TW201205906A - Heat dissipation substrate for LED - Google Patents

Abstract

This invention relates to a heat dissipation substrate for LED that is laminated with a copper foil or a copper alloy foil on one side of a polyimide film and an aluminum foil or an aluminum alloy foil on another side, characterized in that the heat resistance between the surface of the copper or copper alloy foil and the surface of the aluminum or aluminum alloy foil is under 1.8 DEG C/W.

Description

201205906 VI. Description of the Invention: [Technical Field to Be Invented] The present invention is directed to a type of LED recording board. The system is about a thin, foldable and three-dimensionally processed heat sink substrate for LEDs. [Prior Art] In recent years, as power consumption is reduced and life is increasing, the demand for LED lighting devices using LEDs (light-emitting diodes as light sources) is generated by rapid illumination, and when the LEDs become high temperature by the heat, the LEDs Luminous effect = private = low, and it will also affect the life of the LED. Especially because the high output and high-party LEDs become more heat-emitting during lighting, so the LED's divergence, suppress the LED temperature rise It is more important. w and ^ because of the substrate's use of a heat-dissipating heat-dissipating substrate, generally used in the surface of an epoxy resin film as an insulating layer (4) Layered woven loose board. However, it is necessary to use the self-endurance voltage surface imm or so, and at least there is a strictness of the left and right, because of the above-like thick Wei Shulai, its thermal resistance Large, so the thermal resistance is reduced. However, a large amount of the addition of the material of the f-filler as described above, the force, the surface is added 4 base: stupid heat-dissipating substrate, non-foldable, and can not be three-dimensional; dimensional processing, circuit The degree of freedom in design will increase, so it is necessary to use LED for two. Thermal substrate. /, has good flexural characteristics. Patent Document 1 discloses a led lighting body, a root body, 1 or a plurality of surface mount type LEDs, a conductive circuit white board, the substrate body, The heat of the polyimine is used to form a three-dimensional shape; the LED is disposed on the substrate body == formed into a pre-circuit, and is disposed at a position on the surface or the back surface of the substrate body, and the conductive is externally connected The circuit, and illuminate it; the remuneration device H of the LED connecting plate body of the conductive circuit minus the surface, formed by Jin Gucheng's scattered H for the purpose of the base 201205906 - 'specialized 2 towels, as a secret guide a good-quality coating, which is a coating of a copper-clad laminate, and a copper-clad layer laminated on one surface of a multilayer polyimide film, and is formed by laminating a metal plate or a ceramic having good thermal conductivity. The multi-xKlik imine film has a low-heat-expandable double-layer laminate of a base polyimide (8) layer, and a thin metal layer having a specific quinone imide unit has a good thermal conductivity. The thickness of 5_~2mm_= and as the -3" reveals a kind of installation for LED Interphase interconnection, comprising a copper or a butterfly metal layer on the substrate, a poly-amine layer or an adhesive layer adjacent to the metal layer, a layer, a liquid or a film-[[Technical Literature] θ [Patent Document 1] [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2009-073670. The problem of the invention is to provide a three-dimensionally-added curry, (four), fine deflection characteristics. The present invention relates to the following matters. The core il5LED heat dissipation substrate is used in the polyimide film. The surface of the laminated copper 1 == sign = the opposite side of the surface # layer (four) or the thermal resistance between her and the heat of the (four) or age gold wire 2_ as shown in the first item of the LED silk The board is not anodized (oxidized by the film). Pain> Self- or alloy 3. The thickness of the heat-dissipating base film for LEDs according to item 1 or 2 is 3 to 25 μm. The heat-dissipating substrate for a coffee according to any one of the items of the present invention, wherein the poly-201205906 surface and the alloy container of the fourth aspect are the heat-dissipating substrate for the LED, wherein The arm-heated polyimide layer is double-sided laminated with a thermocompression-bonded polyimide layer. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, a heat-dissipating substrate, wherein the heat-resistance between the surface of the sheet metal falling on the surface of the sheet metal or the surface of the sheet metal or the surface of the alloy 'It is usually made into fine Asia. [The effect of the invention] Alloy heat:: It is very thin, has good flexural properties, and has excellent post-ability. Therefore, the thickness can be reduced to obtain a sufficient heat-dissipating substrate for the coffee. Since the film becomes very thin, the present invention can be used in three-dimensional processing. The invention is made. The fault is made by the continuous (to-to-Roll) method of good readability, and the purpose is to make the high-adhesiveness of the anode. It is used for the "fl or is alloy fg, and the second is used for the anodizing treatment." At this time, the heat dissipation base for the LED has a plate = 曲 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The thermal resistance between the surface of the aluminum or aluminum alloy foil is 1.8t, which is better than the ideal ϋ Τ Τ Τ & % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % The surface underneath is between the surface of the fine alloy fl and f', for example, the ideal form is arc/w or more, and the upper part is .5 C/W or more, and the most ideal form is a2<; 3c / w to use people 3 Ming tef using adhesives, etc. 'directly laminated copper box in the wake-up imine film;;: ί = 面 surface, and fine gold == two m2 special metal adhesion The best poly-Asian record, but more ideal Lang Er Zhao people ^ metal adhesion of the hot crimping polyimine layer.单, a single layer of imine film with good adhesion to these metals, i can also be a double-sided laminate of her polyimine layer* with == ΐίϊίΐί ϊ 'and especially for heat resistance The double-sided lamination of the pro-imine layer is more interesting than the imine layer. According to the machine;: =imine layer is more ideal' and more ideally "for lamination =:: polyimine diamine, amine film laminated copper alloy, ageing ί, can be used for poly (4), etc. The scale of the imine precursor is coated on steel files or

S 201205906 ϊ ϊ ϊ d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d d Method of making. The use of the copper $ steel alloy is not particularly limited, but a copper belay, particularly a rolled copper foil or an electrolytic copper foil, may be suitably used. More = or ίί gold thickness is 9~200_ is ideal, and 18~2_m phase is produced with a thickness of 35~8G_ copper fi or copper alloy, and '_ or copper alloy is thick and thick. Suitable for high-current copper foil or copper alloy foil, indicating the following surface roughness, more ideally, the state is 2_ or less, and the most = wide = 3 - too small 'can also extend copper or copper alloy fine alloy ―Or such copper. In the invention, (10)!gf| or !g alloy 羯 is not limited by copper, and the 33 alloy may be an alloy of other metals with a main component. Age-age gold: For example, a sinter alloy (Al G gold such as JIS 50002, etc., JIS 5000 series, g 糸〇 gold), which is the main additive substance, may be cited. Example characteristic =: R contains at least weaving alloy _ good change song

The Al-Mg alloy can be used regardless of the composition of the component f = 5% by mass. The more desirable state is 2 to 3 f%, and the strength = the latter is preferable. For example, the above-mentioned: because it can obtain good flexural characteristics, and if it is less than 4μιη ' and then 3μηι or less 'especially fine gold drop is ideal', the most ideal county is anodized Or Ming Green. In addition, when the aluminum foil or the aluminum alloy foil of the anodic oxidation treatment or the anodizing treatment is used, it is excellent in flex resistance and is bonded to the polyimide film by thermocompression bonding. It is not easy to cause poor appearance. Further, it is also possible to use a name box or an alloy case for performing electrolytic treatment (tantalum treatment) using an alkaline electrolyte containing a surfactant, for example,

Pumkawa_SkyAluminumCorp.: KO processing plate, but the ideal form is to use aluminum foil or aluminum alloy foil not treated with KO. 0 Shao Foil or Ming alloy foil, the surface of the laminated side with the poly-imine film, can also be treated with extreme oxidation (also known as oxidation treatment, or sulfuric acid oxidation treatment), or treatment, but From the viewpoint of heat resistance and folding property, it is preferable to use an aluminum foil or an aluminum alloy foil which has not been subjected to extreme oxidation treatment or κ〇 treatment. The surface of the aluminum foil or aluminum alloy foil bonded to the polyimide film, in order to go or = the oil of the manufacture of the oil, the organic solvent is better than aluminum, or the thickness of the aluminum alloy foil is ideal. The form is 2〇〇μιη~1ηι1η, and the more mode is 250~500μηι, and the most ideal form is ·~·μηι. In general, a thin aluminum foil or aluminum alloy foil is suitable for folding applications. In addition, it can be welded (four) or 1S alloy in the (four) shaft alloy hybrid heat sink (four), for example, by using Toyo Steel Co., Ltd. <Knife Co., Ltd.: SAP丨ate Can be welded directly. In the case of Qiaoming, when the polyimide film and the metal drop (the copper box and the sci-fi adjacent side have a clever layer, the thickness of the thermocompression layer is more ideal than the gold g 7 When the surface roughness (Rzjis) of the adhesion surface of the imine film is less than the surface roughness (Rzjis) of the metal foil, the gas yoke film and the metal _ peel strength are obtained according to the environment. However, there is a non-uniform sentence followed by 'the following description of the polyimine film. Polyimine film, there is no particular limitation, as long as it is ideal for the bismuth copper pen (4), it can be side-stacked; Electrical insulation or flexibility is good. Again! 'The heat-resistant support gold can be used, or can not be taken as needed; used in 201205906 with the mi liquid greatly affected. The shape of the board. Multilayer film, sheet, or layer of 2 layers or more in the early layer or the layer of the layer, "Yu Xin" (Tao Yu name), but it is not limited to this. The thickness of the imine film is thick. — Insulation performance, the more _ good, it is reasonable to get enough electricity for two ~ 35 pottery, the more ideal form is 5 ~ 25 pottery, especially the 忒 5 ~ 15_, The most ideal form is 9~15. The reason of the evil is 7 峨, and the ideal form is 4 _point. It is reasonable to say that the sample is 9:15 and the second is based on the solder resistance. The heat I uses a surface-treated polyimine film which is at least surface-treated with a surface such as a corona discharge treatment, an electric surface, a southing treatment, a physical roughening treatment, or a zea smelting coupling agent. The single-layer hot-pressing condition usually does not require surface treatment with a surface treatment agent. (4) "Functional surface agent, propylene coupling agent for various substances., hospital coupling agent, specific (4), may be exemplified by vinyl trimethoxy Wei, Ethylene 5 ginseng P-Methane ethoxy), Ethyl phenyl trimethoxy sulphur succinyl dipropenyl dimethoxy oxime, γ-glycidoxypropyl trimethoxy shi = , 4-epoxypropylbutyltrimethoxywei, γ-aminopropyltriethoxywei, (aminoethyl)γ-aminopropyltrimethoxydecane, Ν-3—(4- (3-month-female, oxy]butoxy]propyl-3-aminopropyltrimethoxy-aged, sodium-des-decane, triazaindane, γ-mercaptopropyltrimethoxyindole Etc. The surface treatment agent of polyamidoxime is preferably an amine-based decane-based or epoxy-based decane-based flaming coupling agent. ^ 201205906 . Further, instead of a decane coupling agent, it is made by titanate. When the system is treated with a doll or a dynasty coupler, the same effect or wrong salt can be obtained. Further, the surface treatment using the Wei coupler can be performed according to a known method. Coupling fresh surface treatment to treat (the sputum can be contained in order to maintain the original state, also in the polyamine or poly 'amine precursor, or the state of:: contains: Ξ by 320 ~5耽_^ The amine film 'is difficult to handle when the substrate is difficult to handle, etc., can be used in the film or substrate which can be peeled off in the I-step of LiLf: The heat resistant layer (sai) and the bonded two screens have thermocompression bonding properties and/or using a plurality of layers having thermocompression bonding and a layer of i 2 or more. An example of the rhyme structure is Sa2/Sal/Sa2, ScSai^fl1//Sa2*. Further, a polyimide film having an early layer of a layer (10) having thermocompression bonding property may also be used. ,) The layer (sa2) used for the bonding and/or adhesion is made. The woven fabric and the human (4) layer (5) are selected from the group consisting of a layer having thermocompression bonding and a layer having adhesiveness. Two or more layers of polyacrylonitrile film having thermocompression bonding and/or adhesion, the layer having heat resistance (Sal) and the thickness of the layer having thermocompression bonding and/or adhesion can be Appropriate choice. However, in the present invention, as described above, the thickness of the outermost two pressure-bonding and/or adhesive layer (Sa2) is preferably a bonding surface of the five-component foil and the polyimide film. The surface roughness (Μ.) or more is more desirable. The form is 0.5 or more, and the more ideal form is _ or more. The most ideal form is set to be more than 2 divisions. Further, the thickness of the layer (Sa2) having thermocompression bonding properties or adhesiveness is preferably 3 μm or less. - the heat-dissipating substrate for LED of the present invention is a laminated copper foil or a copper alloy foil, a polyyttrium yam (polyimine layer), an aluminum foil or an aluminum alloy foil, and according to the manufacturing method thereof, 201205906 is not limited herein. The bite is now used on the side of the poly-imide film to laminate the copper box-bonding material), by heating and/or adding μ to laminate i = two in copper or copper alloy boxes, and (4) The alloy is rubbed into a 孰 = guamine solution or a polyimide precursor solution (poly phthalate hydrazine), which is heated and dried depending on the island. • 醯 imidization, and can also be heated by yttrium imide film. It is obtained by lamination or the like. In the copper _ "all ^ two two jf liquid special", if necessary, heat drying, 醯 imidization, and then, can also be added by the domain of the alloy is heated or pressurized The film and metal foil (copper foil, aluminum foil) are directly laminated and compared with the gold, so that the addition of m, force ^ or force is two: Ϊ 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚The layer car is a resin coated with a polyimide or a metal box, or coated with a polyimide, which is coated with two === oil shouting, slit coater (slitcoater) ), cloth money (c〇 job acoater) #, generally used in the implementation of the method. Wind #日# will ΐΐϊί f layer or thermocompression resin layer of metal box and polyimine _ crystallized use heating The heat treatment condition and the pressurization condition of the sputum, the pressurizing device or the pressurizing twisting device are appropriately selected according to the material to be used: 3, the stack of the gold fine concentrating film may be continuous or =, Although it is not particularly limited, it is possible to suitably use heat resistance by using a roll lamination (m (7 is preferably carried out continuously) and 曰_u_nate) or an amine film polyimide film such as double-strand extrusion. Insulation, etc., can be used to make the eucalyptus of the family layer, or to make the melamine on the sputum. The type of melamine can also be used. ^ 201205906 The face film ' can be produced by a known method. For example, a single-layered polystyrene film can be obtained by the following methods. The brother ± will be used as a precursor of the brewing imine. A method in which an amine acid solution is cast or coated on a ruthenium support, and the ruthenium is imidized; a hot polyimine solution is cast or coated on a support, and 2 or more layers are added as needed. The ruthenium imine film can be obtained by the following methods: ancient; ^ as a precursor of the poly-imine, the poly-tantoic acid solution scale or coated on the glutinous acid: and, in the polyamic acid layer On the top surface, a polyamic acid solution of a polyimine precursor of ',, or more than θ is sequentially cast or coated, and the ruthenium is imidized; η η main ϋ* is used as the second layer The polyamic acid solution of the above-mentioned poly-imine precursor is the same as the method of "coating on the support and imidating the ruthenium; (5) casting the poly-proline solution Or a method of coating on the support, and the top surface is sequentially heated by the poly-Asian view of the second layer or more of the scale cloth; ^6) simultaneously casting the second layer of the polyimine solution or A method of applying on the support and heating as needed; and a method of laminating two or more of the polyiminoimide films obtained in the above (1) to (6) directly or through an adhesive. Everyone can't use the copper box of the heat-dissipating substrate of the LED or the copper, the whistle or the Ming & gold ^1 as the support, and the polyimine film is directly formed on the upper side. The sub-type film is particularly suitable for use in the heat-resistant polyimine layer (Μ) of the double-sided yoke-containing polyimide layer (10). i = two (S2) early layer of polyimide film. In the polyimine film having thermocompression bonding property, the thickness of the heat-resistant polyimide layer (S1) and the heat-reactive W-imine layer (S2) can be appropriately selected. However, in the present invention,

The thickness of S 12 201205906, the mouth should be; the second layer of the thermo-compressive polyimine layer (S2) of the outer layer of the scorpion is enough to make the ideal adhesion ^2 = 1 is 1, (called thickness, ideal state = μη^τ ligament _ imine layer by heat-bonded polyimide layer (S) in the heat-resistant polyimide layer (S2), and can be set thickness In the substantially same resistant polyimide film, 'as a heat-resistant polyimide layer (si) layer (Ti%, at least two of (1) to (4)) and the following characteristic i. In combination with (3), etc., and especially suitable for the heart (in the case of il in the case of a poly-imine film, the glass transition temperature is 3 〇〇. The 〇 state is not the glass transition temperature of 330t or more. More ideally, in the case of a single polyimide film, the linear expansion coefficient (5 〇 ~ 200. 〇i mesh If approximate to the 张 系数 在 在 在 在 在 近似 近似 近似 近似 近似 近似 近似Specifically, g, the thermal expansion coefficient of the polyimide film is more than - cm ~ 28x [6 (10) / 啦 / ΐ, and more ideally the state is 9xl0 - t20xl0 - 6 / cm / C, more ideally 12xl〇-6~18xl〇_6cm/cm/〇c (3) In the case of a single polyimine film, the tensile modulus (md, ASTM "D88'2) is 300 kg/nmi2 or more, and the preferred state is 5 〇〇kg/mm or more. The ideal state is 7 〇〇kg/miTi2 or more. (4) The preferred mode is that the heat shrinkage rate is 0.05% or less. The heat, the polyimide layer (Si) can be used by the following components The synthesized poly-imine, § hai and other components comprise: will be selected from 3, 3, 4, 4, a biphenyl tetracarboxylic dianhydride (s - BPDA), pyromellitic dianhydride (PMDA) And an acid component containing a component of benzophenone IV 201205906 carboxylic acid dianhydride (BTDA) as a main component; and a selected from p-phenylenediamine (PPD) and 4,4,diaminobiphenyl a diamine component containing a component of ether (DADE) as a main component. 4,4'-diaminodiphenyl ether (DADE), which may be partially or completely substituted with 3,4'-diaminodiphenyl ether (DADE) The heat-resistant polyimine layer (S1), for example, the following polyimine is preferable. (1) From 3,3',4,4'-biphenyltetracarboxylic dianhydride (5::6? 0 VIII) with polyphenyleneimine manufactured by p-phenylenediamine (PPD), and according to Further, it is further polymerized with 4,4'-diaminodiphenyl ether (DADE). In this case, PPD/DADE (Morby) is preferably 100/0 to 85/15. 2) From 3,3',4,4'-biphenyl tetra-acidic two-needle (s-BPDA) and pyromellitic dianhydride (PMDA) with p-phenylenediamine (ppd) and 4,4, one or two Polyimine produced by aminodiphenyl ether (DADE). In this case, BPDA/PMDA (Morby) is 15 / 85 to 85 / 15, while PPD / DADE (Morbi) is ideal for 90/10 ~ 10 / 90. (3) Polyimine produced by pyromellitic dianhydride (pmj) A) and p-phenylenediamine (ppD) and 4, <-monoaminobiphenyl shim (DADE). In this case, DAD: /PPD (Morby ratio) is preferably 90/10 to 10/90. (4) from 3,3',4,4'-dibenzophenone tetracarboxylic dianhydride (311) VIII) and benzene tetrahydrofuran anhydride (PMDA) and p-phenylenediamine (ρρ£) and 4,4,monodiaminodiphenyl ether (polyimine produced by DADE. In this case, BTDA/PMDA (Mo 80^90^10 , ^ PPD/DADE ^ 30/^90/10 : Ideally. In addition, other tetracarboxylic dianhydrides or diamines may be used in the range which does not impair the physical properties of the heat-resistant polyimide. The synthesis of the heat-resistant polyimide of the imine layer (S1 layer) , 根福Γ Γ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

S 14 201205906 Ingredients' The diamine component is reacted with an acid component (four kinds of acid buffered organic solvent, and is placed as a poly-branched amine coffee, ~^

Si is 4 = after using 'the formation of the doping liquid II = can be made heat-resistant poly styrene = R when the polyphosphonium quinone imine is cyclized to take a ^:: Ming t ' in heat-resistant polyimine After the film of the doping liquid is laminated on the film of the doping liquid, both sides can be simultaneously imidized. The film of the J, ί, 参 杂 与 与 与 与 与 与 聚 amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp amp After the doping of the liquid layer, the double lysine can be simultaneously aminated. The method is described below. The rn曰t surface is a thermocompression-bonded polyamicimide of the thermocompression-bonded polyamicimide layer (S2). It has a thermocompression bonding property with a metal|| The thermocompression-bonded polystyrene 4 is more desirable: it is a temperature at which the temperature of the thermocompression-bonded polyimine is above the glass transition temperature to below C, and can be bonded to the metal n-layer. amine. The thermocompression-bonded polyimine of the second pressure-sensitive polyimide layer (S2) preferably has at least one of the following special resins (2) to (5). _(2) The peeling strength of the metal foil and the polyimide (S2) is 〇7^/face or more, that is, after 7 hours of heat treatment at 150 C for 168 hours, the retention of the peel strength is also 9% or more, or even 95% or more. The best is more than 1%. (3) The glass transition temperature is 130 to 330. (:) (4) The tensile modulus of elasticity is 1〇〇~7〇〇Kg/mm2. (5) Linear expansion coefficient (50~200°C) (MD) is 13~30x10-6cm /cm/〇c 〇 The thermocompression-bonding polyimine of the thermocompression-bonded polyimide layer (S2) may be selected from various known thermoplastic polyimine. For example, polyimine synthesized from the following components may be used. The components comprise: a material selected from the group consisting of 2, 3, 3, 4, a biphenyltetracarboxylic dianhydride <^a BPDA), 3,3,4,4, a biphenyltetracarboxylic acid Anhydride (s-BPDA), pyromellitic dianhydride (PMDA), 3,3',4,4'-dibenzophenone tetracarboxylate dianhydride (BTDA), 3,3,,4,4, 15 201205906 - 二_四麟二gf, 4,4'-oxydiphthalic dianhydride (qd carboxy 酉 yiyi anhydride 4) is a knife, and the ideal form includes An acid component; and a benzene group selected from the group consisting of 1,4-bis(4-aminophenoxy)benzene~phenoxy)benzene, i,3-bis(3~aminophenoxy)benzene, Aminophenoxy)phenyl]propane, 2,2-bis[4-p-amine" = calcined, bis[4-(4-gphenoxy)phenyl]-hard, bis[4-bru- benzene Basis The diamine component having at least three benzene rings in the main chain is preferably a diamine component which is contained as a main component and optionally has one or two benzene rings in the main chain. The pressure-bonded polyamidiamine is especially suitable for use in the selection of 2,3,3,4,2-biphenyltetrasporin-(a-BPDA), 3,3',4,4'-biphenyl Tetracarboxylic dianhydride (s-BpDA) anhydride (/ should be A), and 3,3,,4,4,-dibenzophenone four thieves two _ ^ ^ spoon - Wencheng knife: and remote from 1,4 - bis(4-aminophenoxy)benzene, bis-bis-benzoic benzene, U-bis(3-aminophenoxy)benzene, and 2,2-bis[4 phenylf-yl)benzene a polyimine synthesized by a diamine component of a propylene group. 1 Γ, Η: ϊ ( ( ( 四 四 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视 视An amine component and an acid component. The pressure-sensitive polyimine component, in particular, a diamine component containing 8 〇 mol% or more, including u-bis (4-aminophenoxyl group, also referred to as TPER) , 3,3,4,4'-biphenyltetracarboxylic dianhydride (s-BpDA) and / 3 3, 4, - = tetra-jujuic anhydride (a-BPDA) The creation of the bribe is ideal. The love ! ΓΒ Α Α Α Α Α 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在Within the range of physical properties, it can also be replaced by a tetra-dianhydride, for example, 2,2-bis(3,4-di-phenyl) propyl sinter, 2,3,6,7-naphthalenetetracarboxylic acid Anhydride, etc. The thermocompression-bonded imine can be produced as follows. First, each of the above-mentioned organic solvents is about 1 (ΚΓ(:, Τ, the temperature is 2G~攸), and it is reacted with other tetracarboxylic dianhydrides and other diamines in an organic solvent.

S 16 201205906 is a solution of polylysine. Then, the polyamidiamine is doped and then heated, and the self-doping solution is cyclized using 'poly" acid-imine to produce thermocompression bonding to remove 'at the same time, and will be as described above. The manufacturing is made up of, for example, 250t, and the imidization agent is added at 15〇. $, the spoon solution is heated to a 150-degree reaction, and after cyclization with the amine, the solvent J, ' _ ^ 曰 = 15 to 50 ° C is heated to become a powder, and then the powder is decomposed by 1 An organic solvent solution of a heterojunar mixture in a solvent. The solution and the organic agent can be obtained by hot pressing in order to obtain the thermocompression-type polylinimide, and the molar amount of the base in the organic solvent is used as the dianhydride relative to the anhydride oxime. The total amount of red is ^:Tu 'and the most ideal one is -there is a counter-contact with the anhydride, and the amount used is the ratio of the molar amount of the base, which can be __ below _. The anhydride of tetrawei-anhydride is hot pressed, and in the production of a polyimine, when it is obtained, the laminate with the metal foil, that is, the blade 1 of the LED of the present invention has a small decrease. The bonding of the LED-shaped heat-dissipating substrate is strong, and in order to limit the gelation of the poly-proline, the relative concentration of the body component (polymer) is added to the (10) μμ phosphorus stabilizer, such as phosphorous acid. Triphenyl ester 'triphenyl phosphate 0, dry inside and 'to promote the brewing imidization, can be added to the dope. For example, imidazole, 2-mercaptoimidazole, anthracene, 2-bi-branched phenyl ♦ sitting, benzene holding, dissimilar material, substituted coffee, ^ 〇.〇5~1〇% by weight, especially The ratio of αι to 2% by weight = ^acid' low temperature forms w Yalai, so in order to avoid the lack of sub-sector; r is more, for the purpose of stabilizing the bonding strength, can also be used for amine poly-proline The solution is added with an organoaluminum compound or an inorganic aluminum compound. For example, the amount of aluminum hydroxide can be more than 1 ppm with respect to ^= tin ^, and the ratio of 丨 丨 丨 8 8 8 8 , , , , , , , , , The organic solvent used in the preparation of polyamines by the diamine component, that is, 201205906 = N-mercapto-2 can also be used for any of heat-resistant polyimide and thermocompression-bonded polyimide. - pyrrolidone, N,N-dimethyldecylamine, N,N-dimethylhydrazine.醯月女, N,N-diethyl acetamide, dimethyl sulphate, hexamethyl spiramine, sinus sinensis, 曱g classification, etc. These organic solvents may be used singly or in combination of two or more. Heat-resistant heteroimine and thermocompression-bonded poly-amine, for the (iv) amine terminal i with λ anhydride, such as 'can use phthalic _ _ and its substituents, hexahydro-ortho = heat, (3)) one or both sides A hot-mixed polystyrene film is prepared by a four-part heat-bonding polyimide film, which is preferably formed by co-extrusion of a casting film (also known as a glutinous imine) a method of doping a doped liquid of S1) with a thermocompression-bonded polyimine (8)) into a multi-layered polyimine film; or a doping of (i) imine (S1) The coating is applied to the support, and the amine film is dried and dried, and the imidization is obtained to obtain a multi-layered polyaluminum. =======辞3—Deletion No. 43 (曰- Example ^ The following table is not a heat-resistant polyimine (sn' amine (S2) poly-proline solution produced by a three-layer polyimide film having a double-sided splicing property, by means of ^ and ^ The mold for forming a polythene, which is cast on a non-recorded steel mirror to give a three-layer extruded cloth on the support surface, so that the heat-resistant cast coating is 45-, and the hot-dust jointed polyimine layer on both sides thereof Degree is 4~~20μηι. Then, at 1〇〇~ as: θ) The sum of the best is 1 C, and the cast film is dried to obtain a self-supporting film of a self-supporting film (4) which is a semi-hardened 18 201205906. The poly-growth = film is in the = 2 00 == In the case of the squamous membrane, the membrane is self-supporting in the form of a splicing property. 乂 and/or 疋 酿 酿 酿 为 为 为 为 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂% by mass, and the most ideal form is 3G~5◦When the V is tied to the self-supporting film, the temperature is raised to dry • The imidization: = The temperature rises = ^:; The temperature rises above the town is divided by Zhang Kezhen The line ___ 增加 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于When the device is solid, the shape of Ji:!! = the temperature of 〇p, the drying and heat is the best, and the ideal form is W1 ^; ::i; t (two) machine solvent And the formation of water and other components of the wave 2

Sit is less than or equal to the weight of Sit, and the solvent or the like is self-supporting, and the self-supporting ΐ ί 自 置 置 置 置 皮带 皮带 皮带 皮带 皮带 皮带 皮带 皮带 皮带 皮带

° ^5 itiiZ Tensile rate i Shrinkage T is the most: two films = the right or the longitudinal direction with a suitable shrinkage device. The sample of the heart G.5~5% expansion ratio) stretched again / 19 201205906 can iJf tension under the temperature of 100 ~ Du (10), by heat treatment, the ideal aging age is hot on both sides and 'manufactured long The polyimide film having a bell-bonding property on both sides can be wound into a roll shape by a known method. And - the film of the doped liquid of the yttrium imide film and the film on the side adjacent to the support ϊ ί ί Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ 掺杂 掺杂 掺杂 掺杂 掺杂 掺杂 ' ' ' ' ' ' ' ' ' ' ' ' In the method of the above-mentioned peak-resistant polyimide layer (S1), the method for producing a heat-dissipating substrate for LEDs is described. 'I'm coming to Asia and the United States to use the heat-dissipating substrate for LEDs. For example, in the heat-resistant work, that is, the heat-resistant substrate of the object, it is more desirable. The thermocompression-bonded polyimide layer is used in the surface of the thermocompression hybrid imine layer (S2) (straight. imine film 'or copper alloy 羯' and thermo-compression bonding Direct lamination (4) or alloy § §. 2) Lai surface (B side) As a method for manufacturing a double-sided thermal substrate for thermocompression-bonded polyimide film, Led for 1) long strip-shaped metal foil (copper foil or copper alloy / °: · · crimping polyimide film, long strips of heat, the order overlaps 3 pieces, and Send to the heating and crimping ί set the self-power ^) according to the use of hot air supply device or infrared heater, etc. At this time, immediately before the introduction, along the line 50 to 25 (). Second, the ideal state of the car is around 250C', especially above 15〇. [ 20 201205906 · And 25 〇 t: The following temperature, preheating is preferably about 2 to 12 seconds. 't) Using a pair of crimped or double strip extrusions, the temperature in the heated crimp zone is 20 higher than the glass transition temperature of the brewed imine (S2). 〇 Above the temperature to 400. 3 temperature range, especially in the glass transition temperature of the brewing imine (S2) is higher than 3 (rc above the temperature to 40 (TC temperature range, metal foil / poly 醯3 pieces of imine/metal foil are superimposed under pressure and hot-pressed. / 3) Especially in the case of double-belt extrusion, it is cooled under pressure in the cooling zone, and is cooled to the more iminoimine. S2) The glass has a low temperature and is cooled to a temperature of at least 3 Torr, and is wound on a double-sided layer of a polyimide film, and is wound into a roll. In the manufacturing method of the rolled LED, the pre-heating before the thermocompression bonding prevents the lamination of the laminated crucible after the thermocompression bonding, such as the water confinement of the poly-Asian woman. The appearance of the bubble is not good, and the foaming at the time of the formation of the soldering bath during the formation of the electronic circuit can be prevented, and the yield of the crucible can be deteriorated according to the result. Further, the thermocompression bonding apparatus is integrally disposed. The method in the furnace can also be considered 'but because the thermocompression bonding device is substantially limited to such as a small one, the shape of the led ίίΐ substrate is limited, and thus · X, that is, in the shape of '^^β to the layer of 钊 酿 酿 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 亦 钊 钊 钊 钊 钊 钊 钊 钊 钊 钊 钊 钊 钊 钊 钊 钊 钊 钊& squeezing, which is a high-temperature heating-cooling under pressure, and the use of the addition, ', " quality hydraulic type is ideal. The imide film and the metal drop are double-strand extruded by thermocompression under pressure-cooling and lamination, and the charging speed can be appropriately set to above 'and' and the strip can be obtained and the width is about 4QQmm or more. The wide red joint strength is large, and there is no wrinkle on the surface of the gold metal. [Buy gold (four) laminated poly-Asian _ (.led heat substrate). Acid imide LED heat sink substrate, supply heat pressure Contact poly (that is, 2 pieces of protective material), thermocompression under pressure - cooling and straight brakes are also rational & protective material 'as long as it is non-thermal pressure bonding and good surface smoothness 201205906 regardless of material Use, for example, gold shirt, and especially * copper drop, not high resistance New Zealand Yalai (made by Yixing Co., Ltd., LhXS) The thickness of the temple is about 5 to 125 μm. The heat-dissipating substrate for LED obtained as described above is formed into a metal wire by a 'wire or copper alloy case' according to a known method, and a metal 卽 曰曰 曰曰 is formed. The LED of the present invention. Using a heat sink substrate, heat dissipation is good,

I LPT) Illumination, LED f light, and a large number of LEDs on the substrate can also suppress the temperature rise of the LED and the decrease in luminous efficiency. ,』J

[Examples] The present invention will be described in more detail with reference to the examples, but the present invention is not limited thereto (evaluation method), and the strength and strength are 9 〇 according to 瓜·C5〇16. , 5 sides wide condition The peel strength between the polyimide film and the aluminum foil was measured. A laminate of 醯ίamine/(iv) was measured. Determination of peel strength, implementation =

And welding heat resistant 260 c · 3 seconds after treatment. M (2) Solder heat resistance: according to the laminate of ns · C6481 聚亚亚_; while the side of the polyimide layer of the laminate was observed to have n heat and heat resistance. Bubble, X: There is foaming. of". The imine has a surface which becomes the outer side and _ or less ==' 〇 · no crack, and X: there is a crack. (Reference Example 1: Heat-resistant polyimine S1 in N-methyl-2--will be S, U, M, 22 201205906: Biphenyltetra-dianhydride (s-BPDA) face: 998 molar ratio Add, the concentration of the early body becomes 18% (% by weight, the same in the same town), and the viscosity of the solution of the polyacid solution is 25t: the viscosity of the solution is about 3 kPa (the viscosity of the unit (test case 2: heat) Manufacture of Crimped Polyimine S2 with Doping Solution) In the case of N-mercapto-2-indenyl milk, 1>3-bis(4-aminophenoxy)benzene (TPE-R) and 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BpDA) and 3 3, 4 bucket, -biphenyl acid dianhydride (S-BPDA) to 1〇〇〇: 2〇〇 : 8 〇〇 Mo Er Bi Jia /, 俾 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体 单体The viscosity of the solution of the polyamic acid solution is about 1680 poise. (Reference Example 3, 4: manufacture of thermocompression-bonded multilayer polyimide film A1, A2) The film-making device of the mold (multi-manifold type mold) changes the thickness of the three-layer extruded face, and dissolves the grain and the poly-branched acid of Reference Example 2 Casted on a metal support and dried continuously with 14 (r hot air of rc, and then peeled off to form a self-supporting film. The self-supporting crucible peeled from the support is slowly heated from 150 ° C by twisting. Until the thief, the removal of the solvent was followed by imidization. Two types of long-length three-layered polyimide membranes having different thicknesses were produced and wound into a roll. 'Evaluated three-layered polyfluorene The results of the imine film (layer composition: S2/S1//S2) are shown here. (Thermal pressure-bonded multilayer polyimide film A1) • Thickness: 2.5 μm / 7.5 μπι / 5 μίη (total 12.5μηι) • Glass transition temperature of S2 layer: 240°C • Glass transition temperature of S1 layer: above 3〇〇°c, no clear temperature can be confirmed. } 4W^WMt(50~20(TC): MD19ppm/t:, TDl8pjpm/t: • Mechanical properties (test method: ASTM · D882) 1) Tensile strength: MD, TD each 520MPa, 2) Tensile rate: md, td each 90%, 3) Stretching Elastic coefficient: mdjd each 7200MPa. 23 201205906 • Electrical characteristics (test method: ASTM · D149)]) breakdown voltage (breakdownvoltage): 4.9kV. (Thermal pressure-bonding multilayer polyimide film A2) ^ • Thickness composition: 4μηι/17μπι/4μηι (total 25μηι). • Glass transition temperature of the S2 layer: 240 °C. • Glass transition temperature of S1 layer: above 30 (TC, no clear temperature can be confirmed. • Linear expansion coefficient (50~200°C): MD19ppm/t:, TD18ppm/t: • Mechanical properties (test method: ASTM · D882) 1) Tensile strength: 520 MPa for MD and TD, 2) Tensile ratio: 100% for MD and TD, 3) Tensile modulus: md, TD 72 MPa each. • Electrical characteristics (test method: ASTM · D149) Ο Crash voltage: 7.1 kV. The thermocompression-bonded multilayer polyimide film (A1, A2) has a thickness of 12 5 μm 2 25 μm, which is thinner than an epoxy resin film (thickness: 1.2 mm) which is conventionally used for general heat dissipation substrates for LEDs, but is electrically The insulation is the same. In the following examples, a copper foil was laminated on the A side of the polyimide film, and a case was laminated on the B side of the polyimide film. In order to remove the oil adhering to the surface, it is treated with an organic solvent. (Examples 1 to 3) (Production of heat-dissipating substrate for LED) 3-layer brewing which was preheated by heating in an in-line of 2 〇〇 ° C immediately before the double-belt extrusion One side (A side) of the imine film A2 is laminated with an electrolytic steel foil (thickness 丄18 μm, Rz=〇.6 pm), and laminated on the opposite side (B side) as shown in Table 1 without treatment or surface. The treated Al_Mg alloy foil (manufactured by Furukawa-SkyAluminum Corp., A5052-H34, thickness: 300 μη〇, and = the polyimide film 2 was sent to a heating zone (maximum heating temperature: 33 〇. 〇, then sent to the cooling zone ( Minimum cooling temperature: 丨8 (rc), at crimping pressure: 3 9MPa,

S 24 201205906 I Table 1] ~ Surface treatment of aluminum foil on the side of the laminate side of the polyimide film No. Example No treatment Example 2 氧化铝 Alumina sulfate film treatment Example 3 Treatment (treatment layer: about 1.5 Μηι) 压 2 minutes during crimping, continuous thermocompression bonding - cooling and lamination, manufacturing a heat dissipation substrate for LED (width: 540 mm, length: 30 m), and winding into a roll shape. Table 2 shows the results of evaluation of the peel strength, solder heat resistance and bending workability of the heat-dissipating substrate for LED obtained. The evaluation of solder heat resistance was carried out at 25 ° C.

Peeling strength (N/mm) I (between AI film/polyimine) Evaluation of solder heat resistance (250〇C) Evaluation of bending workability Initial heat and humidity after welding heat f Copper foil outer curved copper foil bending Example 1 2.7 3.1 2.9 3.1 〇〇〇 4 < 3.6 X 〇 X Example 3 4 < 4 < 4 < X 〇 X (Examples 4 to 5) (Manufacture of heat-dissipating substrate for LED) Immediately after double-belt extrusion The front line is 2 miles. One side (a side) laminated calendered copper foil (thickness: rough grading grade, Κ_ζ=1.2μηι) of the preheated three-layer polyimide film is heated for 30 seconds by the hot air of the crucible and is on the opposite side. (B side) laminated untreated Al~~Mg alloy foil (manufactured by Furukawa-SkyAluminum Corp., Α5052 - H34, thickness: 3〇〇μπ〇, and the polyimide film is sent to the heating zone (maximum heating temperature) .330C), then sent to the cooling zone (minimum cooling temperature: 18 〇 it), f crimping pressure: 3.9 MPa, crimping time 2 minutes, continuous thermocompression bonding - cooling and lamination, manufacturing heat sink substrate for LED (width: 540 mm, length: 3 〇 m), and wound up in a roll shape. Table 3 shows the results of evaluation of peel strength, solder heat resistance, and bending workability of the heat-dissipating substrate for LED obtained. 270 ° C. 25 201205906 [Table 3] Polyimide film stripping f (A ya strength (Ϊ [film / poly 1 si / mm) between the imine) Welding heat resistance evaluation, bending processability evaluation initial damp heat Post-weld heat-resistant 250〇C 270〇C copper chain outer bending||Foil bending 4 Example A1 1.7 1.6 1. 7 〇〇〇〇 Example 5 A2 3.1 3.3 3.5 〇X 〇〇 (Evaluation of Thermal Resistance) The thermal resistance of the heat-dissipating substrate for LEDs manufactured in Example 4 and Example 5 was evaluated by the following method. The heat-dissipating substrate for the LED was cut into a size of 5 cm of icmxl. Next, a thin heat-conductive grease was applied to the aluminum foil side of the heat-dissipating substrate made of copper and the surface of the heat-dissipating substrate for LEDs having an area of 10 cm x 10 cm, and the two were attached. After that, a very thin thermal conductive grease was applied to the copper foil side of the heat dissipation substrate for LED and the transistor (2SC3258) having a side surface of 1 cm x 1.5 cm, and the two were attached. For measuring the transistor and the LED. The temperature Th1 of the outermost surface of the transistor side of the interface of the heat dissipation substrate and the temperature T1 of the outermost surface of the water-cooled plate side of the contact portion of the water-cooling plate and the copper foil for the heat-dissipating substrate for the LED are previously set on the surface of the transistor and the water-cooled plate. a groove for inserting a fine galvanic couple. Use a heat-dissipating substrate for LEDs manufactured as described above and mount it (|copper foil/small imide film/Al-Mg alloy foil/water-cooled plate and fine thermocouple „ Next, Apply 5 to 3 stomach power to the transistor p, given waiting calorimetry measurement Th, Tl. based thermal resistance Rth is calculated by the following formula.

Rth=(Th-Tl) /P-2xRg Rg is the thermal resistance of the thermal conductive grease 1 layer (〇: 35.〇/"). π find f the heat of the LED heat sink substrate manufactured in Example 4. The resistance is L'm and its if is a good thermal resistance. Furthermore, the LED produced by the embodiment 5 is obtained, and the thermal resistance of the substrate is Ofc/w, and is a good thermal resistance. (Example 6) ', (manufacturing of heat-dissipating substrate for LED) is heated by hot air of ·C for 3G seconds immediately before the double-belt extrusion and pre-26 *

S 201205906 A three-layer laminated polyimide film Ai laminated with an electrolytic copper foil (thickness: 18μηι), and laminated on the opposite side of the surface of Al-Mg alloy foil (Fumkawa-SkyAluminimi forp, manufactured by JIS5052-H32) A5052—H32), thickness: 300μη〇, and the polyimine film Α1 is sent to the heating zone (maximum heating temperature: 33 (rc), then

Sit卩, (minimum cooling temperature: 18G °C), laminated at a crimping pressure: 3.9 MPa, L. 2 'continuous thermocompression-cooling, to manufacture a loose-area laminate for LEDs, and (4) == A1 —Mg with her spoon double-sided metal sway and has good (four) LED recording and subtraction board, which is folded, foldable (evaluation of thermal resistance), heat-dissipating substrate, heat, 6 manufacturing, LED [industrial use], .c/w, and good Thermal resistance. As described above, according to the present invention, the L¥D xiao heat-dissipating substrate having excellent detachment and squeezing properties, for example, is folded inwardly and outwardly. Very binding, and has good flexural characteristics, [simplified description of the schema] Benefit Description] [Main component benefits

Claims (1)

201205906 VII. Patent application scope: 1. A heat dissipation substrate for LEDs, in which a copper foil or an alloy foil is laminated on one side of a polyimide film, and an aluminum foil or an aluminum alloy foil is laminated on the opposite side surface, which is characterized by ' ° The heat between the surface of the copper foil or copper alloy foil and the surface of the aluminum foil or aluminum alloy foil is 1.8 ° C / W or less. ‘, ', 2. If you apply for a patent scope! The item 1^ uses a heat-dissipating substrate in which the aluminum or the alloy 羯 is not anodized (oxidized by a film). 3. For the heat-dissipating substrate for LEDs of claim 1 or 2, the thickness of the polyimide film is 3 to 25 μm. Eight 〇Α 4_ such as the scope of patent application! The heat-dissipating substrate for LEDs according to any one of the preceding claims, wherein the bonding surface of the polyimide film to the copper box or the copper alloy, and the bonding surface with the aluminum foil or the aluminum alloy foil are thermocompression bonded. Polyimine layer. /·For example, the heat-dissipating substrate for LEDs of the fourth application patent scope, wherein the poly-Asian female membrane is a thermocompression-bonded polyaniline layer laminated on the double-sided heat-resistant polyimide layer . The heat-dissipating substrate for LEDs according to any one of claims 1 to 5, wherein the thickness of the copper foil or the copper alloy foil is 9 to 2 〇〇μηη, and the thickness of the aluminum foil or aluminum alloy is 200 μπι~lmm . The heat-dissipating substrate for LEDs according to any one of claims 1 to 6, wherein the polyimide film, the copper foil or the copper alloy foil, the aluminum foil or the aluminum alloy foil are pressurized The forming device is heated and bonded. Eight, schema: no. 28 . S