-resistant film of the polyimides that comprises certain three dimensional form;
The LED of one or more surface installing types, described LED is installed in the appropriate location of substrate body; And
Conducting channel, described conducting channel are installed in surface or the back side of described substrate body, and LED is connected to external circuit and opens LED;
Wherein, metal heat dissipating layer is formed on the described substrate body and is relative with described conducting channel.
Patent document 2 discloses a kind of copper-clad thin plate that solves heat radiation, and this copper-clad thin plate has high heat conductance, comprising:
Multilayer polyimide film, wherein polyimide bottom layer (X) has lower thermal coefficient of expansion, two polyimide coatings (Y) comprise laminated together and integrated specific acid imide unit, and described polyimide coating (Y) is laminated to the both sides of described polyimide bottom layer (X);
Copper Foil, described copper foil layer are pressed on the side of described polyimide film; And
Sheet metal or ceramic thin plate with high heat conductance comprise that thickness is the aluminium sheet of 5 μ m to 2mm, and described aluminium sheet is laminated on the opposite side of described polyimide film.
In addition, patent document 3 discloses a kind of laminated sheet for LED installation and interconnection, comprises copper or aluminum metal layer on the substrate, polyimide layer or the adhesive linkage of contiguous described metal level, copper foil layer and liquid or film solder mask.
The reference document inventory
Patent document
Patent document 1:JP-A-2008-293692
Patent document 2:JP-A-2003-71982
Patent document 3:WO 2009/073670
Summary of the invention
The problem to be solved in the present invention
The object of the present invention is to provide a kind of LED heat-radiating substrate, this substrate is thin plate and has good heat dispersion and withstand voltage properties also have good bending property, therefore is three-dimensional machinable.
The means of dealing with problems
The present invention relates to following content:
(1) a kind of LED heat-radiating substrate comprises:
Polyimide film;
Copper Foil or copper alloy foil, it is laminated to a side of described polyimide film; And
Aluminium foil or alloy foil, it is laminated to the opposite side of described polyimide film;
Wherein, the thermal resistance between the surface of the surface of described Copper Foil or copper alloy foil and described aluminium foil or alloy foil is 1.8 ℃/W or less.
(2) according to (1) described LED heat-radiating substrate, wherein said aluminium foil or alloy foil do not pass through anodization (alumite (alumite treatment)).
(3) according to (1) or (2) described LED heat-radiating substrate, the thickness of wherein said polyimide film is 3 μ m to 25 μ m.
(4) according to (1) to (3) each described LED heat-radiating substrate, the surface that wherein is engaged to the described polyimide film of Copper Foil or copper alloy foil comprises the hot press polyimide layer with the surface that is engaged to the described polyimide film of aluminium foil or alloy foil.
(5) according to (4) described LED heat-radiating substrate, wherein said polyimide film comprises heat-proof polyimide layer and hot press polyimide layer, and wherein said hot press polyimide layer is laminated to the both sides of described heat-proof polyimide layer.
(6) according to (1) to (5) each described LED heat-radiating substrate, the thickness of wherein said Copper Foil or copper alloy foil is 9 μ m to 200 μ m, and the thickness of described aluminium foil or alloy foil is 200 μ m to 1mm.
(7) according to (1) to (6) each described LED heat-radiating substrate, wherein said polyimide film, described Copper Foil or copper alloy foil, described aluminium foil or alloy foil use heat pressing forming machines to be bonded together.
Herein, the thermal resistance between the surface of the surface of Copper Foil or copper alloy foil and aluminium foil or alloy foil (being also referred to as " thermal resistance between Copper Foil and the aluminium foil ") is generally equal to the thermal resistance of described polyimide film.
The invention effect
LED heat-radiating substrate of the present invention comprises Copper Foil or copper alloy foil, and aluminium foil or alloy foil, and they are laminated to respectively a side and the opposite side of polyimide film; Thermal resistance between the surface of the surface of described Copper Foil or copper alloy foil and described aluminium foil or alloy foil is 1.8 ℃/W or less.Still do not have such LED heat-radiating substrate: it is thin, have good bending property, have excellent heat dispersion and withstand voltage.
Polyimide film has excellent insulation property, and therefore thinner polyimide film provides enough resistance to pressures.Because polyimide film can be very thin, LED heat-radiating substrate of the present invention has the gross thickness of reduction, low thermal resistance and excellent heat dispersion also have excellent mechanical machinability (machining property) and good bending property, and therefore are three-dimensional machinable.LED heat-radiating substrate of the present invention can " reel-to-reel " method (roll-to-roll process) be produced, and the method is fit to produce in enormous quantities.
Aluminium foil or alloy foil pass through anodization (alumite) usually, in order to improve tack.Yet, having from the teeth outwards the thick oxide-film that thickness is about 4 μ m through anodized aluminium foil or alloy foil, this oxide-film is harder.Therefore, comprise that the aluminium foil of this type or the LED heat-radiating substrate of alloy foil can have the bending property of reduction.According to the present invention, can preferably use and not pass through anodized aluminium foil or alloy foil.
Embodiment
LED heat-radiating substrate of the present invention comprises Copper Foil or copper alloy foil, and aluminium foil or alloy foil, and described Copper Foil or copper alloy foil and aluminium foil or alloy foil are laminated to respectively a side and the opposite side of polyimide film; Thermal resistance between the surface of the surface of described Copper Foil or copper alloy foil and described aluminium foil or alloy foil is 1.8 ℃/W or less.Thermal resistance between the surface of the surface of described Copper Foil or copper alloy foil and described aluminium foil or alloy foil can be preferably 1.2 ℃/W or less, and more preferably 0.8 ℃/W or less is particularly preferably 0.6 ℃/W or less.
The lower limit of the thermal resistance between the surface of the surface of described Copper Foil or copper alloy foil and described aluminium foil or alloy foil for example can be preferably, but is not limited to, 0.1 ℃/W or larger, and more preferably 0.15 ℃/W or larger is particularly preferably 0.2 ℃/W or larger.
According to the present invention, Copper Foil or copper alloy foil, and aluminium foil or alloy foil preferably contact laminating on described polyimide film, and do not use adhesive etc.Therefore, be engaged to the surface of the polyimide film of Copper Foil or copper alloy foil, and the surface that is engaged to the polyimide film of aluminium foil or alloy foil can be preferably the polyimide layer that metal is represented excellent adhesion, more preferably metal represented the hot press polyimide layer of excellent adhesion.This polyimide film can be the individual layer polyimide film that metal is represented excellent adhesion, the individual layer hot press polyimide film that particularly metal is represented excellent adhesion, or can be a kind of like this polyimide film: wherein, two polyimide layers that metal is represented excellent adhesion are laminated to the both sides of heat-proof polyimide layer, a kind of like this polyimide film particularly: wherein, two hot press polyimide layers that metal is represented excellent adhesion are laminated to the both sides of heat-proof polyimide layer.With regard to the mechanical performance of excellence, such polyimide film preferably: wherein metal is represented two polyimide layers of excellent adhesion, more preferably hot press polyimide layer, be laminated to heat-proof polyimide layer both sides.
Among the present invention, polyimide film can the form with polyimide film provide when the LED heat-radiating substrate is finished.LED heat-radiating substrate of the present invention is not limited to by polyimide film, Copper Foil or copper alloy foil, and aluminium foil or the alloy foil substrate of making laminated together.LED heat-radiating substrate of the present invention can make by following: for example curtain coating or use polyimide precursor solution on Copper Foil or copper alloy foil, for example polyamic acid solution; Heat described solution to produce imidization, make thus polyimide film; Then aluminium foil or alloy foil are laminated on the polyimide film, such as by hot press etc.
The manufacture method of polyimide film and LED heat-radiating substrate hereinafter will be described.
The Copper Foil that uses among the present invention or copper alloy foil can be preferably, but are not limited to, and Copper Foil is particularly preferably rolled copper foil or electrolytic copper foil.
The thickness of Copper Foil or copper alloy foil can be preferably 9 μ m to 200 μ m, more preferably 1g μ m to 200 μ m.In some embodiments, the thickness of Copper Foil or copper alloy foil can be preferably 35 μ m to 80 μ m.Copper Foil or copper alloy foil with larger thickness can be more suitable for large electric current application usually.
The surface roughness Rz of Copper Foil or copper alloy foil can be preferably 3 μ m or less, and more preferably 2 μ m or less are particularly preferably 0.5 μ m to 1.5 μ m.When Rz hour, the surface of Copper Foil or copper alloy foil can be carried out surface treatment before use.
The example of Copper Foil comprises rolled copper foil and electrolytic copper foil, and calendering copper alloy foil and cathode copper Alloy Foil.Particularly preferably can be rolled copper foil.
The aluminium foil or the alloy foil that use among the present invention are not limit, and alloy foil can be made as any alloy of key component and one or more other metals by aluminium.The example of alloy foil comprises that magnesium as the aluminium alloy (Al-Mg alloy) of main additive, such as JIS 5000 series alloys, comprises JIS 5052 alloys.
Among the present invention, contain at least the alloy foil of aluminium and magnesium because its good bending property can be preferred.
All can be used for the present invention although have any Al-Mg alloy of any composition, but preferably magnesium content is 1.5wt% to 5wt%, the more preferably Al-Mg alloy of 2wt% to 3wt% is because it has excellent intensity.
As mentioned above, can preferably use and not pass through anodized aluminium foil or alloy foil, or (for example has quite thin anodic oxide coating, thickness is less than 4 μ m, 3 μ m or less more preferably, be particularly preferably 2 μ m or less) aluminium foil or alloy foil, more preferably use and do not pass through anodized aluminium foil or alloy foil, because they can obtain to have the LED heat-radiating substrate of good bending property and excellent machinability.Do not pass through anodized aluminium foil or alloy foil when using, or when using aluminium foil with quite thin anodic oxide coating or alloy foil, can realize excellent pliability, and join in the situation of polyimide film by thermo-compressed at aluminium foil or alloy foil, be not easy to cause open defect.
In addition, the aluminium foil or the alloy foil that---wherein use the alkaline electrolyte solution that contains surfactant---although the present invention can use through alternating current electrolysis processing (KO processing), for example the thin plate of the KO processing of Furukawa-Sky Aluminum Corp. manufacturing still can preferably use aluminium foil or the alloy foil of not processing through KO.
Can pass through anodization (being also referred to as " alumite " or " sulphuric acid anodizing processing ") although be laminated to aluminium foil on the polyimide film or the surface of alloy foil, or KO processes, but with regard to thermal endurance and bending property, can preferably use aluminium foil or the alloy foil also do not processed through KO through anodization.
The surface that is engaged to the aluminium foil of polyimide film or alloy foil can preferably be processed to remove with organic solvent and be attached to lip-deep oil in the process that makes aluminium foil or alloy foil.
The thickness of aluminium foil or alloy foil can be preferably 200 μ m to 1mm, and more preferably 250 μ m to 500 μ m are particularly preferably 300 μ m to 400 μ m.Aluminium foil or alloy foil with less thickness can be more suitable for crooked the application usually.
According to the present invention, for strengthening heat radiation, fin is attachable to aluminium foil or alloy foil.But can weld aluminium foil or welding aluminum alloy paper tinsel using, Toyo Kohan Co. for example, in the situation of " SAPlate " that Ltd. makes, fin can be welded direct to aluminium foil or alloy foil.
Among the present invention, when the hot press layer of polyimide film when joining metal forming (Copper Foil, aluminium foil) surperficial to, the thickness of described hot press layer can preferably be equal to or greater than the surface roughness (Rzjis) on the surface of the metal forming that is engaged to polyimide film.When the thickness of hot press layer during less than the surface roughness (Rzjis) of metal forming, the LED heat-radiating substrate of gained can have between polyimide film and metal forming with the very large peel strength of change in location.
Now polyimide film will be described.
Polyimide film can be, but be not limited to, the polyimide film that Copper Foil and aluminium foil is represented excellent adhesion, can be preferably the hot press polyimide film, wherein the lamination metal forming such as Copper Foil thereon can be removed by etching, and has excellent thermal endurance, electrical insulation capability and bending property.In case of necessity, polyimide film can be enough to supporting layer and press thereon metal forming, and, in case of necessity, can not be used to form severe exacerbation under the effect of the developer of photoresist layer of metal line or remover in removal.
Polyimide film can be film, sheet or the plate of individual layer, perhaps is film, sheet or the plate of two-layer or multilayer.
The example of polyimide film includes, but not limited to Ube Industries, " UPILEX (VT) " (trade mark) of Ltd.
Although the thickness of polyimide film is not limit, but thin polyimide film more preferably, as long as described polyimide film has suitable electrical insulation capability.The thickness of polyimide film can be preferably 3 μ m to 50 μ m, 4 μ m to 35 μ m more preferably, and 5 μ m to 25 μ m more preferably, more preferably 7 μ m to 15 μ m are particularly preferably 9 μ m to 15 μ m.
The thickness of polyimide film is considered soldering resistance, can be preferably 4 μ m to 15 μ m, and more preferably 7 μ m to 12.5 μ m consider soldering resistance and thermal endurance, can be preferably 9 μ m to 15 μ m.
Among the present invention, polyimide film can use afterwards through at least one surface to surface treatment (surface to surface treatment), such as Corona discharge Treatment, plasma treatment, chemical surface roughening processing, physical surface roughening processing and use surface treatment such as the surface conditioning agent of silane coupler.In the situation of individual layer hot press polyimide film, and the hot press polyimide layer of polyimide film directly is engaged in the situation of metal, do not need to use the surface treatment of surface conditioning agent.
The example of the silane coupler that the surface treatment of polyimide film is used comprises various silane couplers; such as the most frequently used amino functional silane coupler and epoxide function silane coupler, and sulfydryl function silane coupler, alkene function silane coupler and acryloyl group function silane coupler.
The object lesson of silane coupler comprises vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, the ethenylphenyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrimethoxy silane, 4-glycidol butyl trimethoxy silane, gamma-aminopropyl-triethoxy-silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-3-(4-(the amino propoxyl group of 3-) butoxy) propyl group-3-aminopropyl trimethoxysilane, imidazoles silane, triazine silane and γ mercaptopropyitrimethoxy silane.The surface conditioning agent of polyimide film can be preferably silane coupler, such as amino silicane coupling agent and epoxy silane coupling agent.
When using based on the coupling agent of titanate esters or based on the coupling agent of zirconate, when replacing silane coupler to process polyimide film surperficial, can reach similar effect.
Can carry out surface treatment with silane coupler according to any known method.
The situation that comprises that the surface conditioning agent that contains in the surface of polyimide film does not change " uses such as the surface conditioning agent of silane coupler and process (surface treatment) " to term, and the surface conditioning agent that contains in the polyimide film is for example causing the variation situation of (comprising chemical change) by heat treatment under 320 ℃ to 550 ℃ the temperature in polyimides or polyimide precursor or its organic solution.
When polyimide film has not enough good handling property when---for example the low rigidity of substrate---, the rigid film that can peel off from this polyimide film or plate can be engaged to the back side at the substrate that uses in subsequent step.
Among the present invention, polyimide film can be multi hot press joint and/or the bonding polyimide film with two-layer or multilayer, and described film comprises refractory layer (Sa1) and hot press and/or tack coat (Sa2), comprises one deck adhesive in the both sides of refractory layer.The example of layer configuration comprises Sa2/Sa1/Sa2, and Sa2/Sa1/Sa2/Sa1/Sa2.Alternately, polyimide film can comprise single hot press layer (Sa2).
The hot press of polyimide film and/or tack coat (Sa2) are adapted to couple to metal forming.Hot press and/or tack coat (Sa2) can be selected from any hot press layer and any tack coat.
In the multi hot press joint with two-layer or multilayer and/or bonding polyimide film, can suitably select the thickness of refractory layer (Sa1) and hot press and/or tack coat (Sa2).Yet, in the present invention, preferably be equal to or greater than the aforesaid surface roughness (Rzjis) that is incorporated into the metal foil surface of polyimide film waiting as the hot press of outermost layer (superficial layer) and/or the thickness of tack coat (Sa2), and can be preferably 0.5 μ m or larger, more preferably 1 μ m or larger is particularly preferably 2 μ m or larger.In addition, the thickness of hot press and/or tack coat (Sa2) can be preferably 3 μ m or less.
LED heat-radiating substrate of the present invention is characterised in that Copper Foil or copper alloy foil, polyimide film (polyimide layer) and aluminium foil or alloy foil are laminated together.The present invention should not be subjected to the restriction of production method.
The LED heat-radiating substrate for example can be, Copper Foil or copper alloy foil are laminated to the laminated sheet that polyimide film one side and aluminium foil or alloy foil are laminated to the opposite side of polyimide film, lamination can be the mode of utilizing heating and/or pressurization, contact laminating or by adhesive (hot press material) lamination.Alternately, the LED heat-radiating substrate can be by using polyimide solution or the polyimide precursor solution (for example polyamic acid solution) that is converted into the hot press polyimide layer at Copper Foil or copper alloy foil and aluminium foil or alloy foil respectively, in case of necessity, heat subsequently, drying and imidization, then the laminated sheet at gained utilizes the mode lamination polyimide film of heating and/or pressurization to make.Alternately, the LED heat-radiating substrate can be by using polyimide solution or the polyimide precursor solution (for example polyamic acid solution) that is converted into the hot press polyimide layer at Copper Foil or copper alloy foil, in case of necessity, heat subsequently, drying and imidization, then the laminated sheet at gained utilizes mode lamination aluminium foil or the alloy foil of heating and/or pressurization to make.
Preferably, metal forming (Copper Foil, aluminium foil) contact laminating is on polyimide film.When enough the adhering to that can't realize by heating, pressurization or the two combination between polyimide film surface and the metal forming, metal forming preferably is pressed on the polyimide film by adhesive layer.
Can use adhesive or hot press organic material or resin at polyimide film and/or metal forming by method commonly used arbitrarily, or the resin of one-tenth polyimide film to be transformed, for example by roll coater, slit coater or unfilled corner wheel coating machine.
The metal foil layer that can use heater, pressue device or pressurization and heater to have adhesive layer or hot press resin bed polyimide film with on it forces together, or alternately, laminated together the polyimide film that has adhesive layer or hot press resin bed on metal forming and its.Preferably, can suitably select heating condition and pressurized conditions according to the type of the material that uses.The method of laminated metal foil and polyimide film has no particular limits, as long as it can be in a continuous manner or mode intermittently.The method can preferably use roll-type laminating machine, biobelt press (double-belt press) etc. to carry out continuously.
Among the present invention, can be fit to use the polyimide film with excellent heat resistance and electrical insulation capability.
Polyimide film can be the individual layer polyimide film, or has the laminated multi-layer polyimide film of two or more polyimide layers.The type of polyimides has no particular limits.
Polyimide film can make by known method.The individual layer polyimide film can for example be prepared as follows:
(1) curtain coating or application polyamic acid solution, i.e. polyimide precursor solution on supporter; Then this polyamic acid of imidization; Perhaps
(2) curtain coating or application polyamic acid solution on supporter; In case of necessity, then heat this polyamic acid solution.
Multilayer polyimide film with two or more polyimide layers can for example be prepared as follows:
(3) curtain coating or application polyamic acid solution, i.e. polyimide precursor solution on supporter; Curtain coating or application polyamic acid solution on the polyamic acid layer, namely polyimide precursor solution repeats this operation continuously, to form two or more polyamic acid layers; Then this polyamic acid of imidization;
(4) curtain coating or use two or more polyamic acid solutions simultaneously on supporter, i.e. polyimide precursor solution is to form two or more polyamic acid layers; Then this polyamic acid of imidization;
(5) curtain coating or application polyimide solution on supporter; Curtain coating or application polyimide solution repeat this operation, continuously to form two or more polyimide layers on polyimide layer; In case of necessity, then heat this polyamic acid solution;
(6) curtain coating or use two or more polyimide solutions simultaneously on supporter is to form two or more polyimide layers; In case of necessity, then heat this polyimide solution; Perhaps
(7) contact laminating or press each two or more polyimide films that make in the method for stating (1) to (6) by adhesive layer.
In addition, in the LED heat-radiating substrate as supporter, polyimide film can be formed directly on Copper Foil or copper alloy foil, or on aluminium foil or the alloy foil.
Polyimide film can be preferably the hot press polyimide film with three layers or multilayer, and this film comprises heat-proof polyimide layer (S1) and at the hot press polyimide layer (S2) of these heat-proof polyimide layer (S1) both sides.The example of the layer configuration of multilayer polyimide film comprises S2/S1/S2 and S2/S1/S2/S1/S2.Alternately, polyimide film can comprise single hot press polyimide layer (S2).
In the hot press polyimide film, can suitably select the thickness of heat-proof polyimide layer (S1) and hot press layer (S2).Yet, in the present invention, preferably be equal to or greater than the aforesaid surface roughness (Rzjis) that is incorporated into the metal foil surface of polyimide film waiting as the thickness of the hot press polyimide layer (S2) of outermost layer (superficial layer).Have in the both sides of heat-proof polyimide layer (S1) in the situation of polyimide film of hot press polyimide layer (S2), should be enough to realize Copper Foil or the enough tacks of aluminium foil by hot press as the thickness of outermost described hot press polyimide layer (S2).The thickness of hot press polyimide layer (S2) can be preferably 0.5 μ m to 10 μ m, more preferably 1 μ m to 7 μ m, more preferably 2 μ m to 5 μ m.In addition, the thickness of hot press polyimide layer (S2) can be preferably 3 μ m or less.
When two the hot press polyimide layer (S2) of same thickness is laminated to the both sides of heat-proof polyimide layer (S1) basically, can reduce the curling of polyimide film.
In the hot press polyimide film, the heat-proof polyimide that is used for heat-proof polyimide layer (S1) can have at least one of following feature (1) to (4), particularly have at least two [(1) and (2) in the following feature (1) to (4), (1) and (3), (2) and the combination of (3) etc.], particularly preferably have all following features.
(1) during the form of independent polyimide film, glass transition temperature is 300 ℃ or higher, is preferably 330 ℃ or higher, and more preferably glass transition temperature can't detect.
(2) during the form of independent polyimide film, thermal coefficient of expansion (50 ℃ to 200 ℃) is (MD) close to the metal forming that is laminated on the polyimide film, such as the thermal coefficient of expansion of Copper Foil.Particularly, the thermal coefficient of expansion of polyimide film is preferably 5 * 10
-6Cm/cm/ ℃ to 28 * 10
-6Cm/cm/ ℃, more preferably 9 * 10
-6Cm/cm/ ℃ to 20 * 10
-6Cm/cm/ ℃, more preferably 12 * 10
-6Cm/cm/ ℃ to 18 * 10
-6Cm/cm/ ℃.
(3) during the form of independent polyimide film, tensile modulus of elasticity (MD, ASTM-D882) is 300kg/mm
2Or larger, be preferably 500kg/mm
2Or larger, 700kg/mm more preferably
2Or larger.
(4) percent thermal shrinkage is preferably 0.05% or less.
The polyimides that can be used for heat-proof polyimide layer (S1) is made by acid constituents and diamine components, described acid constituents comprises and is selected from 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (s-BPDA), pyromellitic acid anhydride (PMDA) and 3,3 ', 4,4 '-in the group that Benzophenone carboxylic acid dianhydride (BTDA) forms at least one be as key component, described diamine components comprise be selected from p-phenylenediamine (PPD) (PPD) and 4,4 '-in the group that diaminodiphenyl ether (DADE) forms at least one be as key component.Part or all of 4,4 '-diaminodiphenyl ether (DADE) can be by 3,4 '-diaminodiphenyl ether (DADE) replaces.
For example, following polyimides can be suitable for heat-proof polyimide layer (S1).
(1) polyimides by 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (s-BPDA) and p-phenylenediamine (PPD) (PPD) and alternatively 4,4 '-diaminodiphenyl ether (DADE) makes.In this polyimides, the ratio of PPD/DADE (mol ratio) is preferably 100/0 to 85/15.
(2) polyimides by 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (s-BPDA), pyromellitic acid anhydride (PMDA) and p-phenylenediamine (PPD) (PPD) and 4,4 '-diaminodiphenyl ether (DADE) makes.In this polyimides, the ratio of BPDA/PMDA (mol ratio) is preferably 15/85 to 85/15, PPD/DADE ratio (mol ratio) and is preferably 90/10 to 10/90.
(3) polyimides by pyromellitic dianhydride (PMDA) and p-phenylenediamine (PPD) (PPD) and 4,4 '-diaminodiphenyl ether (DADE) makes.In this polyimides, the ratio of DADE/PPD (mol ratio) is preferably 90/10 to 10/90.
(4) polyimides by 3,3 ', 4,4 '-Benzophenone carboxylic acid dianhydride (BTDA), pyromellitic acid anhydride (PMDA) and p-phenylenediamine (PPD) (PPD) and 4,4 '-diaminodiphenyl ether (DADE) makes.In this polyimides, the ratio of BTDA/PMDA (mol ratio) is preferably 20/80 to 90/10, PPD/DADE ratio (mol ratio) and is preferably 30/70 to 90/10.
Also can in the situation of not damaging heat-proof polyimide character, use other tetracarboxylic dianhydride and other diamines.
The heat-proof polyimide that is used for heat-proof polyimide layer (S1 layer) can be synthetic by atactic polymerization or the block polymerization of acid constituents and diamine components, and described acid constituents and described diamine components all have the final composition in the above-mentioned scope.The heat-proof polyimide that is used for heat-proof polyimide layer (S1 layer) also can synthesize to form homogeneous phase solution by mix these polyamic acid solutions behind synthetic two kinds of polyamic acids under reaction condition.
Heat-proof polyimide can make by following.At first, the above-mentioned diamine components of equimolar amounts basically and above-mentioned acid constituents (tetracarboxylic dianhydride) are reacted in organic solvent and make polyamic acid solution.In polyamic acid solution, can carry out the part imidization, as long as described polyamic acid solution keeps homogeneous phase.Subsequently, polyamic acid solution uses with the form of jelly, and forms the film of jelly, and then heat to evaporate and remove solvent in the described film, and the described polyamic acid of imidization, make thus heat-proof polyimide.
According to the present invention, hot press polyimides jelly film can be laminated on the heat-proof polyimide jelly film, simultaneously these jellies is carried out imidization subsequently.According to the present invention, but coextrusion heat-proof polyimide jelly and hot press polyimides jelly, to form the laminated sheet of heat-proof polyimide jelly film and hot press polyimides jelly film, then simultaneously these jellies are carried out imidization.After a while these processes can be described.
The hot press polyimides that is used for hot press polyimide layer (S2) is: (1) hot pressing is engaged to the polyimides of metal forming.The hot press polyimides can be preferably in the temperature laminated of the glass transition temperature to 400 of this hot press polyimides ℃ to metal forming.
In addition, the hot press polyimides that is used for hot press polyimide layer (S2) can preferably have at least one of following feature (2) to (5).
(2) peel strength between metal forming and the polyimides (S2) is 0.7N/mm or larger, and after 168 hours, the retention rate of peel strength is 90% or larger 150 ℃ of lower heat treatments, more preferably 95% or larger, be particularly preferably 100% or larger.
(3) glass transition temperature is in 130 ℃ to 330 ℃ scope.
(4) tensile modulus of elasticity is at 100kg/mm
2To 700kg/mm
2Scope in.
(5) thermal coefficient of expansion (50 ℃ to 200 ℃) is (MD) 13 * 10
-6Cm/cm/ ℃ to 30 * 10
-6In cm/cm/ ℃ the scope.
The thermoplastic polyimide conduct that capable of choosing multiple is known is used for the hot press polyimides of hot press polyimide layer (S2).Spendable hot press polyimides, the polyimides of the following material preparation of for example can serving as reasons:
Acid constituents for example comprises and is selected from 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride (a-BPDA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (s-BPDA), pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-Benzophenone carboxylic acid dianhydride (BTDA), 3,3 ', 4,4 '-the diphenyl sulfone tetracarboxylic dianhydride, 4,4 '-the two phthalic anhydrides (ODPA) of oxygen, TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydride) and 3,3 ', 4,4 '-in the group that ethylene glycol bisthioglycolate benzoic ether tetracarboxylic dianhydride forms at least one, preferably, acid constituents comprises it as key component, and
Diamine components, for example comprise at least one diamines that has at least three phenyl ring on the main chain, described diamines is selected from 1, two (the 4-ammonia phenoxy group) benzene of 4-, 1, two (the 4-ammonia phenoxy group) benzene of 3-, 1, two (the 3-ammonia phenoxy group) benzene of 3-, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, the group that two [4-(4-amino-benzene oxygen) phenyl] sulfone and two [4-(3-amino-benzene oxygen) phenyl] sulfone form, preferably, diamine components comprises it as key component, and in case of necessity, diamine components can comprise the diamines that has one or two phenyl ring on the main chain.
The polyimides that is suitable as the hot press polyimides can be by being selected from 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride (a-BPDA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (s-BPDA), pyromellitic acid anhydride (PMDA) and 3,3 ', 4,4 '-acid constituents of the group that Benzophenone carboxylic acid dianhydride (BTDA) forms and be selected from 1, two (the 4-ammonia phenoxy group) benzene of 4-, 1, two (the 4-ammonia phenoxy group) benzene of 3-, the diamine components of the group that two (the 3-ammonia phenoxy group) benzene of 1,3-and two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-form makes.In case of necessity, this hot press polyimides can comprise the diamines that has one or two phenyl ring on the main chain, and/or other diamine components, and/or other acid constituents.
Particularly preferred hot press polyimides can be to be no less than 80 % by mole 1 by comprising, benzene (hereinafter for 3-two (4-ammonia phenoxy group), sometimes be abbreviated as " TPER ") and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (s-BPDA) and/or 2,3,3 ', 4 '-polyimides that the diamine components of biphenyl tetracarboxylic dianhydride (a-BPDA) makes.In this polyimides, the ratio of s-BPDA/a-BPDA (mol ratio) is preferably 100/0 to 5/95.Also can in the situation of not damaging hot press polyimides character, use two (3,4-dicarboxyl phenyl) the propane dianhydrides of other tetracarboxylic dianhydrides such as 2,2-and 2,3,6,7-naphthalene tetracarboxylic acid dianhydride.
The hot press polyimides can make by the following method.At first, at about 100 ℃ or lower, particularly under 20 ℃ to 60 ℃ the temperature, in organic solvent, make above-mentioned diamine components and above-mentioned acid constituents, and alternatively in addition the tetracarboxylic dianhydride and in addition diamines react and make polyamic acid solution.Subsequently, polyamic acid solution uses as jelly, and forms the film of jelly, and then heat to evaporate and remove solvent in the described film, and the described polyamic acid of imidization, make thus the hot press polyimides.
The organic solvent solution of hot press polyimides can make by following.At first, the polyamic acid solution that makes of said method heats that under 150 ℃ to 250 ℃ temperature imidization occurs.Alternately, in polyamic acid solution, add imidization reagent, then at 150 ℃ or lower, particularly under 15 ℃ to 50 ℃ the temperature, make polyamic acid solution generation imidization.Subsequently, the hot press polyimide powder makes by evaporating solvent, or alternately, makes by precipitation hot press polyimides in poor solvent.Then, this powder dissolution in organic solvent, thereby make the organic solvent solution of hot press polyimides.
By above-mentioned preparation hot press polyimides the time, described diamines (according to the molal quantity of amino) can be preferably 0.95 to 1.0 with the ratio of acid anhydrides (according to the molal quantity of anhydride group in tetracarboxylic dianhydride and the dicarboxylic anhydride) in organic solvent, be particularly preferably 0.98 to 1.0, more preferably 0.99 to 1.0.When dicarboxylic anhydride was used for reaction, with respect to the molal quantity of anhydride group among the tetracarboxylic dianhydride, the ratio of the dicarboxylic anhydride of use can be 0.05 or less.
When the molecular weight of the polyamic acid that obtains in the preparation of hot press polyimides hangs down, can reduce the adhesive strength of the laminated sheet of polyimide film and metal forming composition, described laminated sheet is LED heat-radiating substrate of the present invention.
In order to prevent the gelatification of polyamic acid, in the polymerization process of polyamic acid, can be to the phosphorus-containing stabilizers of adding in the solution based on solid (polymer) content meter 0.01wt% to 1wt%, such as triphenyl phosphite and triphenyl phosphate.
In order to accelerate imidization, can in jelly, add alkaline organic compound.For example, can be to imidazoles, the glyoxal ethyline, 1 of adding in the jelly based on polyamic acid meter 0.05wt% to 10wt%, particularly 0.1wt% to 2wt%, the pyridine of 2-methylimidazole, 2-phenylimidazole, benzimidazole, isoquinolin, replacement etc.Contingent insufficient imidization when using these compounds to can be used for avoiding forming polyimide film at a lower temperature.
In addition, in order to stablize adhesiveness, can add organo-aluminum compound in the polyamic acid solution, without machine aluminium compound or organo-tin compound, to make the hot press polyimides.For example, with regard to aluminum metal, can in polyamic acid solution, add based on polyamic acid meter 1ppm or more, particularly 1ppm to 1 aluminium hydroxide of 000ppm, praseodynium aluminium etc.
For heat-proof polyimide and hot press polyimides, the example that is prepared the organic solvent that uses in the polyamic acid by acid constituents and diamine components comprises: METHYLPYRROLIDONE, N, dinethylformamide, N, N-dimethylacetylamide and N, N-diethyl acetamide, dimethyl sulfoxide (DMSO), hexamethyl phosphoramide, N-methyl caprolactam and cresols.These organic solvents can use separately or two or more being used in combination.
When preparation heat-proof polyimide and hot press polyimides, end-blocking amine end can use dicarboxylic anhydride, such as the derivative of phthalic anhydride and replacement thereof, the derivative of the derivative of hexahydrophthalic anhydride and replacement thereof and succinyl oxide and replacement thereof, particularly phthalic anhydride.
Suitably, can prepare by the following method the hot press polyimide film that has hot press polyimide layer (S2) in heat-proof polyimide layer (S1) one or both sides:
(i) a kind of method, wherein by at the supporter of film laminate form by coextrusion the tape casting (being sometimes referred to as " coetrusion ") curtain coating heat-proof polyimide (S1) jelly and hot press polyimides (S2) jelly, then dry the and described jelly of imidization forms multilayer polyimide film; Or
(ii) a kind of method, wherein by use hot press polyimides (S2) jelly in self-supported membrane (glued membrane) one or both sides, then the dry and described jelly of imidization forms multilayer polyimide film, and described self-supported membrane makes by curtain coating heat-proof polyimide (S1) jelly on supporter and dry this jelly.
Can use the coextrusion method of describing among the JP-A-1991-180343 (JP-B-1995-102661).
The below has description the example of manufacture method of three layers polyimide film, and wherein the both sides of film are hot press.
The polyamic acid solution that is used for the polyamic acid solution of heat-proof polyimide (S1) and is used for hot press polyimides (S2) is admitted to three layers of extrusion die, and on supporters such as stainless steel mirror and stainless steel zone face, go out the method curtain coating with three-layer co-extruded, so that the thickness of heat-proof polyimide layer (S1 layer) is in the scope of 4 μ m to 45 μ m, and the gross thickness of the hot press polyimide layer (S2 layer) on heat-proof polyimide layer (S1 layer) both sides is in the scope of 1 μ m to 20 μ m.Subsequently, casting films is dry under 100 ℃ to 200 ℃ temperature, makes thus the polyimide film as self-supported membrane (A) of semi-cured state or the drying regime at the initial stage of being in.
In preparation hot press polyimides process, for example when casting films when being higher than 200 ℃ high-temperature heating, can reduce adhesiveness.Term " is in semi-cured state or the partial desiccation state at initial stage " and refers to that film is in the self-supporting state by heating and/or chemical imidization reaction.
For the polyimide film (A) of self-supported membrane can preferably contain solvent and water, described solvent and water form by described reaction, and its amount is about 25wt% extremely about 60wt%, particularly preferably 30wt% to 50wt%.Self-supported membrane can preferably be heated to the temperature of carrying out drying/imidization within the relatively short time, for example, self-supported membrane can be preferably with 10 ℃/min or larger heating rate heating.
In drying/imidization process, when applying larger tension force to self-supported membrane, the polyimide film that finally obtains (A) can have lower thermal coefficient of expansion.
Prepare after the drying steps of above-mentioned self-supported membrane, use with its fixture that moves etc. fixedly when at least one opposite side of self-supported membrane, continuously or discontinuous, to self-supported membrane at the high temperature that is higher than above-mentioned baking temperature, for example preferred 200 ℃ to 550 ℃, particularly preferably 300 ℃ to 500 ℃ temperature is carried out drying and heating preferred about 1min to 100min, particularly preferably 1min to 10min.The polyimide film that both sides are hot press by fully remove solvent in the self-supported membrane etc. and fully imidization consist of the polymer of film (such as by reacting the volatile contents such as the organic solvent that produces and water) forms so that the final polyimide film that obtains preferably has 1wt% or lower volatile content.
The preferred fixture of above-mentioned self-supported membrane for example can be, a device like this: wherein for example have a pair of band of many equidistant pins or clip or chain is arranged on continuously along its length or two edges of the self-supported membrane of off and on feeding, and the self-supported membrane with continuous or index(ing) feed moves when fixing this film.In addition, the fixture of above-mentioned self-supported membrane can be when heat treatment, can be on Width or length direction stretches and/or the device of shrink film with suitable stretching or shrinkage ratio (being particularly preferably about 0.5% to about 5%).
Preferably, the both sides that make according to the method described above are the polyimide film of hot press can be further under 100 ℃ to 400 ℃ temperature, under without tension force or low-tension, preferably 4N or lower, particularly preferably under 3N or the lower low-tension, heating 0.1min to 30min, so that the polyimide film with improvement dimensional stability to be provided, particularly, both sides are the polyimide film of hot press.
The both sides that make thus are the long polyimide film of hot press and can roll up by suitable known method coiled.
Wherein the surface of the polyimide film that contacts with supporter of curtain coating jelly is considered as the B side, and wherein the surface (air side) of the polyimide film that do not contact with supporter of curtain coating jelly is considered as the A side.
The example of the method for making the LED heat-radiating substrate will be described herein, as mentioned above, described substrate particularly comprises having heat-proof polyimide layer (S1) and at the hot press polyimide layer (S2) of described heat-proof polyimide layer (S1) both sides.
For example, as indicated above, the LED heat-radiating substrate can be by in heat-proof polyimide layer (S1) both sides, contact laminating or by adhesive lamination metal forming, i.e. Copper Foil or copper alloy foil, and aluminium foil or alloy foil and prepare.
The polyimide film that the LED heat-radiating substrate can be preferably has a hot press polyimide layer (S2) by above-mentioned both sides makes, by directly going up laminated metal foil at hot press polyimide layer (S2), be Copper Foil or copper alloy foil, and aluminium foil or alloy foil make.
With regard to peel strength, the polyimide film that the LED heat-radiating substrate can be more preferably has a hot press polyimide layer (S2) by above-mentioned both sides makes,, and directly make at film surface (B side) lamination aluminium foil or the alloy foil of hot press polyimide layer (S2) at the film of hot press polyimide layer (S2) surface (A side) lamination Copper Foil or copper alloy foil by directly.
Wherein metal foil layer is pressed in the example of manufacture method of LED heat-radiating substrate of the both sides of hot press polyimide film, comprises following method:
1) grows in this order lamination of metal forming (Copper Foil or copper alloy foil), long hot press polyimide film and long metal forming (aluminium foil or alloy foil), and send into inferior thermal bonding device (heating and pressue device).Metal forming and hot press polyimide film can be preferably about 150 ℃ to about 250 ℃ temperature, particularly preferably in being higher than 150 ℃ but be not higher than under 250 ℃ the temperature preheating about 2 seconds to about 120 seconds, use is such as the preheating device of hot air blower and infrared heater, online preheating device is set before preferably just in time in introducing hot-pressing jointing device.
2) three layer by layer pressing plate (metal foil/polyimide/metal forming) be equal to or higher than than the high 20 ℃ temperature of glass transition temperature of polyimides (S2) but be not higher than 400 ℃ temperature, particularly preferably in being equal to or higher than than the high 30 ℃ temperature of glass transition temperature of polyimides (S2) but be not higher than under 400 ℃ the temperature, in the hot press zone, use a pair of pressure roller or a biobelt press pressurization to carry out hot press.
3) in the situation of biobelt press, particularly after the hot press, laminated sheet cools off under pressure, preferably be cooled to be equal to or less than temperature than low 20 ℃ of the glass transition temperature of polyimides (S2) at cooled region, particularly preferably be cooled to be equal to or less than the temperature than low 30 ℃ of the glass transition temperature of polyimides (S2), so that metal foil layer is pressed in the both sides of polyimide film, then with this laminated sheet coiled volume.
Thereby the form that the LED heat-radiating substrate can be rolled up makes.
In the method, before hot press, carry out preheating, open defect appears in the laminated sheet that can prevent gained after hot press, this defective is because the foaming that the water in the polyimides etc. cause, and in weldering is bathed, bubble in the impregnation process can prevent from consisting of electronic circuit the time, this can prevent the minimizing of output.It is unpractical placing whole hot-pressing jointing device in heating furnace, because the hot-pressing jointing device that will use is limited to compact devices basically, has limited the shape of LED heat-radiating substrate.If carry out online preheating, polyimides can absorb water before lamination, and thereby may be owing to bubble, be difficult to prevent after the hot press the apparent defective of gained laminated sheet and weld stable on heating reduction.
The biobelt press can carry out cooling off under high-temperature heating/pressure, and the fluid pressure type press of use thermal medium is preferred.
When cooling is pressed in metal foil layer on the polyimide film that both sides are hot press under by the hot press/pressure of biobelt press, the speed of service is preferably 1m/min or larger, long and wide metal foil laminated polyimide film (LED heat-radiating substrate) can be provided, the width of this film is about 400mm or wider, about 500mm or wider especially, and bonding strength is high (namely, peel strength between metal forming and the polyimide layer is high), to such an extent as to and outward appearance well basically do not observe fold in metal foil surface.
Preferably, with one or more combinations of hot press polyimide film and metal forming, send into together together with diaphragm (that is, two diaphragms), each diaphragm places between outermost layer and the band; And cool off lamination by under hot press/pressure, so that batch production has the LED heat-radiating substrate of good appearance.Can use any diaphragm, no matter what material, as long as this film is that unhot-pressing closes and has excellent surface flatness.The preferred example of diaphragm comprises metal forming, and particularly Copper Foil, stainless steel foil or aluminium foil and highly heat-resistant polyimide film (deriving from Ube Industries, the UPILEX S of Ltd.), their thickness are that about 5 μ m are to about 125 μ m.
According to any known method, can partly remove Copper Foil or copper alloy foil forms metal line at the LED heat-radiating substrate that obtains thus by etching method, led chip can be installed in the metal line side.LED heat-radiating substrate of the present invention has excellent heat dispersion, therefore can reduce the rising of LED temperature and the reduction of LED luminous efficiency, even when on the substrate that uses in LED light-emitting device or the LED-backlit a lot of LED being installed.
Embodiment
Below with reference to embodiment the present invention is described in more detail.Yet the present invention is not limited to these embodiment.
(evaluation method)
(1) peel strength: according to JIS C5016, under the condition of 90 ° and 5mm width, measure the peel strength between polyimide film and aluminium foil.The sample of measuring is the laminated sheet of polyimides/aluminium foil, makes by peeling off Copper Foil from the LED heat-radiating substrate.The measurement of peel strength is carried out at three some places, that is, without the starting point of any processing, after the humid heat treatment (85 ℃, after 85%Rh processed 1000 hours), and after 260 ℃ of sweating heats processed 30 seconds.
(2) welding thermal endurance: estimate the welding thermal endurance according to JIS C6481.The sample of measuring is the laminated sheet of polyimides/aluminium foil, makes from LED heat-radiating substrate removal of copper paper tinsel with etching method.As the welding Evaluation of Heat Tolerance, after 250 ℃ or 270 ℃ of sweating heats are processed 30 seconds, have or not foaming in the polyimide film of visual observation laminated sheet.
Zero: do not observe foaming.
*: observe foaming.
(3) crooked machinability: the measurement sample is the laminated sheet of Copper Foil/polyimides/aluminium foil.The flex layers pressing plate is so that laminated sheet has the overall diameter of about 1.0mm and the interior diameter of about 0.6mm.Subsequently, make sweep get back to initial state, the sweep of visual observation aluminium foil has flawless.Flex layers pressing plate in two ways, that is, and outwardly-bent Copper Foil, and the Copper Foil that curves inwardly.
Zero: do not observe crackle.
*: observe crackle.
(reference example 1: the preparation of the jelly of heat-proof polyimide S1)
In METHYLPYRROLIDONE, add mol ratio and be the p-phenylenediamine (PPD) (PPD) and 3,3 of 1000:998 ', 4,4 '-biphenyl tetracarboxylic dianhydride (s-BPDA) so that monomer concentration is 18% (by weight, hereinafter applicable equally).Subsequently, mixture was 50 ℃ of lower reactions 3 hours.The polyamic acid solution that obtains thus has the solution viscosity of about 1680 pools under 25 ℃.
(reference example 2: the preparation of the jelly of heat-resisting joint polyimides S2)
In METHYLPYRROLIDONE, add mol ratio and be 1000: 200: 800 1, two (the 4-ammonia phenoxy group) benzene (TPE-R) and 2 of 3-, 3,3 ', 4 '-biphenyl tetracarboxylic dianhydride (a-BPDA) and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (s-BPDA), so that monomer concentration is 18%.Subsequently, to wherein adding the triphenyl phosphate of counting 0.5 % by weight with respect to monomer, then mixture was 40 ℃ of reactions 3 hours.The polyamic acid solution that obtains thus has the solution viscosity of about 1680 pools under 25 ℃.
(reference example 3 and 4: the preparation of hot press multilayer polyimide film A1 and A2)
The film-forming machine of three layers of extrusion die (multiple flow passages mould) is equipped with in use, the polyamic acid solution that on metal support, makes with the thickness curtain coating reference example 1 and 2 of three layers of different extrusion dies, then continuous drying under 140 ℃ hot-air, and peel off from supporter, to form self-supported membrane.The self-supported membrane of peeling off from supporter is heated to 450 ℃ from 150 ℃ gradually heating furnace, to remove solvent and to carry out imidization.Therefore, make three layers of long polyimide film of two kinds of different-thickness, and the coiled volume.
(layer configuration: performance S2/S1/S2), the result is as follows to estimate thus obtained three strata acid imide films.
(hot press multilayer polyimide film A1)
The thickness configuration: 2.5 μ m/7.5 μ m/2.5 μ m are (total: 12.5 μ m)
The glass transition temperature of S2 layer: 240 ℃
The glass transition temperature of S1 layer:
Temperature can not clearly observe Tg at 300 ℃ or when higher.
Thermal coefficient of expansion (50 ℃ to 200 ℃):
MD?19ppm/℃，TD?18ppm/℃，
Mechanical performance (method of testing: ASTM-D882)
1) hot strength: MD, TD 520MPa (every layer)
2) percentage elongation: MD, TD 90% (every layer)
3) tensile modulus of elasticity: MD, TD 7200MPa (every layer)
Electric property (method of testing: ASTM-D149)
1) dielectric breakdown voltage: 4.9kV
(multi hot press engages polyimide film A2)
The thickness configuration: 4 μ m/17 μ m/4 μ m are (total: 25 μ m)
The glass transition temperature of S2 layer: 240 ℃
The glass transition temperature of S1 layer:
Temperature can not clearly observe Tg at 300 ℃ or when higher.
Thermal coefficient of expansion (50 ℃ to 200 ℃):
MD?19ppm/℃，TD?18ppm/℃，
Mechanical performance (method of testing: ASTM-D882)
1) hot strength: MD, TD 520MPa (every layer)
2) percentage elongation: MD, TD 100% (every layer)
3) tensile modulus of elasticity: MD, TD 7200MPa (every layer)
Electric property (method of testing: ASTM-D149)
1) dielectric breakdown voltage: 7.1kV
The thickness that multi hot press engages polyimide film A1 and A2 is respectively 12.5 μ m and 25 μ m, this is than the epoxy resin film that uses in tradition and the most frequently used LED heat-radiating substrate (thickness: 1.2mm) thinner, and have the electrical insulation capability that is equivalent to epoxy resin film.
In following embodiment, copper foil layer is pressed in the A side of polyimide film, and aluminium foil laminate is in the B of polyimide film side.
Use processes to remove the aluminium foil behind the grease that sticks to the surface with organic solvent.
(embodiment 1 to 3)
(manufacturing of LED heat-radiating substrate)
The biobelt press is sent in the hot-air online preheating of three strata acid imide film A2 by 200 ℃ 30 seconds afterwards immediately.Electrolytic copper foil (thickness: 18 μ m, Rz:0.6 μ m) is laminated to the side (A side) of polyimide film A2, and being untreated or surface-treated Al-Mg Alloy Foil (A5052-H34 shown in the table 1, Furukawa-Sky Aluminum Corp. makes, thickness: the opposite side (B side) that 300 μ m) is laminated to polyimide film A2.Subsequently, laminated sheet is admitted to the thermal treatment zone (maximum heating temperature is 330 ℃), then send into cooling zone (minimum chilling temperature is 180 ℃) and engage and cooling to carry out continuous hot-press, wherein hot press pressure is 3.9MPa, and the hot press time is 2min.Therefore, LED heat-radiating substrate (width: 540mm, length: 30m), and with its coiled volume have been made.Measure peel strength, welding thermal endurance and the crooked machinability of the LED heat-radiating substrate that obtains thus.The result is as shown in table 2.Under 250 ℃ temperature, weld stable on heating evaluation.
Table 1
Table 2
(embodiment 4 to 5)
(manufacturing of LED heat-radiating substrate)
The biobelt press is sent in the hot-air online preheating of three strata acid imide films shown in the table 3 by 200 ℃ 30 seconds afterwards immediately.Rolled copper foil (thickness: 35 μ m, roughness grade number Rz:1.2 μ m) is laminated to the side (A side) of polyimide film, untreated Al-Mg Alloy Foil (A5052-H34, Furukawa-SkyAluminum Corp. makes, thickness: the opposite side (B side) that 300 μ m) is laminated to polyimide film.Subsequently, laminated sheet is admitted to the thermal treatment zone (maximum heating temperature is 330 ℃), then send into cooling zone (minimum chilling temperature is 180 ℃) and engage and cooling to carry out continuous hot-press, wherein hot press pressure is 3.9MPa, and the hot press time is 2min.Therefore, (width: 540mm, length: 30m), and coiled is rolled up to have made the LED heat-radiating substrate.Measure peel strength, welding thermal endurance and the crooked machinability of the LED heat-radiating substrate that obtains thus.The result is as shown in table 3.Under the temperature of 250 ℃ and 270 ℃, weld stable on heating evaluation.
Table 3
(Evaluation of Heat Tolerance)
The thermal endurance of the LED heat-radiating substrate that makes among the embodiment 4 and 5 is estimated according to following method.
At first, the LED heat-radiating substrate that makes is cut into the size of 1cm * 1.5cm.Subsequently, the cooled plate that becomes in the copper of 10cm * 10cm size (area) and the aluminium foil of LED heat-radiating substrate are coated with the thin thermal grease conduction of one deck, then both are sticked together.Subsequently, be coated with the thin thermal grease conduction of one deck at the Copper Foil of LED heat-radiating substrate and the transistor (2SC3258) of 1cm * 1.5cm edge size, then both sticked together.In the surface of transistorized surface and cooled plate, be provided for inserting in advance the groove of thin thermocouple, in order to measure the temperature (Th) on the transistor surface of interface between transistor and the LED heat-radiating substrate, and the surface temperature (T1) of the interface cooled plate between the Copper Foil of cooled plate and LED heat-radiating substrate.
As mentioned above, use the LED heat-radiating substrate that makes, the laminated sheet of transistor/Copper Foil/polyimides/Al-Mg Alloy Foil/cooled plate is set, and thin thermocouple.
Then, apply the electrical power (P) of 5W to 35W to transistor, after thermocouple indication constant value, measure Th and Tl.
Calculate thermal resistance (Rth) by following formula.
Rth＝(Th-Tl)/P-2×Rg
Wherein, Rg represents (0.35 ℃/W) thermal resistance of one deck thermal grease conduction.
According to said method, measure the thermal resistance of the LED heat-radiating substrate that makes among the embodiment 4, calculate 0.22 ℃/W.The LED heat-radiating substrate has good thermal endurance.In addition, measure the thermal resistance of the LED heat-radiating substrate that makes among the embodiment 5, calculate 0.58 ℃/W.The LED heat-radiating substrate has good thermal endurance.
(embodiment 6)
(manufacturing of LED heat-radiating substrate)
With the hot-air online preheating of three strata acid imide film A1 by 200 ℃ 30 seconds, then send into immediately the biobelt press.Electrolytic copper foil (thickness: 18 μ m) be laminated to the side of polyimide film A1, and Al-Mg Alloy Foil (JIS 5052-H32 (A5052-H32), Furukawa-Sky Aluminum Corp. makes, and thickness is 300 μ m) be laminated to the opposite side of polyimide film A1.Subsequently, laminated sheet is admitted to the thermal treatment zone (maximum heating temperature is 330 ℃), then send into cooling zone (minimum chilling temperature is 180 ℃) and engage and cooling to carry out continuous hot-press, wherein hot press pressure is 3.9MPa, and the hot press time is 2min.Thus, (width: 540mm, length: 30m), and coiled is rolled up to have made the LED heat-radiating substrate.The LED heat-radiating substrate that obtains thus is the bilateral metal foil laminate of Copper Foil/polyimide film A1/Al-Mg Alloy Foil, for flexible, and has good bending property, and tradition and modal LED heat-radiating substrate can not be crooked.
(Evaluation of Heat Tolerance)
The thermal endurance of the LED heat-radiating substrate that makes among the embodiment 6 by with embodiment 4 in identical mode estimate.Thermal resistance is 0.24 ℃/W, and this LED heat-radiating substrate has good thermal endurance.
Industrial applicibility
As mentioned above, the present invention can provide a kind of LED heat-radiating substrate, and this substrate is thin plate and has good heat radiation and withstand voltage properties also have good bending property, for example can curve inwardly with outwardly-bent, therefore is three-dimensional machinable.
Claims (7)
1. LED heat-radiating substrate comprises:
Polyimide film;
Copper Foil or copper alloy foil, described Copper Foil or copper alloy foil are laminated to a side of described polyimide film; And
Aluminium foil or alloy foil, described aluminium foil or alloy foil are laminated to the opposite side of described polyimide film;
Wherein, the thermal resistance between the surface of the surface of described Copper Foil or copper alloy foil and described aluminium foil or alloy foil is 1.8 ℃/W or less.
2. LED heat-radiating substrate according to claim 1, wherein said aluminium foil or alloy foil are without anodization (alumite).
3. LED heat-radiating substrate according to claim 1 and 2, the thickness of wherein said polyimide film is 3 μ m to 25 μ m.
4. according to claim 1 to 3 each described LED heat-radiating substrates, wherein be engaged to the surface of the described polyimide film of described Copper Foil or copper alloy foil, with the surface of the described polyimide film that is engaged to described aluminium foil or alloy foil, comprise the hot press polyimide layer.
5. LED heat-radiating substrate according to claim 4, wherein said polyimide film comprises heat-proof polyimide layer and hot press polyimide layer, it is laminated to the both sides of described heat-proof polyimide layer.
6. according to claim 1 to 5 each described LED heat-radiating substrates, the thickness of wherein said Copper Foil or copper alloy foil is 9 μ m to 200 μ m, and the thickness of described aluminium foil or alloy foil is 200 μ m to 1mm.
7. according to claim 1 to 6 each described LED heat-radiating substrates, wherein said polyimide film, described Copper Foil or copper alloy foil and described aluminium foil or alloy foil use heat pressing forming machines to be bonded together.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010092685 | 2010-04-13 | ||
| JP2010-092685 | 2010-04-13 | ||
| PCT/JP2011/058649 WO2011129232A1 (en) | 2010-04-13 | 2011-04-05 | Heat dissipation substrate for led |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102939671A true CN102939671A (en) | 2013-02-20 |
Family
ID=44798609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800268541A Pending CN102939671A (en) | 2010-04-13 | 2011-04-05 | Heat dissipation substrate for led |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20130199771A1 (en) |
| JP (1) | JP5920213B2 (en) |
| KR (1) | KR101763974B1 (en) |
| CN (1) | CN102939671A (en) |
| TW (1) | TWI591865B (en) |
| WO (1) | WO2011129232A1 (en) |
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| CN104393162A (en) * | 2014-11-05 | 2015-03-04 | 共青城超群科技股份有限公司 | Copper column type substrate-encapsulated LED |
| CN116406090A (en) * | 2023-05-15 | 2023-07-07 | 台山市科伟电子科技有限公司 | Production process of aluminum-based copper-clad aluminum foil plate |
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| WO2014141340A1 (en) * | 2013-03-11 | 2014-09-18 | パナソニック株式会社 | Lighting apparatus and display apparatus |
| US9381717B2 (en) * | 2014-01-22 | 2016-07-05 | Asia Vital Components Co., Ltd | Manufacturing method of heat dissipation structure applied to mobile device |
| EP3276655A1 (en) * | 2016-07-26 | 2018-01-31 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Method and system for bonding a chip to a substrate |
| CN113507780A (en) * | 2021-07-08 | 2021-10-15 | 江西柔顺科技有限公司 | Heat dissipation circuit board and preparation method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI591865B (en) | 2017-07-11 |
| US20130199771A1 (en) | 2013-08-08 |
| JPWO2011129232A1 (en) | 2013-07-18 |
| KR101763974B1 (en) | 2017-08-01 |
| JP5920213B2 (en) | 2016-05-18 |
| WO2011129232A1 (en) | 2011-10-20 |
| TW201205906A (en) | 2012-02-01 |
| KR20130086936A (en) | 2013-08-05 |
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Application publication date: 20130220 |