WO2010150810A1 - 光反射基板およびその製造方法 - Google Patents
光反射基板およびその製造方法 Download PDFInfo
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- WO2010150810A1 WO2010150810A1 PCT/JP2010/060629 JP2010060629W WO2010150810A1 WO 2010150810 A1 WO2010150810 A1 WO 2010150810A1 JP 2010060629 W JP2010060629 W JP 2010060629W WO 2010150810 A1 WO2010150810 A1 WO 2010150810A1
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- light
- light reflecting
- reflecting substrate
- aluminum
- aluminum plate
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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
- 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
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/13—Discrete devices, e.g. 3 terminal devices
- H01L2924/1301—Thyristor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0058—Processes relating to semiconductor body packages relating to optical field-shaping elements
Definitions
- the present invention relates to a light reflecting substrate having an insulating layer and a metal layer used for a light emitting element. More specifically, the present invention relates to a light reflecting substrate used in a light emitting diode (hereinafter referred to as LED) light emitting element, and more particularly to an improvement in the reflecting substrate of the LED light emitting element.
- LED light emitting diode
- a white LED light emitting element an LED light emitting element for illuminating a display device that performs color display using an RGB color filter is generally used, and a multicolor mixed type LED light emitting element is used.
- This multi-color mixed type LED light emitting element emits white light by simultaneously emitting LEDs of three colors of RGB, and performs color display by using the white light and a color filter of a display device.
- this multi-color mixed type LED light emitting element emits light from each of RGB LEDs, so that each color has high purity and excellent color rendering.
- a large number of LEDs are required. And there is a problem that the price becomes high.
- FIG. 5 is a schematic view showing a configuration example of a phosphor-mixed white LED light-emitting element described in Patent Documents 1 and 2, and may be used as a part of the structure in the light-emitting element of the present invention. It ’s good.
- reference numeral 100 denotes a white LED light emitting unit.
- a blue LED 110 is face-down bonded to a substrate 140 having external connection electrodes 120 and 130, and YAG fluorescent particles 150 are mixed into the blue LED 110. Molded with a transparent resin 160.
- White light is emitted from the white LED light emitting unit 100 in the direction of the arrow on the light emitting surface side by the light excited by the YAG fluorescent particles 150 and the afterglow of the blue LED 110.
- the thickness of the transparent resin 160 mixed with the fluorescent particles 150 is increased in order to increase the white light emission output. It is considered preferable to take measures such as increasing the thickness or increasing the content of the fluorescent particles 150 of the transparent resin 160. However, when these measures are taken, depending on the thickness of the transparent resin 160 and the content of the fluorescent particles 150 in the transparent resin 160, the blue light transmission from the blue LED 110 becomes weak, and a white light emitting output is obtained. Will not improve. For this reason, in order to improve the white light emission output, it is further desired to improve the phosphor mixed color white light emitting diode device.
- Patent Document 3 For the purpose of improving the light emission output in this way, for example, as disclosed in Patent Document 3 and the like, there is a method for suppressing light emission loss and improving the light emission output by using an aluminum metal substrate as a light reflecting substrate.
- the upper surface of the metal substrate 11 is covered with an insulating resin 13, and the light emitting element 15 is mounted on the upper surface of the conductive pattern 14 formed on the upper surface of the insulating resin 13. Yes.
- improvement and improvement of the reflectance over the entire visible light region specifically, whitening of the reflective substrate itself is desired.
- a white resin is used as the insulating layer, there is a problem that the white resin deteriorates due to heat generated by a high current when the luminance itself of the light emitting element is improved.
- the LED light-emitting member is required to have a design that increases the directivity in the vertical direction with respect to the light-emitting surface, and a reflection characteristic with a small viewing angle dependency is desired.
- an object of the present invention is to provide a light reflecting substrate that improves white light emission output.
- the present inventor has found that a light reflecting substrate composed of an insulating layer and a metal layer having irregularities of a specific size on the surface is extremely excellent in light reflectivity, a wide wavelength region, and a wide The viewing angle dependence of light reflection is small at the viewing angle. That is, the present invention provides the following.
- the total reflectance of light having a wavelength of more than 320 nm to 700 nm is 50% or more, and 300 nm to A light reflecting substrate having a total reflectance of 320 nm wavelength light of 60% or more.
- the method of manufacturing a light reflecting substrate according to any one of (1) to (6) Prepare an aluminum plate, Roughening the surface of the aluminum plate; An insulating layer is formed by anodizing the roughened surface; Manufacturing method of light reflecting substrate.
- the light reflecting substrate according to (6) which is formed by stacking sheets.
- (10) In the routing process, when a cutting part for individually separating the chips is provided around the plurality of chips, and a part of the cutting part has a connecting part for connecting the plurality of chips to the aluminum plate.
- the thickness of the connecting part of the aluminum plate is designed to be thinner than the part that becomes the chip in advance, the connecting part is left on the aluminum plate by routing processing, and the cutting part is cut out, and then the aluminum plate is anodized After that, the connecting part is cut off, and the routing process for obtaining the individual chip is achieved by reducing or eliminating the area of the aluminum portion formed after the connecting part is cut in the thickness direction of the individual chip after being cut off.
- the light reflecting substrate of the present invention has small viewing angle dependence of light reflection in a wide wavelength region and wide viewing angle.
- FIG. 10A is a cross-sectional view of a light reflecting substrate in which the aluminum plate is planar and the insulating layer is also planar.
- FIGS. 10B1, 10B2, and 10B3 are cross-sectional views of a light reflecting substrate in which an aluminum plate has a shape with a recess and an insulating layer is formed on the surface of the recess.
- FIGS. 10C1, C2, and C3 are cross-sectional views illustrating other examples of the light reflecting substrate having the same shape as that of FIGS. 10B1, B2, and B3.
- FIGS. 11 (A1), (A2), (A3), and (A4) show that the connection part cut off after routing is exposed to metal aluminum, and the insulation is insufficient. It is a schematic diagram explaining the state which becomes.
- 11 (B1) and 11 (B2) show the shape of the connecting portion of the aluminum plate before anodization for attaching an anodized film to the disconnected connecting portion to maintain the insulation property, and the shape of the connecting portion after the anodizing. It is sectional drawing explaining the side surface of the light reflection substrate chip
- the light reflecting substrate of the present invention has an insulating layer and a metal layer provided in contact with the insulating layer, and has a light reflectance of more than 320 nm to 700 nm wavelength light of 50% or more and a wavelength of 300 nm to 320 nm.
- the light reflectance is 60% or more.
- the total reflectance is measured by, for example, a spectrophotometer.
- the light reflecting substrate of the present invention preferably has irregularities with an average wavelength of 0.01 to 100 ⁇ m in order to satisfy the above reflectance. Moreover, you may take the shape where the unevenness
- Concavities and convexities with an average wavelength of 5 to 100 ⁇ m are preferably an average wavelength of 7 to 75 ⁇ m and more preferably an average wavelength of 10 to 50 ⁇ m from the viewpoint of improving the light scattering effect. More preferred.
- the surface of the light reflecting substrate of the present invention preferably has a structure having either the above-described unevenness or the following unevenness.
- Concavities and convexities having an average wavelength of 0.5 to 5 ⁇ m (hereinafter also referred to as “medium wave structure”) have an average wavelength of 0.7 to 4 ⁇ m in that light scattering properties are increased and the light absorption effect is suppressed.
- the average wavelength is more preferably 1 to 3 ⁇ m.
- Concavities and convexities having an average wavelength of 0.01 to 0.5 ⁇ m are preferable to have an average wavelength of 0.015 to 0.4 ⁇ m from the viewpoint of suppressing the interference effect of visible light.
- the wavelength is more preferably 0.02 to 0.3 ⁇ m.
- the surface of the light reflecting substrate of the present invention has at least one selected from the group consisting of the above-described large wave structure, medium wave structure, and small wave structure. It is preferable to have these two or more concavo-convex structures superimposed on each other in that the reflectance can be further increased, and it is more preferable to have all three superimposed.
- the light reflecting substrate of the present invention has the above-described specific irregularities on the surface, it is possible to extract light uniformly over a wide viewing angle, and the viewing angle dependency is small (the difference in reflectance is small depending on the viewing angle).
- the surface of the light reflecting substrate of the present invention has the above-mentioned specific unevenness, it has excellent heat dissipation because of its high adhesion to a transparent resin having a fluorescent light emitter described later due to the uneven anchor effect.
- the light reflecting substrate of the present invention has an actual area S x determined by an approximate three-point method from three-dimensional data obtained by measuring 512 ⁇ 512 points in a 50 ⁇ m ⁇ 50 ⁇ m range of the surface using an atomic force microscope.
- the surface area difference ⁇ S obtained by the following formula (1) is preferably 5% or more and 90% or less, and more preferably 10% or more and 80% or less. More preferably, it is 20% or more and 70% or less from the viewpoint of whiteness improvement (scattering improvement) of the reflective substrate.
- the surface area difference ⁇ S is one of the factors indicating the degree of unevenness on the reflective substrate surface. If ⁇ S is large, light can be scattered more.
- the surface shape is measured by an atomic force microscope (AFM) to obtain three-dimensional data.
- the measurement can be performed, for example, under the following conditions. That is, the light reflecting substrate is cut to a size of 1 cm square, set on a horizontal sample stage on a piezo scanner, the cantilever is approached to the sample surface, and when it reaches the region where the atomic force works, it scans in the XY direction. At that time, the unevenness of the sample is captured by the displacement of the piezo in the Z direction.
- a piezo scanner that can scan 150 ⁇ m in the XY direction and 10 ⁇ m in the Z direction is used.
- a cantilever having a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m (SI-DF20, manufactured by NANOPROBE) is used for measurement in the DFM mode (Dynamic Force Mode). Further, the reference plane is obtained by correcting the slight inclination of the sample by approximating the obtained three-dimensional data by least squares. At the time of measurement, the surface of 50 ⁇ m ⁇ 50 ⁇ m is measured at 512 ⁇ 512 points.
- the resolution in the XY direction is 1.9 ⁇ m
- the resolution in the Z direction is 1 nm
- the scan speed is 60 ⁇ m / sec.
- the shape of the light reflecting substrate of the present invention is not limited.
- a light reflecting substrate 30 in which an aluminum plate as the metal layer 33 is planar and the insulating layer 32 is also planar may be used.
- the shape which has the hollow 34 as shown to FIG. 10 (B2) may be sufficient. If an LED element is mounted in the depression 34, the light reflection on the side surface of the depression of the light reflecting substrate can also be used effectively.
- FIGS. 10A a light reflecting substrate 30 in which an aluminum plate as the metal layer 33 is planar and the insulating layer 32 is also planar may be used.
- the shape which has the hollow 34 as shown to FIG. 10 (B2) may be sufficient. If an LED element is mounted in the depression 34, the light reflection on the side surface of the depression of the light reflecting substrate can also be used effectively.
- FIGS. 10B1 and 10B2 are cross-sectional views of a light reflecting substrate in which an aluminum plate, which is a metal layer, has a recess 34 (cavity), and an insulating layer 32 is also formed on a recess-shaped surface.
- the method for manufacturing the light reflecting substrate of the present invention shown in FIG. 10 (B3) is not limited.
- the metal layer 33 having the depression 34 may be formed in the aluminum plate 1 by pressing the mold 36 in the direction of the arrow.
- FIG. 10B2 shows a cross-sectional view of a state in which the depression 34 is formed in the metal layer 33. If an aluminum plate having a shape as shown in FIG. 10B2 is anodized, FIG.
- FIGS. 10C1, 10C2 and 10C3 are cross-sectional views showing another example of manufacturing a light reflecting substrate having the same shape as that shown in FIGS. 10B1, 10B2 and 10B3.
- the light reflecting substrate includes a light reflecting substrate 30 having no through hole and having at least an insulating layer 32 and a metal layer 33 as shown in FIG. 10 (C2), and a through hole 35 as shown in FIG. 10 (C1).
- two other light reflecting substrates 301 having an insulating layer 321 and a metal layer 331 are prepared.
- the light reflecting substrate 303 having the depression 34 is formed by overlapping two light reflecting substrates.
- the two light reflecting substrates may be bonded.
- the light reflecting substrate 301 shown in FIG. 10C1 may be manufactured by forming an insulating layer 321 by anodizing after forming a through hole 35 in an aluminum plate in advance.
- Through-hole processing can be formed by inexpensive drilling, and the control of the shape and size of the through-hole is very simple, so the same shape as before can be achieved by stacking and bonding two processed substrates as described above.
- the light reflecting substrate having the cavity structure can be manufactured at a low cost.
- a light reflecting substrate using an anodized aluminum anodized substrate suitable for the light reflecting substrate of the present invention will be described.
- a light reflecting substrate having an alumina layer which is anodized aluminum as an insulating layer and an aluminum metal layer continuous therewith has high light reflectivity and excellent heat resistance and weather resistance.
- a known aluminum plate can be used for the production of the light reflecting substrate of the present invention.
- the aluminum plate used in the present invention is a metal whose main component is dimensionally stable aluminum, and is made of aluminum or an aluminum alloy.
- an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements can also be used.
- various substrates made of the above-described aluminum or aluminum alloy are collectively referred to as an aluminum plate.
- the foreign elements that may be contained in the aluminum alloy include silicon, iron, copper, manganese, magnesium, chromium, zinc, bismuth, nickel, titanium, etc., and the content of the foreign elements in the alloy is 10% by mass or less. It is.
- the composition of the aluminum plate used in the present invention is not specified.
- a conventionally known material described in the fourth edition of the Aluminum Handbook (1990, published by the Light Metal Association) for example, JIS Al-Mn based aluminum plates such as A1050, JIS A1100, JIS A1070, JIS A3004 containing Mn, and internationally registered alloy 3103A can be appropriately used.
- JIS Al-Mn based aluminum plates such as A1050, JIS A1100, JIS A1070, JIS A3004 containing Mn, and internationally registered alloy 3103A
- an Al—Mg alloy or an Al—Mn—Mg alloy (JIS A3005) in which 0.1% by mass or more of magnesium is added to these aluminum alloys can also be used.
- an Al—Zr alloy or an Al—Si alloy containing Zr or Si can also be used.
- an Al—Mg—Si based alloy can also be used.
- JP-A-59-153861 JP-A-61-51395, JP-A-62-146694, JP-A-60-215725, JP-A-60-215726, JP-A-60- No.
- JP-A-7-81264, JP-A-7-305133, JP-A-8-49034, JP-A-8-73974, JP-A-8-108659, and JP-A-8-92679 is disclosed. Are listed.
- JP-B-62-5080, JP-B-63-60823, JP-B-3-61753, JP-A-60-203396, JP-A-60-203497, JP-B-3-11635 are used.
- JP-A-62-86143, JP-A-3-222296, JP-B-63-60824, JP-A-60-63346, JP-A-60-63347 and JP-A-60-63347 are disclosed. No. 1-293350, European Patent No. 223,737, US Pat. No. 4,818,300, British Patent No. 1,222,777 and the like.
- the Al—Zr alloy is described in Japanese Patent Publication Nos. 63-15978, 61-51395, 63-143234, and 63-143235.
- the Al—Mg—Si alloy is described in British Patent No. 1,421,710.
- a molten aluminum alloy adjusted to a predetermined alloy component content is subjected to a cleaning process and cast according to a conventional method.
- a cleaning process in order to remove unnecessary gas such as hydrogen in the molten metal, flux treatment, degassing process using argon gas, chlorine gas, etc., so-called rigid media filter such as ceramic tube filter, ceramic foam filter, A filtering process using a filter that uses alumina flakes, alumina balls or the like as a filter medium, a glass cloth filter, or a combination of a degassing process and a filtering process is performed.
- These cleaning treatments are preferably carried out in order to prevent defects caused by foreign substances such as non-metallic inclusions and oxides in the molten metal and defects caused by gas dissolved in the molten metal.
- filtering of the molten metal JP-A-6-57432, JP-A-3-162530, JP-A-5-140659, JP-A-4-231425, JP-A-4-276031, JP-A-5-311261, and JP-A-5-311261 are disclosed. It is described in each publication of JP-A-6-136466. Further, the degassing of the molten metal is described in JP-A-5-1659, JP-A-5-49148, and the like. The applicant of the present application has also proposed a technique relating to degassing of molten metal in Japanese Patent Application Laid-Open No. 7-40017.
- the casting method there are a method using a fixed mold represented by a DC casting method and a method using a driving mold represented by a continuous casting method.
- DC casting solidification occurs at a cooling rate of 0.5 to 30 ° C./second. When the temperature is less than 1 ° C., many coarse intermetallic compounds may be formed.
- DC casting is performed, an ingot having a thickness of 300 to 800 mm can be produced. The ingot is chamfered as necessary according to a conventional method, and usually 1 to 30 mm, preferably 1 to 10 mm, of the surface layer is cut.
- soaking treatment is performed as necessary. When soaking treatment is performed, heat treatment is performed at 450 to 620 ° C. for 1 to 48 hours so that the intermetallic compound does not become coarse. If the heat treatment is shorter than 1 hour, the effect of soaking may be insufficient.
- hot rolling and cold rolling are performed to obtain a rolled aluminum plate.
- a suitable starting temperature for hot rolling is 350 to 500 ° C.
- An intermediate annealing treatment may be performed before or after hot rolling or in the middle thereof.
- the conditions for the intermediate annealing treatment are heating at 280 to 600 ° C. for 2 to 20 hours, preferably 350 to 500 ° C. for 2 to 10 hours using a batch annealing furnace, or 400 to 600 ° C. using a continuous annealing furnace. Heating is performed for 6 minutes or less, preferably 450 to 550 ° C. for 2 minutes or less.
- the crystal structure can be made finer by heating at a heating rate of 10 to 200 ° C./second using a continuous annealing furnace.
- the flatness of the aluminum plate finished to a predetermined thickness, for example, 0.1 to 0.5 mm by the above steps may be further improved by a correction device such as a roller leveler or a tension leveler.
- the flatness may be improved after the aluminum plate is cut into a sheet shape, but in order to improve productivity, it is preferably performed in a continuous coil state. Further, a slitter line may be used for processing into a predetermined plate width.
- the continuous casting method a twin roll method (hunter method), a method using a cooling roll typified by the 3C method, a double belt method (Hazley method), a cooling belt or a cooling block typified by Al-Swiss Caster II type
- the method using is industrially performed.
- the continuous casting method solidifies at a cooling rate of 100 to 1000 ° C./second. Since the continuous casting method generally has a higher cooling rate than the DC casting method, it has a feature that the solid solubility of the alloy component in the aluminum matrix can be increased.
- JP-A-3-79798 JP-A-5-201166, JP-A-5-156414, JP-A-6-262203, and JP-A-6-122949.
- JP-A-6-210406 JP-A-6-26308, and the like.
- a cast plate having a thickness of 1 to 10 mm can be directly continuously cast, and the hot rolling step is omitted.
- a method using a cooling roll such as the Hunter method
- a cast plate having a thickness of 10 to 50 mm can be cast.
- a hot rolling roll is arranged immediately after casting and continuously rolled.
- a continuous cast and rolled plate having a thickness of 1 to 10 mm can be obtained.
- the crystal structure of the aluminum plate may cause poor surface quality when the surface of the aluminum plate is subjected to chemical or electrochemical surface roughening. It is preferably not too coarse.
- the crystal structure on the surface of the aluminum plate preferably has a width of 200 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, and the length of the crystal structure is 5000 ⁇ m or less. Is preferably 1000 ⁇ m or less, and more preferably 500 ⁇ m or less.
- the alloy component distribution of the aluminum plate when chemical surface roughening treatment or electrochemical surface roughening treatment is performed, poor surface quality occurs due to non-uniform distribution of the alloy component on the surface of the aluminum plate. Therefore, it is preferable that the surface is not very uneven. With respect to these, techniques proposed by the applicant of the present application are described in Japanese Patent Laid-Open Nos. 6-48058, 5-301478, and 7-132689.
- the size and density of the intermetallic compound may affect the chemical roughening treatment or the electrochemical roughening treatment.
- techniques proposed by the present applicant are described in Japanese Patent Laid-Open Nos. 7-138687 and 4-254545.
- an aluminum plate as shown above can be used by forming irregularities by lamination rolling, transfer, etc. in the final rolling step or the like.
- the aluminum plate used in the present invention may be an aluminum web or a sheet-like sheet.
- the packing form of aluminum is, for example, laying hardboard and felt on an iron pallet, applying cardboard donut plates to both ends of the product, wrapping the whole with a polytube, and inserting a wooden donut into the inner diameter of the coil Then, a felt is applied to the outer periphery of the coil, the band is squeezed with a band, and the display is performed on the outer periphery.
- a polyethylene film can be used as the packaging material, and needle felt and hard board can be used as the cushioning material.
- the present invention is not limited to this method as long as it is stable and can be transported without being damaged.
- the thickness of the aluminum plate used in the present invention is about 0.1 to 2.0 mm, preferably 0.15 to 1.5 mm, and more preferably 0.2 to 1.0 mm. This thickness can be appropriately changed according to the user's wishes or the like.
- the surface treatment for producing the reflective substrate of the present invention includes a roughening treatment and an anodizing treatment.
- the manufacturing process of the porous alumina support may include various processes other than the roughening process and the anodizing process.
- a method of sequentially performing mechanical surface roughening treatment, alkali etching treatment, desmutting treatment with an acid and electrochemical surface roughening treatment using an electrolytic solution on an aluminum plate A method of performing mechanical surface roughening treatment, alkali etching treatment, acid desmutting treatment and electrochemical surface roughening treatment using different electrolytes on an aluminum plate a plurality of times, alkali etching treatment, acid desmutting treatment on an aluminum plate, and Examples include a method of sequentially performing an electrochemical surface roughening treatment using an electrolytic solution, a method of subjecting an aluminum plate to an alkali etching treatment, a desmutting treatment with an acid, and an electrochemical surface roughening treatment using different electrolytic solutions multiple times.
- the present invention is not limited to these. In these methods, after the electrochemical roughening treatment, an alkali etching treatment and an acid desmutting treatment may be further performed.
- a mechanical surface roughening treatment and nitric acid are mainly used.
- Preferred examples include a method of sequentially performing an electrochemical surface roughening treatment using an electrolytic solution and an electrochemical surface roughening treatment using an electrolytic solution mainly composed of hydrochloric acid.
- an electrolytic solution mainly composed of hydrochloric acid is used, and only an electrochemical surface roughening process is performed in which the total amount of electricity involved in the anode reaction is increased.
- an electrolytic solution mainly composed of hydrochloric acid is used, and only an electrochemical surface roughening process is performed in which the total amount of electricity involved in the anode reaction is increased.
- the mechanical surface roughening treatment can form a rough surface with an average wavelength of 5 to 100 ⁇ m at a lower cost than the electrochemical surface roughening treatment. It is effective as a processing means.
- Examples of the mechanical surface roughening treatment include, for example, a wire brush grain method in which the aluminum surface is scratched with a metal wire, a ball grain method in which the aluminum surface is grained with a polishing ball and an abrasive, JP-A-6-135175, and Japanese Patent Publication
- a brush grain method in which the surface is grained with a nylon brush and an abrasive described in Japanese Patent No. 50-40047 can be used.
- a transfer method in which the uneven surface is pressed against the aluminum plate can also be used.
- a fine groove may be cut from two directions using a die, a cutting tool, a laser or the like on the roll surface, and the surface may be provided with square irregularities.
- the roll surface may be subjected to a known etching process or the like so that the formed square irregularities are rounded.
- quenching, hard chrome plating, or the like may be performed.
- mechanical surface roughening treatment methods described in JP-A Nos. 61-162351 and 63-104889 can be used. In the present invention, the above-described methods can be used in combination in consideration of productivity and the like. These mechanical surface roughening treatments are preferably carried out before the electrochemical surface roughening treatment.
- the brush grain method used suitably as a mechanical roughening process is demonstrated.
- the brush grain method uses a roller-shaped brush in which a large number of synthetic resin bristles made of synthetic resin such as nylon (trademark), propylene, and vinyl chloride resin are implanted on the surface of a cylindrical body.
- This is a method in which one or both of the surfaces of the aluminum plate are rubbed while a slurry liquid containing an abrasive is sprayed onto the roller-shaped brush.
- a polishing roller which is a roller having a polishing layer on the surface can be used.
- flexural modulus preferably 10,000 ⁇ 40,000kgf / cm 2, and more is preferably 15,000 ⁇ 35,000kgf / cm 2, and the strength of hair waist preferably Brush hair of 500 gf or less, more preferably 400 gf or less is used.
- the diameter of the bristles is generally 0.2 to 0.9 mm.
- the length of the brush bristles can be appropriately determined according to the outer diameter of the roller brush and the diameter of the cylinder, but is generally 10 to 100 mm.
- abrasives such as pumicestone, silica sand, aluminum hydroxide, alumina powder, silicon carbide, silicon nitride, volcanic ash, carborundum, and gold sand; a mixture thereof can be used.
- pumiston and silica sand are preferable.
- silica sand is preferable in terms of excellent surface roughening efficiency because it is harder and less likely to break than Pamiston.
- the average particle diameter of the abrasive is preferably 3 to 50 ⁇ m, more preferably 6 to 45 ⁇ m, from the viewpoints of excellent surface roughening efficiency and a narrow graining pitch.
- the abrasive is suspended in water and used as a slurry.
- the slurry liquid may contain a thickener, a dispersant (for example, a surfactant), a preservative, and the like.
- the specific gravity of the slurry liquid is preferably 0.5-2.
- an apparatus suitable for the mechanical surface roughening treatment for example, an apparatus described in Japanese Patent Publication No. 50-40047 can be given.
- electrochemical roughening treatment For the electrochemical roughening treatment (hereinafter also referred to as “electrolytic roughening treatment”), an electrolytic solution used for an electrochemical roughening treatment using a normal alternating current can be used. Among them, it is preferable to use an electrolytic solution mainly composed of hydrochloric acid or nitric acid because the above-described surface shape can be easily obtained.
- Electrolytic surface roughening can be performed according to, for example, the electrochemical grain method (electrolytic grain method) described in Japanese Patent Publication No. 48-28123 and British Patent No. 896,563.
- This electrolytic grain method uses a sinusoidal alternating current, but it may be performed using a special waveform as described in JP-A-52-58602. Further, the waveform described in JP-A-3-79799 can also be used.
- the methods described in JP-A-3-267400 and JP-A-1-141094 can also be applied.
- Examples of the acidic aqueous solution as the electrolytic solution include nitric acid and hydrochloric acid, U.S. Pat. Nos. 4,671,859, 4,661,219, 4,618,405, 4,600, 482, 4,566,960, 4,566,958, 4,566,959, 4,416,972, 4,374,710,
- the electrolyte solution described in each specification of 4,336,113 and 4,184,932 can also be used.
- the concentration of the acidic aqueous solution is preferably 0.5 to 2.5% by mass, but it is particularly preferably 0.7 to 2.0% by mass in consideration of use in the smut removal treatment.
- the liquid temperature is preferably 20 to 80 ° C., more preferably 30 to 60 ° C.
- An aqueous solution mainly composed of hydrochloric acid or nitric acid is an aqueous solution of hydrochloric acid or nitric acid with a concentration of 1 to 100 g / L, such as nitric acid compounds having nitrate ions such as aluminum nitrate, sodium nitrate and ammonium nitrate, or aluminum chloride, sodium chloride and ammonium chloride.
- nitric acid compounds having hydrochloric acid ions can be used by adding in a range from 1 g / L to saturation.
- the metal contained in aluminum alloys such as iron, copper, manganese, nickel, titanium, magnesium, a silica, may melt
- a solution obtained by adding aluminum chloride, aluminum nitrate or the like to an aqueous solution of hydrochloric acid or nitric acid having a concentration of 0.5 to 2% by mass so that aluminum ions are 3 to 50 g / L is preferably used.
- the compound capable of forming a complex with Cu include ammonia; hydrogen atom of ammonia such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, cyclohexylamine, triethanolamine, triisopropanolamine, EDTA (ethylenediaminetetraacetic acid).
- ammonium salts such as ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, and ammonium carbonate are also included.
- the temperature is preferably 10 to 60 ° C, more preferably 20 to 50 ° C.
- the AC power source wave used for the electrochemical surface roughening treatment is not particularly limited, and a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave or the like is used, but a rectangular wave or a trapezoidal wave is preferable, and a trapezoidal wave is particularly preferable.
- a trapezoidal wave means what was shown in FIG. In this trapezoidal wave, the time (TP) until the current reaches a peak from zero is preferably 1 to 3 msec. If it is less than 1 msec, processing irregularities such as chatter marks that occur perpendicular to the traveling direction of the aluminum plate are likely to occur.
- TP exceeds 3 msec, especially when a nitric acid electrolyte is used, it is easily affected by trace components in the electrolyte typified by ammonium ions and the like that spontaneously increase by electrolytic treatment, and uniform graining is performed. It becomes hard to be broken.
- a trapezoidal wave AC duty ratio of 1: 2 to 2: 1 can be used. However, as described in Japanese Patent Laid-Open No. 5-195300, in an indirect power feeding method that does not use a conductor roll for aluminum. A duty ratio of 1: 1 is preferable.
- a trapezoidal AC frequency of 0.1 to 120 Hz can be used, but 50 to 70 Hz is preferable in terms of equipment. When the frequency is lower than 50 Hz, the carbon electrode of the main electrode is easily dissolved, and when the frequency is higher than 70 Hz, it is easily affected by an inductance component on the power supply circuit, and the power supply cost is increased.
- One or more AC power supplies can be connected to the electrolytic cell.
- the current ratio between the anode and cathode of the alternating current applied to the aluminum plate facing the main electrode is controlled to achieve uniform graining and to dissolve the carbon of the main electrode.
- 11 is an aluminum plate
- 12 is a radial drum roller
- 13a and 13b are main poles
- 14 is an electrolytic treatment solution
- 15 is an electrolyte supply port
- 16 is a slit.
- the ratio of the amount of electricity involved in the cathodic reaction and the anodic reaction is preferably 0.3 to 0.95.
- electrolytic cell electrolytic cells used for known surface treatments such as a vertical type, a flat type, and a radial type can be used, but a radial type electrolytic cell as described in JP-A-5-195300 is particularly preferable.
- the electrolytic solution passing through the electrolytic cell may be parallel to the traveling direction of the aluminum web or may be a counter.
- Irregularities having an average wavelength of 0.5 to 5 ⁇ m can be formed by electrochemical surface roughening using an electrolytic solution mainly composed of nitric acid.
- the electrolytic reaction is concentrated, and irregularities exceeding the wavelength of 5 ⁇ m are also generated.
- the total amount of electricity involved in the anode reaction of the aluminum plate at the time when the electrolytic reaction is completed is preferably 1 to 1000 C / dm 2 , and preferably 50 to 300 C / dm 2. It is more preferable that The current density at this time is preferably 20 to 100 A / dm 2 . Further, for example, electrolysis is performed at 30 to 60 ° C.
- a nitric acid electrolytic solution having a high concentration for example, a nitric acid concentration of 15 to 35% by mass, or a high temperature using a nitric acid electrolytic solution having a nitric acid concentration of 0.7 to 2% by mass.
- a small wave structure having an average wavelength of 0.20 ⁇ m or less can be formed by performing electrolysis at 80 ° C. or higher. As a result, ⁇ S can be increased.
- the total amount of electricity involved in the anodic reaction of the aluminum plate at the end of the electrolytic reaction is preferably 1 to 100 C / dm 2 , and preferably 20 to 70 C / dm 2 . More preferably.
- the current density at this time is preferably 20 to 50 A / dm 2 .
- a large crater-like swell is simultaneously formed by increasing the total amount of electricity involved in the anode reaction to 400 to 2000 C / dm 2. It is also possible. In this case, fine irregularities having an average wavelength of 0.01 to 0.4 ⁇ m are formed on the entire surface by superimposing on a crater-like wave having an average wavelength of 10 to 30 ⁇ m. In this case, a medium wave structure with an average wavelength of 0.5 to 5 ⁇ m is not generated.
- ⁇ S it is effective to provide many small irregularities on the surface.
- electrolytic surface roughening treatment using an electrolytic solution mainly composed of hydrochloric acid electrolytic rough surface using an electrolytic solution mainly composed of high-concentration and high-temperature nitric acid
- the treatment is performed.
- ⁇ S is also increased by mechanical surface roughening treatment or electrolytic surface roughening treatment using an electrolytic solution mainly composed of nitric acid, the degree is small.
- cathodic electrolysis treatment it is preferable to perform cathodic electrolysis treatment on the aluminum plate before and / or after the electrolytic surface-roughening treatment performed in the electrolytic solution such as nitric acid and hydrochloric acid.
- the electrolytic solution such as nitric acid and hydrochloric acid.
- smut is generated on the surface of the aluminum plate, and hydrogen gas is generated to enable more uniform electrolytic surface roughening treatment.
- Cathodic electrolysis is carried out in an acidic solution with a cathodic charge of preferably 3 to 80 C / dm 2 , more preferably 5 to 30 C / dm 2 .
- the electrolytic solution may be the same as or different from the solution used in the electrolytic surface roughening treatment.
- the alkali etching treatment is a treatment for dissolving the surface layer by bringing the aluminum plate into contact with an alkali solution.
- the alkali etching treatment performed before the electrolytic surface roughening treatment removes rolling oil, dirt, natural oxide film, etc. on the surface of the aluminum plate (rolled aluminum) when the mechanical surface roughening treatment is not performed.
- the edge portion of the unevenness generated by the mechanical surface roughening treatment is dissolved, and the steep unevenness is converted into a surface having smooth undulations. It is done for the purpose of changing.
- the etching amount is preferably 0.1 to 10 g / m 2 , and more preferably 1 to 5 g / m 2 . If the etching amount is less than 0.1 g / m 2 , rolling oil, dirt, natural oxide film, etc. may remain on the surface, so that uniform unevenness cannot be generated in the subsequent electrolytic surface roughening treatment, resulting in unevenness. May occur. On the other hand, when the etching amount is from 1 to 10 g / m 2 , the surface of the rolling oil, dirt, natural oxide film and the like are sufficiently removed. An etching amount exceeding the above range is economically disadvantageous.
- the etching amount is preferably 3 to 20 g / m 2 , and more preferably 5 to 15 g / m 2 . If the etching amount is less than 3 g / m 2 , the unevenness formed by mechanical surface roughening may not be smoothed, and uniform unevenness may not be formed in the subsequent electrolytic surface roughening treatment. On the other hand, when the etching amount exceeds 20 g / m 2 , the concavo-convex structure may disappear.
- the alkali etching treatment performed immediately after the electrolytic surface roughening treatment is performed for the purpose of dissolving the smut generated in the acidic electrolyte and dissolving the uneven edge portion formed by the electrolytic surface roughening treatment.
- the unevenness formed by the electrolytic surface roughening treatment varies depending on the type of the electrolytic solution, and therefore the optimum etching amount varies.
- the etching amount of the alkali etching treatment performed after the electrolytic surface roughening treatment is 0.1 to 5 g / m. 2 is preferred. When a nitric acid electrolyte is used, the etching amount needs to be set larger than when a hydrochloric acid electrolyte is used.
- an alkali etching treatment can be performed as necessary after each treatment.
- Examples of the alkali used in the alkaline aqueous solution include caustic alkali and alkali metal salts.
- caustic alkali include caustic soda and caustic potash.
- alkali metal salt include alkali metal silicates such as sodium metasilicate, sodium silicate, potassium metasilicate, and potassium silicate; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium aluminate and alumina.
- Alkali metal aluminates such as potassium acid; alkali metal aldones such as sodium gluconate and potassium gluconate; dibasic sodium phosphate, dibasic potassium phosphate, tribasic sodium phosphate, tertiary potassium phosphate, etc.
- An alkali metal hydrogen phosphate is mentioned.
- a caustic alkali solution and a solution containing both a caustic alkali and an alkali metal aluminate are preferable from the viewpoint of high etching rate and low cost.
- an aqueous solution of caustic soda is preferable.
- the concentration of the alkaline solution can be determined according to the etching amount, but is preferably 1 to 50% by mass, more preferably 10 to 35% by mass.
- the concentration of aluminum ions is preferably 0.01 to 10% by mass, and more preferably 3 to 8% by mass.
- the temperature of the alkaline solution is preferably 20 to 90 ° C.
- the treatment time is preferably 1 to 120 seconds.
- Examples of the method of bringing the aluminum plate into contact with the alkaline solution include, for example, a method in which the aluminum plate is passed through a tank containing the alkaline solution, a method in which the aluminum plate is immersed in a tank containing the alkaline solution, The method of spraying on the surface of a board is mentioned.
- pickling is preferably performed in order to remove dirt (smut) remaining on the surface.
- the acid used include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and borohydrofluoric acid.
- the desmutting treatment is performed, for example, by bringing the aluminum plate into contact with an acidic solution (containing aluminum ions of 0.01 to 5% by mass) having a concentration of 0.5 to 30% by mass such as hydrochloric acid, nitric acid, and sulfuric acid. .
- the method of bringing the aluminum plate into contact with the acidic solution include, for example, a method of passing the aluminum plate through a tank containing an acidic aqueous solution, a method of immersing the aluminum plate in a tank containing an acidic solution, and an acidic solution containing aluminum.
- the method of spraying on the surface of a board is mentioned.
- the acidic solution is mainly composed of an aqueous solution mainly composed of nitric acid or an aqueous solution mainly composed of hydrochloric acid discharged in the above-described electrolytic surface-roughening treatment, or sulfuric acid discharged in an anodic oxidation process described later. It is possible to use a waste solution of an aqueous solution.
- the temperature of the desmut treatment is preferably 25 to 90 ° C.
- the processing time is preferably 1 to 180 seconds.
- Aluminum and aluminum alloy components may be dissolved in the acidic solution used for the desmut treatment.
- through-hole processing for appropriately providing a wiring portion and routing processing for making a chip assuming the final product (individualized into the final product) Can be performed).
- Through-hole processing may be performed before or after the anodizing step.
- the viewpoint of preventing cracks in the insulating layer formed by anodic oxidation and the insulating property to the end face of the substrate caused by the processing can be maintained. . If it is performed after the anodizing process, the efficiency of the anodizing process can be increased and the final product can be processed with high accuracy.
- the size / shape is not particularly limited as long as it can be secured by insertion, but considering the final chip size and reliable wiring formation, a circular shape is preferable, and the size is from 0.01 mm ⁇ to 2 mm ⁇ is preferable, 0.05 mm ⁇ to 1 mm ⁇ is more preferable, and 0.1 mm ⁇ to 0.8 mm ⁇ is particularly preferable.
- the routing processing is the size of a light reflecting substrate (hereinafter referred to as a chip) that is individualized to the final product (the processing product added to the final product), or This is an individual separation process that takes into account the volume expansion caused by anodization to obtain a required size in advance, and is also called patterning or chip formation.
- the routing process may be performed before or after the anodizing step.
- the efficiency of the anodizing process can be increased and the final product can be processed with high accuracy.
- routing processing it is necessary to consider the size / shape of the final chip.
- one side is 0.1 mm from the viewpoint of chip compactness and processing suitability.
- an element portion (not shown, which is not shown) is electrically connected to the element mounting portion (not shown, a portion where the element is later mounted) after routing. It is preferable to process into a shape that provides electrical conductivity to the portion. Suitable methods include, but are not limited to, a method of performing routing processing with a conductive portion provided, a method of connecting element portions with a conductive wire, and the like.
- Suitable methods for performing the above-described through-hole processing and routing processing include, but are not limited to, drill processing, press processing using a die, dicing processing using a dicer, laser processing, and the like.
- the shape corresponding to each chip is further connected to each chip, and the metal aluminum is stripped in the thickness direction of each chip after each chip is separated by the connection.
- Method of making the part insulative> The routing process is not limited.
- the aluminum plate 1 that is a metal plate as shown in FIG. 11A1 is separated from the chip 41 that becomes an individual light reflecting substrate as shown in FIG. 11A2.
- the portion 43 is cut out to the bottom surface of the aluminum plate 1.
- the connecting portion 42 for connecting the chips or the chips to the aluminum plate 1 is left at that time, the chip 41 can be handled as an integrated aluminum plate without being separated. It is. Then, after performing necessary processing such as anodizing treatment as shown in FIG.
- the connecting portion 42 is separated into individual chips 41 as shown in FIG. 11 (A4).
- the metal aluminum which has not been anodized is exposed on the disconnection trace 45 of the connecting portion 42 on the side surface of the chip after being disconnected at that time, the insulating property on the side surface of the individual chip 41 obtained becomes insufficient.
- the thickness of the connecting portion is designed in advance to be twice or less the thickness of the oxide film formed by anodic oxidation.
- the thickness can be less than twice the thickness of the oxide film formed by anodic oxidation.
- the portion that becomes the connecting portion 42 is designed to be thin, as shown in the sectional view in the center of FIGS. 11 (B1) and (B2), after the anodizing treatment, the insulating film that is an anodized film is the portion of the connecting portion. It can be anodized to occupy most of the thickness.
- the aluminum portion of the separation mark 45 has a very small thickness.
- the entire thickness of the connecting portion is anodized.
- ⁇ Anodizing treatment> The aluminum plate that has been surface-treated and processed as described above is further anodized. By anodizing treatment, an anodized film made of alumina is formed on the surface of the aluminum plate, and a porous or non-porous surface insulating layer is obtained.
- the anodizing treatment can be performed by a conventional method.
- an anodized film can be formed by energizing an aluminum plate as an anode in an aqueous solution having a sulfuric acid concentration of 50 to 300 g / L and an aluminum concentration of 5% by mass or less.
- the 2nd, 3rd component may be added.
- the second and third components herein include metal ions such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn; Cation such as ammonium ion; anion such as nitrate ion, carbonate ion, chloride ion, phosphate ion, fluoride ion, sulfite ion, titanate ion, silicate ion, borate ion, etc., 0 to 10,000 ppm It may be contained at a concentration of about.
- the conditions of the anodizing treatment cannot be determined unconditionally because they vary depending on the electrolyte used, but generally the electrolyte concentration is 1 to 80% by mass, the solution temperature is 5 to 70 ° C., and the current density is 0.5. It is appropriate that ⁇ 60 A / dm 2 , voltage 1 ⁇ 100 V, electrolysis time 15 seconds ⁇ 50 minutes, and the anodic oxide film amount is adjusted to a desired amount.
- the methods described in JP-A-207299, JP-A-5-24377, JP-A-5-32083, JP-A-5-125597, JP-A-5-195291 and the like can also be used.
- an aqueous sulfuric acid solution as the electrolytic solution.
- the sulfuric acid concentration in the electrolytic solution is preferably 10 to 300 g / L, and the aluminum ion concentration is preferably 1 to 25 g / L, more preferably 2 to 10 g / L.
- Such an electrolytic solution can be prepared, for example, by adding aluminum sulfate or the like to dilute sulfuric acid having a sulfuric acid concentration of 50 to 200 g / L.
- direct current may be applied between the aluminum plate and the counter electrode, or alternating current may be applied.
- the current density is preferably 1 to 60 A / dm 2 , and more preferably 5 to 40 A / dm 2 .
- a low current of 5 to 10 A / dm 2 is initially introduced so that so-called “burning” does not occur due to current concentration on a part of the aluminum plate. It is preferable to increase the current density to 30 to 50 A / dm 2 or more as the current is passed at the density and the anodization process proceeds.
- the anodizing treatment is continuously performed, it is preferable that the anodizing process is performed by a liquid power feeding method in which power is supplied to the aluminum plate through an electrolytic solution.
- the average pore diameter is about 5 to 1000 nm, and the average pore density is about 1 ⁇ 10 6 to 1 ⁇ 10 10 / mm 2 .
- the thickness of the anodized film is preferably 1 to 200 ⁇ m. If the thickness is less than 1 ⁇ m, the insulation is poor and the withstand voltage is lowered. The thickness of the anodized film is more preferably 2 to 100 ⁇ m.
- FIG. 3 is a schematic view showing an example of an apparatus for anodizing the surface of an aluminum plate.
- the aluminum plate 416 is conveyed as shown by the arrows in FIG.
- the power supply tank 412 in which the electrolytic solution 418 is stored the aluminum plate 416 is charged to (+) by the power supply electrode 420.
- the aluminum plate 416 is conveyed upward by the roller 422 in the power supply tank 412, changed in direction downward by the nip roller 424, and then conveyed toward the electrolytic treatment tank 414 in which the electrolytic solution 426 is stored. The direction is changed horizontally. Next, the aluminum plate 416 is charged to ( ⁇ ) by the electrolytic electrode 430 to form an anodic oxide film on the surface thereof, and the aluminum plate 416 exiting the electrolytic treatment tank 414 is conveyed to a subsequent process.
- the roller 422, the nip roller 424, and the roller 428 constitute a direction changing means, and the aluminum plate 416 is disposed between the power supply tank 412 and the electrolytic treatment tank 414 in the inter-tank section. By 428, it is conveyed into a mountain shape and an inverted U shape.
- the feeding electrode 420 and the electrolytic electrode 430 are connected to a DC power source 434.
- the feature of the anodizing apparatus 410 in FIG. 3 is that the feeding tank 412 and the electrolytic treatment tank 414 are partitioned by a single tank wall 432, and the aluminum plate 416 is conveyed in a mountain shape and an inverted U shape between the tanks. It is in. As a result, the length of the aluminum plate 416 in the inter-tank portion can be minimized. Therefore, the overall length of the anodizing apparatus 410 can be shortened, so that the equipment cost can be reduced.
- by conveying the aluminum plate 416 in a mountain shape and an inverted U shape it is not necessary to form an opening for allowing the aluminum plate 416 to pass through the tank wall 432 of each tank 412 and 414. Therefore, since the liquid feeding amount required to maintain the liquid level height in each tank 412 and 414 at a required level can be suppressed, the operating cost can be reduced.
- a sealing treatment for sealing the existing micropores may be performed as necessary.
- the sealing treatment can be performed according to a known method such as boiling water treatment, hot water treatment, steam treatment, sodium silicate treatment, nitrite treatment, ammonium acetate treatment and the like.
- the sealing treatment may be performed by the apparatus and method described in JP-B-56-12518, JP-A-4-4194, JP-A-5-202296, JP-A-5-179482, and the like. .
- ⁇ Washing treatment> It is preferable to perform water washing after the completion of the above-described processes. For washing, pure water, well water, tap water, or the like can be used. A nip device may be used to prevent the processing liquid from being brought into the next process.
- an inorganic insulating layer made of a white insulating material such as titanium oxide or an organic insulating layer such as a white resist may be provided.
- an insulating layer made of alumina can be colored with a desired color, for example, by electrodeposition.
- Co Ion, Fe ion, Au ion, Pb ion, Ag ion, Se ion, Sn ion, Ni ion, Cu ion, Bi ion, Mo ion, Sb ion, Cd ion, and / or As ion are mixed in the electrolyte. Coloring is performed by electrolytic treatment.
- a sol-gel method as described in paragraphs [0016] to [0035] of JP-A-6-35174 is disclosed.
- a layer can also be provided.
- the sol-gel method is a method in which a sol composed of a metal alkoxide is generally converted into a gel that loses fluidity by hydrolysis and polycondensation reaction, and this gel is heated to form an oxide layer (ceramic layer).
- the metal alkoxide used in the present invention is not particularly limited, but Al (O—R) n, Ba (O—R) n, and B (O—R) are used from the viewpoint of forming a layer having a uniform thickness.
- the (sentences in R may have a substituent, linear, branched, or, cyclic, hydrocarbon radical, n denotes an arbitrary natural number.).
- n denotes an arbitrary natural number.
- the insulating layer is an anodic oxidation layer of aluminum
- Si (O—R) n type which is excellent in reactivity with alumina and excellent in sol-gel layer formability is more preferable.
- the method for forming the sol-gel layer is not particularly limited, but from the viewpoint of controlling the thickness of the layer, a method in which a sol solution is applied and heated is preferable.
- the concentration of the sol solution is preferably 0.1 to 90% by mass, more preferably 1 to 80% by mass, and particularly preferably 5 to 70% by mass.
- the thickness is preferably from 0.01 ⁇ m to 20 ⁇ m, more preferably from 0.05 ⁇ m to 15 ⁇ m, and more preferably from 0.1 ⁇ m to 0.1 ⁇ m, from the viewpoint of high reflectivity and insulation. 10 ⁇ m is particularly preferable. If it is thicker than this range, it is not preferable from the viewpoint of high reflectance, and if it is thinner than this range, it is not preferable from the viewpoint of insulation.
- the light reflecting substrate of the present invention is not particularly limited in the type of LED used and the shape of the light emitting element, and can be used for various applications. Further, it can be used as a light reflecting substrate of a light emitting device using a conventionally known LED. For example, the luminance of the light emitting unit 100 can be improved by using the light reflecting substrate 30 of the present invention instead of the substrate 140 shown in FIG. Further, as shown in FIG. 7, a blue LED 22 is placed on a light reflecting substrate 30 having an insulating layer 32 and a metal layer 33 of the present invention, sealed with a known resin 24, and a fluorescent light emitter is placed on the top.
- FIG. 9 an element 37 such as a light emitting diode mounted on the light reflecting substrate 30 of the present invention having an insulating layer 32 and a metal layer 33 provided in contact with the insulating layer 32 is sealed with a transparent resin 160 having fluorescent particles 150.
- 2 is a cross-sectional view showing a fluorescent light emitting unit 100.
- the element 37 is mounted on the light reflecting substrate 30 by die bonding or the like, the light reflecting substrate 30 is provided with a through hole 35, and the metal layer 33 located below the element 37 is thicker than other substrate portions.
- the heat sink 39 may be formed into a shape.
- the insulating layer 32 is an anodized film of the aluminum metal layer 33, and the inside of the through hole is also anodized to form an insulating layer.
- the element 37 is wire bonded and is electrically connected to the external electrodes 120 and 130. Since the light reflection substrate 30 of the present invention has high total reflectance at a specific wavelength, the luminance of the fluorescent light emitting unit 100 using this as a substrate is high.
- the light emitting diode element 37 is formed by forming a semiconductor such as GaAlN, ZnS, ZnSe, SiC, GaP, GaAlAs, AlN, InN, AlInGaP, InGaN, GaN, or AlInGaN on a substrate as a light emitting layer.
- a semiconductor structure include a homostructure, a heterostructure, or a double heterostructure having a MIS junction, a PIN junction, or a PN junction.
- Various emission wavelengths can be selected from ultraviolet light to infrared light depending on the material of the semiconductor layer and the degree of mixed crystal.
- the material of the transparent resin 160 is preferably a thermosetting resin.
- thermosetting resins it is preferably formed of at least one selected from the group consisting of epoxy resins, modified epoxy resins, silicone resins, modified silicone resins, acrylate resins, urethane resins, and polyimide resins, especially epoxy resins, Modified epoxy resins, silicone resins, and modified silicone resins are preferred.
- the transparent resin 160 is preferably hard to protect the element 37.
- the transparent resin 160 is preferably a resin having excellent heat resistance, weather resistance, and light resistance.
- the transparent resin 160 may be mixed with at least one selected from the group consisting of a filler, a diffusing agent, a pigment, a fluorescent material, a reflective material, an ultraviolet absorber, and an antioxidant in order to have a predetermined function. .
- the fluorescent particles 150 may be anything that absorbs light from the element 37 and converts the wavelength into light of a different wavelength.
- nitride phosphors, oxynitride phosphors, sialon phosphors, ⁇ sialon phosphors, lanthanoids such as Eu, transitions such as Mn which are mainly activated by lanthanoid elements such as Eu and Ce Alkaline earth halogen apatite phosphor, alkaline earth metal borate phosphor, alkaline earth metal aluminate phosphor, alkaline earth silicate phosphor, alkaline earth mainly activated by metal elements Sulfide phosphors, alkaline earth thiogallate phosphors, alkaline earth silicon nitride phosphors, germanate phosphors, rare earth aluminate phosphors mainly activated by lanthanoid elements such as Ce, rare earths It is preferably at least one selected from organic and organic complexes
- the light reflecting substrate of the present invention is used as a light reflecting substrate of a phosphor mixed color type white LED light emitting element using an ultraviolet to blue LED and a fluorescent light emitting material that absorbs the LED and emits fluorescence in the visible light region. It can also be used. These fluorescent light emitters absorb blue light from the blue LED to generate fluorescence (yellowish fluorescent light), and white light is emitted from the light emitting element by the fluorescent light and the afterglow of the blue LED.
- the method described above is a so-called “pseudo white light emission type” in which one chip of a blue LED light source and one kind of yellow phosphor are combined.
- one chip of ultraviolet to near ultraviolet LED light source and red / green / Light-emitting element of light-emitting unit using known light-emitting methods such as “ultraviolet to near-ultraviolet light source type” in which several kinds of blue phosphors are combined, and “RGB light source type” that emits white light with three red / green / blue light sources
- the light reflecting substrate of the present invention can be used as the substrate.
- the substrate of the present invention is compatible with various solvents used in post-processing such as metal wiring layer formation processing, pattern processing, and metal layer formation processing on the LED mounting portion for electric signal transmission to the LED described later. Therefore, protection processing can be performed.
- the protection treatment appropriately changes the hydrophilic / hydrophobic (philic / oleophobic) properties of the anodized film surface as described in JP-A-2008-93652, JP-A-2009-68076, and the like.
- a method of imparting resistance to acid / alkali can be used as appropriate.
- the material is not particularly limited as long as it is a material that conducts electricity, and metal materials such as gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), etc. Are preferable, and may be used alone or in multiple materials.
- metal materials such as gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), etc. are preferable, and may be used alone or in multiple materials.
- the thickness of the metal layer is preferably 0.5 ⁇ m to 1000 ⁇ m, more preferably 1 ⁇ m to 500 ⁇ m, and particularly preferably 5 ⁇ m to 250 ⁇ m, from the viewpoint of conduction reliability and package compactness.
- various plating processes such as an electrolytic plating process, an electroless plating process, and a displacement plating process, a sputtering process, a vapor deposition process, a vacuum bonding process for metal foil, and an adhesion process with an adhesive layer provided. From the viewpoint of high heat resistance, it is preferable to form a metal layer alone, and from the viewpoint of thick film / uniform formation and high adhesion, layer formation by plating treatment is particularly preferable.
- the metal wiring layer thus formed is patterned by a known method according to the LED mounting design.
- a metal layer (including solder) is provided again at a location where the LED is actually mounted, and can be appropriately processed so as to be easily connected by thermocompression bonding, flip chip, wire bonding, or the like.
- a metal material such as solder or gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni) is preferable, and by heating From the viewpoint of mounting LEDs, a method of providing Au or Ag via solder or Ni is preferable from the viewpoint of connection reliability.
- the maximum reached temperature is 220 to 350 ° C. from the viewpoint of performing uniform and reliable mounting.
- 240 to 320 ° C is more preferable, and 260 to 300 ° C is particularly preferable.
- the time for maintaining these maximum temperatures is preferably 2 seconds to 10 minutes, more preferably 5 seconds to 5 minutes, and particularly preferably 10 seconds to 3 minutes.
- a desired value is reached before reaching the maximum temperature.
- a method of performing a heat treatment at a constant temperature of 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes, particularly preferably 20 seconds to 3 minutes can also be employed.
- the desired constant temperature is preferably 80 to 200 ° C, more preferably 100 to 180 ° C, and particularly preferably 120 to 160 ° C. If the temperature and time are less than these, the device may be insufficiently mounted. If the temperature and time are exceeded, the substrate may be deteriorated.
- the temperature at the time of mounting by wire bonding is preferably 80 to 300 ° C., more preferably 90 to 250 ° C., and particularly preferably 100 to 200 ° C. from the viewpoint of reliable mounting as described above.
- the heating time is preferably 2 seconds to 10 minutes, more preferably 5 seconds to 5 minutes, and particularly preferably 10 seconds to 3 minutes. If it is less than these temperatures and times, wire bonding may be insufficient, and if these temperatures and times are exceeded, the substrate may be deteriorated.
- Example 1 to 6 and Comparative Example 1 Production of aluminum reflective substrate Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.005 mass%, Mn: 0.001 mass%, Mg: 0.001 mass%, Zn: 0.001 Ingot containing 500% by weight and Ti: 0.03% by weight, the balance being Al and an inevitable impurity aluminum alloy to prepare a molten metal, performing the molten metal treatment and filtration, and having a thickness of 500 mm and a width of 1200 mm Was made by DC casting.
- the surface was shaved with a chamfering machine with an average thickness of 10 mm, it was kept soaked at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., rolling with a thickness of 2.7 mm using a hot rolling mill A board was used. Furthermore, after performing heat processing using a continuous annealing machine at 500 degreeC, it finished by cold rolling to 0.24 mm in thickness, and obtained the aluminum plate of JIS1050 material. After making this aluminum plate into width 1030mm, it used for the surface treatment shown below and obtained the aluminum reflective board
- the surface treatment was performed by successively performing the treatments indicated by “ ⁇ ” in Table 1 (Part 1) from the left of Table 1 among the following treatments (a) to (j). .
- the liquid was drained with the nip roller.
- FIG. 4 Using an apparatus as shown in FIG. 4, a suspension of slurry (pumice) and water (specific gravity 1.12) is supplied to the surface of the aluminum plate as a polishing slurry. However, a mechanical surface roughening treatment was performed with a rotating roller-like nylon brush.
- 1 is an aluminum plate
- 2 and 4 are roller brushes
- 3 is a polishing slurry
- 5, 6, 7 and 8 are support rollers.
- the average particle size of the abrasive was 40 ⁇ m, and the maximum particle size was 100 ⁇ m.
- the material of the nylon brush was 6 ⁇ 10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm.
- the nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers ( ⁇ 200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.
- the aluminum plate was subjected to an etching treatment by spraying using an aqueous solution having a caustic soda concentration of 2.6 mass%, an aluminum ion concentration of 6.5 mass%, and a temperature of 70 ° C., thereby dissolving the aluminum plate by 6 g / m 2 . . Then, water washing by spraying was performed.
- (C) Desmutting treatment The desmutting treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by mass of aluminum ions), and then washed with water by spraying.
- the nitric acid aqueous solution used for the desmut treatment was a waste liquid from a step of performing an electrochemical surface roughening treatment using alternating current in a nitric acid aqueous solution.
- Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz.
- the electrolytic solution at this time was a 10.5 g / L aqueous solution of nitric acid (containing 5 g / L of aluminum ions and 0.007% by mass of ammonium ions) at a liquid temperature of 50 ° C.
- the AC power supply waveform is the waveform shown in FIG. 1.
- the time TP until the current value reaches the peak from zero is 0.8 msec, the duty ratio is 1: 1, and a trapezoidal rectangular wave AC is used with the carbon electrode as the counter electrode.
- An electrochemical roughening treatment was performed. Ferrite was used for the auxiliary anode.
- the electrolytic cell used was the one shown in FIG.
- the current density was 30 A / dm 2 at the peak current value, and the amount of electricity was 220 C / dm 2 in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Then, water washing by spraying was performed.
- Desmut treatment by spraying was performed with a 15% by weight aqueous solution of sulfuric acid at a temperature of 30 ° C. (containing 4.5% by weight of aluminum ions), and then washed with water by spraying.
- the nitric acid aqueous solution used for the desmut treatment was a waste liquid from a step of performing an electrochemical surface roughening treatment using alternating current in a nitric acid aqueous solution.
- Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz.
- the electrolytic solution at this time was a hydrochloric acid 7.5 g / L aqueous solution (containing 5 g / L of aluminum ions) at a temperature of 35 ° C.
- the AC power supply waveform is the waveform shown in FIG. 1.
- the time TP until the current value reaches the peak from zero is 0.8 msec, the duty ratio is 1: 1, and a trapezoidal rectangular wave AC is used with the carbon electrode as the counter electrode.
- An electrochemical roughening treatment was performed. Ferrite was used for the auxiliary anode.
- the electrolytic cell used was the one shown in FIG.
- the current density was 25 A / dm 2 at the peak current value, and the amount of electricity was 50 C / dm 2 in terms of the total amount of electricity when the aluminum plate was the anode.
- water washing by spraying was performed.
- Desmutting treatment A desmutting treatment by spraying was performed with a 25% by weight aqueous solution of sulfuric acid at a temperature of 60 ° C. (containing 0.5% by weight of aluminum ions), followed by washing with water by spraying.
- the obtained surface-treated aluminum plate was subjected to through-hole processing with a drill, and was further processed into individual pieces having a final size of 3.2 mm ⁇ 2.8 mm by routing processing. For each size, the volume expansion due to the subsequent anodic oxidation was measured in advance and processed in consideration of the amount.
- Anodizing treatment was performed using an anodizing apparatus having a structure shown in FIG.
- Oxalic acid was used as the electrolytic solution supplied to the first and second electrolysis units. All of the electrolyte solutions had an oxalic acid concentration of 60 g / L (containing 0.5 mass% of aluminum ions) and a temperature of 38 ° C. Then, water washing by spraying was performed. The final oxide film thickness was 10 ⁇ m.
- Example 7 Above 1.
- anodizing treatment was performed as follows. That is, a treatment was performed at a sulfuric acid concentration of 60 g / L, a temperature of 15 ° C. and a constant voltage of 25 V for 70 minutes, and then a mixed aqueous solution of boric acid having a concentration of 30 g / L and sodium tetraborate having a concentration of 20 g / L, Treatment was performed at a temperature of 20 ° C. for 5 minutes to form an anodized film having a thickness of 9 ⁇ m.
- Example 8 On the anodic oxide film of the substrate of Example 7 obtained above, as a (k) oxide layer forming treatment, the following coating solution (A) was further applied so as to have a coating thickness of 1 ⁇ m, and at 100 ° C. A heat treatment was performed for 1 minute to form a sol-gel layer.
- Coating liquid (A) Tetraethyl orthosilicate 50.00g ⁇ Concentrated nitric acid 0.05g ⁇ Pure water 21.60g ⁇ Methanol 10.80 g
- Example 9 On the anodic oxide film of the substrate of Example 7 obtained above, (k) as an oxide layer forming treatment, the following coating solution (B) was further applied so as to have a coating thickness of 1 ⁇ m, and at 100 ° C. A heat treatment was performed for 1 minute to form a sol-gel layer.
- Coating liquid (B) Tetraethyl orthosilicate 50.00g ⁇ Concentrated nitric acid 0.05g ⁇ Titanium oxide 1.00g ⁇ Pure water 21.60g ⁇ Methanol 10.80 g
- the average wavelength of the small wave structure The surface of the porous alumina support was photographed at a magnification of 50000 times from directly above using a high resolution SEM, and 50 irregularities of the small wave structure were extracted from the obtained SEM photograph. The average wavelength was calculated by reading the wavelength.
- a cantilever having a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m (SI-DF20, manufactured by NANOPROBE) was used and measured in a DFM mode (Dynamic Force Mode). Further, the reference plane was obtained by correcting the slight inclination of the sample by least-square approximation of the obtained three-dimensional data. At the time of measurement, the surface of 50 ⁇ m ⁇ was measured at 512 ⁇ 512 points.
- the resolution in the XY direction was 1.9 ⁇ m
- the resolution in the Z direction was 1 nm
- the scan speed was 60 ⁇ m / sec.
- Luminance evaluation in LED element mounting unit Using the light reflecting substrates of Examples and Comparative Examples obtained as described above, luminance evaluation of phosphor-mixed white LED light emitting units was performed as follows. It was. That is, the light reflecting substrate of each example and comparative example is provided as the light reflecting substrate 140 in contact with the blue LED 110 of the light emitting unit 100 shown in FIG. 5, and each light emitting unit when the blue LED 110 is driven at 6V is provided. The brightness was compared. As a result, the light emitting unit using the fine structure of Example 1 as the light reflecting substrate was 1.1 to 1.3 times as bright as the light emitting unit using the substrate of Comparative Example 1. It was.
- Example 10 Creation of LED element mounting unit by creating a substrate for LED mounting (lower layer) and a through-hole (upper layer) substrate and stacking two substrates.
- the substrate for LED mounting (lower layer) the light reflecting substrate manufactured in Example 1 was used.
- the through-hole (upper layer) substrate was subjected to the same surface treatment and anodizing treatment as in Example 1 except that an aluminum plate was previously drilled to form a through-hole (upper layer) substrate to obtain a through-hole (upper layer) substrate.
- a tungsten carbide drill a 0.5 mm ⁇ through hole was formed in an aluminum material having a thickness of 0.24 mm at 1500 rpm and a processing time of 20 seconds.
- the two aluminum light-reflecting substrates obtained above were bonded with an epoxy adhesive, and then a dicing process was performed so as to be 3.2 ⁇ 2.8 mm centering on the through hole of 0.5 mm ⁇ . And a mounting substrate having a cavity structure was produced.
- a blue LED of 0.3 mm ⁇ and a 100 ⁇ m wide electric wiring for sending an electric signal to the LED are provided in the through hole of the cavity structure mounting board, and connected by wire bonding to obtain an LED element mounting unit. It was.
Abstract
Description
即ち、本発明は、以下を提供する。
ΔS=[(Sx-S0)/S0]×100(%) (A)
(5)前記光反射基板が、発光素子の発光を発光観測面側に反射する光反射基板である(1)~(4)のいずれかに記載の光反射基板。
(6)前記金属層が窪みを持つ形状であり、前記絶縁層が窪みを持つ形状の表面に設けられている(1)~(5)のいずれかに記載の光反射基板。
(7)前記(1)~(6)のいずれかに記載の光反射基板の製造方法であって、
アルミニウム板を用意し、
該アルミニウム板の表面を粗面化し、
該粗面化した表面を陽極酸化処理して絶縁層を形成する、
光反射基板の製造方法。
該アルミニウム板の表面を粗面化した後、以下の(a)および(b)工程を任意の順序で行う、
(a)発光素子を設けるための配線用スルーホールを形成し、および、基板をチップ化するためのルーティング加工を施す工程、
(b)粗面化した表面を陽極酸化処理して絶縁層を形成する工程、
とを有する光反射基板の製造方法。
(9)一方のアルミニウム基板は、少なくとも1つのスルーホールが形成され、他方のアルミニウム基板はスルーホールが形成されていない、(1)~(4)のいずれかに記載の光反射基板を少なくとも2枚重ねることにより形成される(6)に記載の光反射基板。
(10)前記ルーティング加工において、複数のチップの周りにチップを個別に切り離すための切り離し部を設け、切り離し部の一部に複数のチップをアルミニウム板に連結する連結部を有するように加工する際に、予めアルミニウム板の連結部になる部分をチップとなる部分より板厚を薄く設計して、ルーティング加工でアルミニウム板に連結部を残して切り離し部を切り欠いて、その後アルミニウム板を陽極酸化処理した後に連結部を切り離して、切り離した後の個別のチップの厚さ方向に連結部が切り離された後に形成されるアルミニウム部分の面積を小さくし、または無くした、個別のチップを得るルーティング加工を有する(8)に記載の光反射基板の製造方法。
(c)発光素子への電気信号伝送のための金属配線層を形成し、
上記金属配線層をパターン化する工程と;
(d)発光素子を実装する部分に相当する電極部に再度金属層を設ける加工を施す工程。
(12)(1)~(6)のいずれかまたは(9)に記載の光反射基板の上層に青色発光素子を有し、その周りおよび/または上部に蛍光発光体を備える白色系発光ダイオード装置。
本発明の光反射基板は、絶縁層と、該絶縁層と接して設けられる金属層とを有する320nm超~700nm波長光の光反射率が50%以上であって、且つ、300nm~320nm波長の光反射率が60%以上、であることを特徴としている。ここで全反射率は例えば分光光度計で測定される。
本発明の光反射基板は、上記反射率を満たすべく、その表面が、平均波長0.01~100μmの凹凸を有するのが好ましい。また、異なる波長の凹凸が重畳された形状をとっていてもよい。
本発明の光反射基板の表面がこのような凹凸を有すると、光拡散効果の向上、且つ、発光吸収効果/干渉効果(反射としてのロスとなりうる効果)を抑えることができると推定される。このため、本発明の光反射基板は、その反射性に優れる。
本発明の光反射基板の表面は、上記凹凸か、以下の凹凸かのいずれかを有する構造であるのが好ましい。
平均波長0.5~5μmの凹凸(以下「中波構造」ともいう。)は、光散乱性がより大きくなり、また、光吸収効果が抑えられる点で、平均波長0.7~4μmであるのが好ましく、平均波長1~3μmであるのがより好ましい。
平均波長0.01~0.5μmの凹凸(以下「小波構造」ともいう。)は、可視光の干渉効果が抑えられる点で、平均波長0.015~0.4μmであるのが好ましく、平均波長0.02~0.3μmであるのがより好ましい。
本発明の光反射基板の表面は、上述した大波構造、中波構造および小波構造からなる群から選ばれる少なくとも一つを有する。反射率をより高くすることができる点で、これらの二つ以上の凹凸構造を重畳して有するのが好ましく、三つすべてを重畳して有するのがより好ましい。
本発明の光反射基板は、上記の特定の凹凸を表面に有する場合は広い視野角で均一な光取り出しが可能となり、視野角依存性が小さい(視野角で反射率の差が小さい)。
本発明の光反射基板の表面が上記特定の凹凸を有する場合は、凹凸のアンカー効果により後に説明する蛍光発光体を有する透明樹脂との密着性が高いので放熱性に優れる。
即ち、光反射基板を1cm角の大きさに切り取って、ピエゾスキャナー上の水平な試料台にセットし、カンチレバーを試料表面にアプローチし、原子間力が働く領域に達したところで、XY方向にスキャンし、その際、試料の凹凸をZ方向のピエゾの変位でとらえる。ピエゾスキャナーは、XY方向について150μm、Z方向について10μm、走査可能なものを使用する。カンチレバーは共振周波数120~150kHz、バネ定数12~20N/mのもの(SI-DF20、NANOPROBE社製)を用い、DFMモード(Dynamic Force Mode)で測定する。また、求めた3次元データを最小二乗近似することにより試料のわずかな傾きを補正し基準面を求める。計測の際は、表面の50μm×50μmの範囲を512×512点測定する。XY方向の分解能は1.9μm、Z方向の分解能は1nm、スキャン速度は60μm/secとする。
本発明の光反射基板は、その形状は限定されない。例えば、図10(A)に示すように、金属層33であるアルミニウム板が平面状で絶縁層32も平面状である光反射基板30であってもよい。図10(B2)に示すように窪み34を有する形状であってもよい。窪み34内にLED素子を搭載すれば、光反射基板の窪みの側面の光反射も有効に利用することができる。図10(B2)、(B3)は、金属層であるアルミニウム板が窪み34(キャビティ)を持つ形状であり、絶縁層32も窪み形状の表面に形成されている光反射基板の断面図である。図10(B3)に示す本発明の光反射基板を製造する方法は限定されない。例えば図10(B1)、(B2)に示すように金型36を矢印方向にプレスしてアルミニウム板1に窪み34を持つ金属層33を形成してもよい。図10(B2)は、金属層33に窪み34が形成された状態の断面図を示し、図10(B2)に示すような形状のアルミニウム板を陽極酸化処理すれば、図10(B3)に示す絶縁層32と金属層33とを有する光反射基板30が製造できる。
図10(C1)、(C2)、(C3)は、図10(B1)、(B2)、(B3)と同様の形状の光反射基板の他の製造例を示す断面図である。この光反射基板は、図10(C2)に示す、スルーホールを有さず少なくとも絶縁層32と金属層33とを有する光反射基板30と、図10(C1)に示すように、スルーホール35を有し、絶縁層321と金属層331とを有する他の光反射基板301とを2枚用意する。次に、図10(C3)に示すように、2枚の光反射基板を重ねることにより窪み34を有する光反射基板303を形成する。2枚の光反射基板は接着してもよい。図10(C1)に示す光反射基板301は、アルミニウム板に予めスルーホール35をあけてから陽極酸化処理して絶縁層321を形成して製造してもよい。スルーホール加工は安価なドリル加工で形成でき、またスルーホール形状や大きさの制御も非常に簡便であるため、上記のように2枚の加工基板を重ねたり貼り合せる事で、従来と同じ形状のキャビティ構造を有する光反射基板を安価に製造できる。
本発明の光反射基板の製造には、公知のアルミニウム板を用いることができる。本発明に用いられるアルミニウム板は、寸度的に安定なアルミニウムを主成分とする金属であり、アルミニウムまたはアルミニウム合金からなる。純アルミニウム板のほか、アルミニウムを主成分とし微量の異元素を含む合金板を用いることもできる。
DC鋳造においては、冷却速度が0.5~30℃/秒の範囲で凝固する。1℃未満であると粗大な金属間化合物が多数形成されることがある。DC鋳造を行った場合、板厚300~800mmの鋳塊を製造することができる。その鋳塊を、常法に従い、必要に応じて面削を行い、通常、表層の1~30mm、好ましくは1~10mmを切削する。その前後において、必要に応じて、均熱化処理を行う。均熱化処理を行う場合、金属間化合物が粗大化しないように、450~620℃で1~48時間の熱処理を行う。熱処理が1時間より短い場合には、均熱化処理の効果が不十分となることがある。
アルミニウムウェブの場合、アルミニウムの荷姿としては、例えば、鉄製パレットにハードボードとフェルトとを敷き、製品両端に段ボールドーナツ板を当て、ポリチュ-ブで全体を包み、コイル内径部に木製ドーナツを挿入し、コイル外周部にフェルトを当て、帯鉄で絞め、その外周部に表示を行う。また、包装材としては、ポリエチレンフィルム、緩衝材としては、ニードルフェルト、ハードボードを用いることができる。この他にもいろいろな形態があるが、安定して、キズも付かず運送等が可能であればこの方法に限るものではない。
本発明の反射基板を製造する際の表面処理は、粗面化処理および陽極酸化処理を含む。この多孔質アルミナ担体の製造工程は、粗面化処理および陽極酸化処理以外の各種の工程を含んでいてもよい。
上述した表面形状を形成させるための代表的方法として、アルミニウム板に機械的粗面化処理、アルカリエッチング処理、酸によるデスマット処理および電解液を用いた電気化学的粗面化処理を順次施す方法、アルミニウム板に機械的粗面化処理、アルカリエッチング処理、酸によるデスマット処理および異なる電解液を用いた電気化学的粗面化処理を複数回施す方法、アルミニウム板にアルカリエッチング処理、酸によるデスマット処理および電解液を用いた電気化学的粗面化処理を順次施す方法、アルミニウム板にアルカリエッチング処理、酸によるデスマット処理および異なる電解液を用いた電気化学的粗面化処理を複数回施す方法が挙げられるが、本発明はこれらに限定されない。これらの方法において、前記電気化学的粗面化処理の後、更に、アルカリエッチング処理および酸によるデスマット処理を施してもよい。
機械的粗面化処理は、電気化学的粗面化処理と比較して、より安価に、平均波長5~100μmの凹凸のある表面を形成することができるため、大波構造を形成させる粗面化処理の手段として有効である。
機械的粗面化処理方法としては、例えば、アルミニウム表面を金属ワイヤーでひっかくワイヤーブラシグレイン法、研磨球と研磨剤でアルミニウム表面を砂目立てするボールグレイン法、特開平6-135175号公報および特公昭50-40047号公報に記載されているナイロンブラシと研磨剤で表面を砂目立てするブラシグレイン法を用いることができる。
また、凹凸面をアルミニウム板に圧接する転写方法を用いることもできる。即ち、特開昭55-74898号、特開昭60-36195号、特開昭60-203496号の各公報に記載されている方法のほか、転写を数回行うことを特徴とする特開平6-55871号公報、表面が弾性であることを特徴とする特開平6-24168号公報に記載されている方法も適用可能である。
また、放電加工、ショットブラスト、レーザ、プラズマエッチング等を用いて、微細な凹凸を食刻した転写ロールを用いて繰り返し転写を行う方法や、微細粒子を塗布した凹凸のある面を、アルミニウム板に接面させ、その上より複数回繰り返し圧力を加え、アルミニウム板に微細粒子の平均直径に相当する凹凸パターンを複数回繰り返し転写させる方法を用いることもできる。転写ロールへ微細な凹凸を付与する方法としては、特開平3-8635号、特開平3-66404号、特開昭63-65017号の各公報等に記載されている公知の方法を用いることができる。また、ロール表面にダイス、バイト、レーザ等を使って2方向から微細な溝を切り、表面に角形の凹凸をつけてもよい。このロール表面には、公知のエッチング処理等を行って、形成させた角形の凹凸が丸みを帯びるような処理を行ってもよい。
また、表面の硬度を上げるために、焼き入れ、ハードクロムメッキ等を行ってもよい。
そのほかにも、機械的粗面化処理としては、特開昭61-162351号、特開昭63-104889号等の公報に記載されている方法を用いることもできる。
本発明においては、生産性等を考慮して上述したそれぞれの方法を併用することもできる。これらの機械的粗面化処理は、電気化学的粗面化処理の前に行うのが好ましい。
電気化学的粗面化処理(以下「電解粗面化処理」ともいう。)には、通常の交流を用いた電気化学的粗面化処理に用いられる電解液を用いることができる。中でも、塩酸または硝酸を主体とする電解液を用いるのが、上述した表面形状を得やすいので好ましい。
硝酸を主体とする電解液を用いた電気化学的粗面化処理により、平均波長0.5~5μmの凹凸を形成させることができる。ただし、電気量を比較的多くしたときは、電解反応が集中し、波長5μmを超える凹凸も生成する。
このような表面形状を得るためには、電解反応が終了した時点でのアルミニウム板のアノード反応にあずかる電気量の総和が、1~1000C/dm2であるのが好ましく、50~300C/dm2であるのがより好ましい。この際の電流密度は20~100A/dm2であるのが好ましい。
また、例えば、高濃度、例えば、硝酸濃度15~35質量%の硝酸電解液を用いて30~60℃で電解を行ったり、硝酸濃度0.7~2質量%の硝酸電解液を用いて高温、例えば、80℃以上で電解を行ったりすることで、平均波長0.20μm以下の小波構造を形成させることもできる。その結果、ΔSを大きくすることができる。
塩酸はそれ自身のアルミニウム溶解力が強いため、わずかな電解を加えるだけで表面に微細な凹凸を形成させることが可能である。この微細な凹凸は、平均波長が0.01~0.2μmであり、アルミニウム板の表面の全面に均一に生成する。
このような表面形状を得るためには電解反応が終了した時点でのアルミニウム板のアノード反応にあずかる電気量の総和が、1~100C/dm2であるのが好ましく、20~70C/dm2であるのがより好ましい。この際の電流密度は20~50A/dm2であるのが好ましい。
陰極電解処理は、酸性溶液中で陰極電気量が好ましくは3~80C/dm2、より好ましくは5~30C/dm2で行われる。陰極電気量が3C/dm2未満であると、スマット付着量が不足する場合があり、また、80C/dm2を超えると、スマット付着量が過剰となる場合がある。電解液は、電解粗面化処理で使用する溶液と同一であっても異なっていてもよい。
アルカリエッチング処理は、上記アルミニウム板をアルカリ溶液に接触させることにより、表層を溶解させる処理である。
電解粗面化処理より前に行われるアルカリエッチング処理は、機械的粗面化処理を行っていない場合には、アルミニウム板(圧延アルミ)の表面の圧延油、汚れ、自然酸化皮膜等を除去することを目的として、また、既に機械的粗面化処理を行っている場合には、機械的粗面化処理によって生成した凹凸のエッジ部分を溶解させ、急峻な凹凸を滑らかなうねりを持つ表面に変えることを目的として行われる。
電解粗面化処理またはアルカリエッチング処理を行った後、表面に残留する汚れ(スマット)を除去するために酸洗い(デスマット処理)が行われるのが好ましい。
用いられる酸としては、例えば、硝酸、硫酸、リン酸、クロム酸、フッ化水素酸、ホウフッ化水素酸が挙げられる。上記デスマット処理は、例えば、上記アルミニウム板を塩酸、硝酸、硫酸等の濃度0.5~30質量%の酸性溶液(アルミニウムイオン0.01~5質量%を含有する。)に接触させることにより行う。アルミニウム板を酸性溶液に接触させる方法としては、例えば、アルミニウム板を酸性水溶液を入れた槽の中を通過させる方法、アルミニウム板を酸性溶液を入れた槽の中に浸せきさせる方法、酸性溶液をアルミニウム板の表面に噴きかける方法が挙げられる。デスマット処理においては、酸性溶液として、上述した電解粗面化処理において排出される硝酸を主体とする水溶液もしくは塩酸を主体とする水溶液の廃液、または、後述する陽極酸化処理において排出される硫酸を主体とする水溶液の廃液を用いることができる。デスマット処理の液温は、25~90℃であるのが好ましい。また、処理時間は、1~180秒であるのが好ましい。デスマット処理に用いられる酸性溶液には、アルミニウムおよびアルミニウム合金成分が溶け込んでいてもよい。
本発明の光反射基板においては、発光素子を実装するにあたり、適宜配線部を設けるためのスルーホール加工、並びに、最終製品を想定してのチップ化を行うためのルーティング加工(最終製品に個別化するための加工)を行うこともできる。スルーホール加工は陽極酸化工程の前に行っても後に行ってもよい。後述する陽極酸化による絶縁層形成前に上記加工を行うと、陽極酸化で形成される絶縁層への亀裂を防ぐ観点、及び、上記加工により生じる基板端面部への絶縁性を保持することができる。陽極酸化工程の後で行えば、陽極酸化処理工程の効率を上げられ、また最終製品のサイズに精度よく加工することができる。
ルーティング加工については、最終的なチップの大きさ/形状を考慮する必要があるが、方形型のチップを想定した場合、チップのコンパクト性、及び、加工適性の観点から、1辺が0.1mm~50mmが好ましく、0.2mm~40mmがより好ましく、0.4mm~30mmが特に好ましい。特に、メインパッケージ用の光反射基板を想定する場合には、現在の形状規格例である、3.2mm×2.8mm、1.6mm×0.8mm、等の大きさにルーティングすることが好ましい。
また、ルーティングしたあとの素子搭載部(図示しない、後に素子が搭載される部分)には、後述する陽極酸化処理により絶縁層を設けるために、素子部(図示しない、素子と電気的接続がされる部分)への電気導通性を施す形状に加工しておくことが好ましい。好適な方法としては、導通部を設けた状態でルーティング加工する方法、導通ワイヤ等により素子部を接続しておく方法、等が挙げられるがこれらに限定されない。
ルーティング加工は、限定されないが、例えば図11(A1)に示すような金属板であるアルミニウム板1を、図11(A2)に示すように個別の光反射基板となるチップ41の部分を取り囲む切り離し部43をアルミニウム板1の底面まで切り欠くが、その際チップ同士またはチップをアルミニウム板1に連結する連結部42を残しておくとチップ41がばらばらにならずにアルミニウム板として一体として扱えるので好適である。その後図11(A3)に示すように陽極酸化処理等の必要な処理をした後に、図11(A4)に示すように連結部42を切り離して個別のチップ41とする。ところがその際切り離された後のチップ側面の連結部42の切り離し跡45に、陽極酸化されていない金属アルミニウムが剥き出しになるので得られる個別のチップ41の側面の絶縁性が不十分になる。
これを防ぐために、本発明のルーティング加工では、図11(B1)、(B2)の左端に断面図で示すように金属板であるアルミニウム板1の状態で予め連結部42になる部分をチップ41となる部分より薄く設計する。好ましくは予め連結部分の厚みを、陽極酸化により形成する酸化皮膜厚みの2倍以下に設計する。薄く設計する、または陽極酸化により形成する酸化皮膜厚みの2倍以下にするには、ルーティング加工と同様の各種の加工方法を行うことができる。連結部42になる部分を薄く設計しておけば、図11(B1)、(B2)の中央に断面図で示すように、陽極酸化処理後は、陽極酸化皮膜である絶縁膜は連結部の厚さのほとんどの部分を占めるように陽極酸化することができる。例えば図11(B1)、中央の図で示すように切り離し跡45のアルミニウム部分はごくわずかな厚さとなる。また、図11(B2)、中央の図で示すように連結部はその厚さのすべてが陽極酸化される。このような連結部を切り離すと、図11(B1)、(B2)の右端の図に示すように、個別のチップの切り離し跡45の陽極酸化されていない部分はごく少し[図11(B1)右端]になるか、全くない[図11(B2)右端]個別のチップ41が得られる。
以上のように表面処理され、加工されたアルミニウム板に、更に、陽極酸化処理を施す。陽極酸化処理により、アルミナからなる陽極酸化皮膜がアルミニウム板の表面に形成され、多孔質、あるいは、非孔質の表面絶縁層が得られる。
本発明においては、必要に応じて陽極酸化皮膜が多孔質の場合、存在するマイクロポアを封じる封孔処理を行ってもよい。封孔処理は、沸騰水処理、熱水処理、蒸気処理、ケイ酸ソーダ処理、亜硝酸塩処理、酢酸アンモニウム処理等の公知の方法に従って行うことができる。例えば、特公昭56-12518号、特開平4-4194号、特開平5-202496号、特開平5-179482号の各公報等に記載されている装置および方法で封孔処理を行ってもよい。
上述した各処理の工程終了後には水洗を行うのが好ましい。水洗には、純水、井水、水道水等を用いることができる。処理液の次工程への持ち込みを防ぐためにニップ装置を用いてもよい。
その他、本発明の光反射基板においては、必要に応じて表面に種々の処理を施すことができる。
例えば、反射基板の白色性を高めるために、酸化チタン等の白色性絶縁性材料からなる無機絶縁層、白色レジスト等の有機絶縁層を設けても良い。
また、上記白色以外にも、例えば電着処理により、アルミナよりなる絶縁層に所望の色を着色することができる。具体的には、「陽極酸化」金属表面技術協会編.金属表面技術講座B(1969 PP.195~207)、「新アルマイト理論」カロス出版(1997 PP.95~96)等に記載されているような有色染色性のイオン種、具体的には、Coイオン、Feイオン、Auイオン、Pbイオン、Agイオン、Seイオン、Snイオン、Niイオン、Cuイオン、Biイオン、Moイオン、Sbイオン、Cdイオン、および・またはAsイオンを電解液に混入して、電解処理することにより、着色が施される。
本発明において用いられる金属アルコキシドは、特に限定されないが、厚さが均一性の良い層を形成させる観点から、Al(O-R)n、Ba(O-R)n、B(O-R)n、Bi(O-R)n、Ca(O-R)n、Fe(O-R)n、Ga(O-R)n、Ge(O-R)n、Hf(O-R)n、In(O-R)n、K(O-R)n、La(O-R)n、Li(O-R)n、Mg(O-R)n、Mo(O-R)n、Na(O-R)n、Nb(O-R)n、Pb(O-R)n、Po(O-R)n、Po(O-R)n、P(O-R)n、Sb(O-R)n、Si(O-R)n、Sn(O-R)n、Sr(O-R)n、Ta(O-R)n、Ti(O-R)n、V(O-R)n、W(O-R)n、Y(O-R)n、Zn(O-R)n、Zr(O-R)n、等が挙げられる(文章中Rは、置換基を有してもよい、鎖状、分枝状、または、環状の、炭化水素基、nは任意の自然数を示す。)。中でも、本発明の好ましい態様として、絶縁層がアルミニウムの陽極酸化層であるので、アルミナとの反応性に優れ、ゾルゲル層形成性に優れた、Si(O-R)n系がより好ましい。
なお、ゾルゲル層を形成する方法としては特に限定されないが、層の厚さを制御する観点から、ゾル液を塗布して加熱する方法が好ましい。また、ゾル液の濃度としては、0.1~90質量%が好ましく、1~80質量%がより好ましく、5~70質量%が特に好ましい。なお、層を厚くするために、繰り返し重ねて塗布しても良い。
また、本発明においてゾルゲル層を形成する際には、その厚さは、高反射率、絶縁性の観点から、0.01μm~20μmが好ましく、0.05μm~15μmがより好ましく、0.1μm~10μmが特に好ましい。この範囲より厚くなると、高反射率の観点から好ましくなく、この範囲より薄くなると絶縁性の観点から好ましくない。
本発明の光反射基板は、用いるLEDの種類、及び発光素子の形状、等に特に限定はなく、種々の用途に用いることができる。また、従来公知のLEDを用いる発光装置の光反射基板として用いることができる。
例えば、図5に示す基板140の代わりに本発明の光反射基板30を用いることで発光ユニット100の輝度を向上させることができる。
また、図7に示すように、本発明の絶縁層32と金属層33とを有する光反射基板30上に青色LED22を設置し、公知の樹脂24で封止し、その上部に蛍光発光体を有するバルブ金属の陽極酸化層である微細構造体26(蛍光発光ユニット)を備える構成の蛍光発光素子としてもよい。これらの蛍光発光素子については、特願2009-134007号明細書、特願2009-139261号明細書に記載されている。
図9は、絶縁層32とそれに接して設けられる金属層33を有する本発明の光反射基板30上に載置された発光ダイオード等の素子37を蛍光粒子150を有する透明樹脂160で封止した蛍光発光ユニット100を示す断面図である。素子37は光反射基板30上にダイボンデイング等で載置され、光反射基板30にはスルーホール35が設けられ、素子37の下部に位置する金属層33は、他の基板部分より厚みがある形状に成型されヒートシンク39としてもよい。好ましくは絶縁層32はアルミニウム金属層33の陽極酸化被膜であり、スルーホール内部も陽極酸化されて絶縁層を形成する。素子37はワイヤボンデイングされて外部電極120,130と電気的に接続する。本発明の光反射基板30は、特定の波長における全反射率が高いので、これを基板として用いる蛍光発光ユニット100の輝度が高い。
透明樹脂160の材質は熱硬化性樹脂が好ましい。熱硬化性樹脂のうち、エポキシ樹脂、変性エポキシ樹脂、シリコーン樹脂、変性シリコーン樹脂、アクリレート樹脂、ウレタン樹脂、ポリイミド樹脂からなる群から選択される少なくとも1種により形成することが好ましく、特にエポキシ樹脂、変性エポキシ樹脂、シリコーン樹脂、変性シリコーン樹脂が好ましい。透明樹脂160は、素子37を保護するため硬質のものが好ましい。また、透明樹脂160は、耐熱性、耐候性、耐光性に優れた樹脂を用いることが好ましい。透明樹脂160は、所定の機能を持たせるため、フィラー、拡散剤、顔料、蛍光物質、反射性物質、紫外線吸収剤、酸化防止剤からなる群から選択される少なくとも1種を混合することもできる。
蛍光粒子150は、素子37からの光を吸収し異なる波長の光に波長変換するものであればよい。例えば、Eu、Ce等のランタノイド系元素で主に賦活される窒化物系蛍光体・酸窒化物系蛍光体・サイアロン系蛍光体・βサイアロン系蛍光体、Eu等のランタノイド系、Mn等の遷移金属系の元素により主に付活されるアルカリ土類ハロゲンアパタイト蛍光体、アルカリ土類金属ホウ酸ハロゲン蛍光体、アルカリ土類金属アルミン酸塩蛍光体、アルカリ土類ケイ酸塩蛍光体、アルカリ土類硫化物蛍光体、アルカリ土類チオガレート蛍光体、アルカリ土類窒化ケイ素蛍光体、ゲルマン酸塩蛍光体、又は、Ce等のランタノイド系元素で主に付活される希土類アルミン酸塩蛍光体、希土類ケイ酸塩蛍光体又はEu等のランタノイド系元素で主に賦活される有機及び有機錯体等から選ばれる少なくともいずれか1以上であることが好ましい。
これらの蛍光発光体が青色LEDからの青色光を吸収して蛍光(黄色系蛍光)を生じ、この蛍光と青色LEDの残光とにより、発光素子から白色系光が発光される。
上述した方式は、青色LED光源1チップと黄色蛍光体1種とを組み合わせたいわゆる「擬似白色発光型」であるが、このほかにも、例えば紫外~近紫外LED光源1チップと赤色/緑色/青色蛍光体等を数種組み合わせた「紫外~近紫外光源型」、及び、赤色/緑色/青色3光源で白色発光させる「RGB光源型」、等の公知の発光方法を用いる発光ユニットの発光素子の基板に本発明の光反射基板を用いることができる。
本発明に関わる反射基板においては、LEDを実装するにあたり、実際にLEDへ電気信号を伝送するための金属配線層を設けることができる。
好適な金属層としては、半田、あるいは、金(Au)、銀(Ag)、銅(Cu)、アルミニウム(Al)、マグネシウム(Mg)、ニッケル(Ni)、等の金属素材が好ましく、加熱によるLEDの実装の観点では、半田、あるいは、Niを介してのAu、Agを設ける方法が、接続信頼性の観点から好ましい。
また同加熱処理における本発明基板の、アルミ層とアルミ陽極酸化層の熱膨張率差に起因するアルミ陽極酸化層へのクラック発生を抑止する観点から、上記最高到達温度に到達する前に、所望の一定温度で5秒~10分、より好ましくは10秒~5分、特に好ましくは20秒~3分、の熱処理を施す方法をとることもできる。この場合所望の一定温度としては、80~200℃であることが好ましく、100~180℃がより好ましく、120~160℃が特に好ましい。これらの温度・時間未満であると素子の実装が不十分となる恐れがあり、これらの温度・時間超であると基板が劣化する恐れがある。
(実施例1~6ならびに比較例1)
1.アルミ反射基板の作製
Si:0.06質量%、Fe:0.30質量%、Cu:0.005質量%、Mn:0.001質量%、Mg:0.001質量%、Zn:0.001質量%、Ti:0.03質量%を含有し、残部はAlと不可避不純物のアルミニウム合金を用いて溶湯を調製し、溶湯処理およびろ過を行った上で、厚さ500mm、幅1200mmの鋳塊をDC鋳造法で作成した。表面を平均10mmの厚さで面削機により削り取った後、550℃で、約5時間均熱保持し、温度400℃に下がったところで、熱間圧延機を用いて厚さ2.7mmの圧延板とした。更に、連続焼鈍機を用いて熱処理を500℃で行った後、冷間圧延で、厚さ0.24mmに仕上げ、JIS 1050材のアルミニウム板を得た。このアルミニウム板を幅1030mmにした後、以下に示す表面処理に供し、アルミ反射基板を得た。
図4に示したような装置を使って、研磨剤(パミス)と水との懸濁液(比重1.12)を研磨スラリー液としてアルミニウム板の表面に供給しながら、回転するローラ状ナイロンブラシにより機械的粗面化処理を行った。図4において、1はアルミニウム板、2および4はローラ状ブラシ、3は研磨スラリー液、5、6、7および8は支持ローラである。研磨剤の平均粒径は40μm、最大粒径は100μmであった。ナイロンブラシの材質は6・10ナイロン、毛長は50mm、毛の直径は0.3mmであった。ナイロンブラシはφ300mmのステンレス製の筒に穴をあけて密になるように植毛した。回転ブラシは3本使用した。ブラシ下部の2本の支持ローラ(φ200mm)の距離は300mmであった。ブラシローラはブラシを回転させる駆動モータの負荷が、ブラシローラをアルミニウム板に押さえつける前の負荷に対して7kWプラスになるまで押さえつけた。ブラシの回転方向はアルミニウム板の移動方向と同じであった。ブラシの回転数は200rpmであった。
アルミニウム板をカセイソーダ濃度2.6質量%、アルミニウムイオン濃度6.5質量%、温度70℃の水溶液を用いてスプレーによるエッチング処理を行い、アルミニウム板を6g/m2溶解した。その後、スプレーによる水洗を行った。
温度30℃の硝酸濃度1質量%水溶液(アルミニウムイオンを0.5質量%含む。)で、スプレーによるデスマット処理を行い、その後、スプレーで水洗した。デスマット処理に用いた硝酸水溶液は、硝酸水溶液中で交流を用いて電気化学的粗面化処理を行う工程の廃液を用いた。
60Hzの交流電圧を用いて連続的に電気化学的な粗面化処理を行った。このときの電解液は、硝酸10.5g/L水溶液(アルミニウムイオンを5g/L、アンモニウムイオンを0.007質量%含む。)、液温50℃であった。交流電源波形は図1に示した波形であり、電流値がゼロからピークに達するまでの時間TPが0.8msec、duty比1:1、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的な粗面化処理を行った。補助アノードにはフェライトを用いた。使用した電解槽は図2に示すものを使用した。電流密度は電流のピーク値で30A/dm2、電気量はアルミニウム板が陽極時の電気量の総和で220C/dm2であった。補助陽極には電源から流れる電流の5%を分流させた。その後、スプレーによる水洗を行った。
アルミニウム板をカセイソーダ濃度26質量%、アルミニウムイオン濃度6.5質量%の水溶液を用いてスプレーによるエッチング処理を32℃で行い、アルミニウム板を1.0g/m2溶解し、前段の交流を用いて電気化学的粗面化処理を行ったときに生成した水酸化アルミニウムを主体とするスマット成分を除去し、また、生成した凹凸のエッジ部分を溶解してエッジ部分を滑らかにした。その後、スプレーによる水洗を行った。
温度30℃の硫酸濃度15質量%水溶液(アルミニウムイオンを4.5質量%含む。)で、スプレーによるデスマット処理を行い、その後、スプレーで水洗した。デスマット処理に用いた硝酸水溶液は、硝酸水溶液中で交流を用いて電気化学的粗面化処理を行う工程の廃液を用いた。
60Hzの交流電圧を用いて連続的に電気化学的な粗面化処理を行った。このときの電解液は、塩酸7.5g/L水溶液(アルミニウムイオンを5g/L含む。)、温度35℃であった。交流電源波形は図1に示した波形であり、電流値がゼロからピークに達するまでの時間TPが0.8msec、duty比1:1、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的粗面化処理を行った。補助アノードにはフェライトを用いた。使用した電解槽は図2に示すものを使用した。電流密度は電流のピーク値で25A/dm2、電気量はアルミニウム板が陽極時の電気量の総和で50C/dm2であった。その後、スプレーによる水洗を行った。
アルミニウム板をカセイソーダ濃度26質量%、アルミニウムイオン濃度6.5質量%の水溶液を用いてスプレーによるエッチング処理を32℃で行い、アルミニウム板を0.1g/m2溶解し、前段の交流を用いて電気化学的粗面化処理を行ったときに生成した水酸化アルミニウムを主体とするスマット成分を除去し、また、生成した凹凸のエッジ部分を溶解してエッジ部分を滑らかにした。その後、スプレーによる水洗を行った。
温度60℃の硫酸濃度25質量%水溶液(アルミニウムイオンを0.5質量%含む。)で、スプレーによるデスマット処理を行い、その後、スプレーによる水洗を行った。
図3に示す構造の陽極酸化装置を用いて陽極酸化処理を行った。第1および第2電解部に供給した電解液としては、シュウ酸を用いた。電解液は、いずれも、シュウ酸濃度60g/L(アルミニウムイオンを0.5質量%含む。)、温度38℃であった。その後、スプレーによる水洗を行った。最終的な酸化皮膜の厚さは10μmであった。
上記1.アルミ反射基板の作製 において、(j)陽極酸化処理を、以下の方法とした以外は、実施例6と同様の処理を施した。
すなわち、硫酸濃度60g/L、温度15℃で、25V定電圧にて70分間処理を施し、その後、濃度30g/Lのホウ酸、濃度20g/Lの四ホウ酸ナトリウム、の混合水溶液にて、温度20℃で5分間処理し、厚さ9μm厚さの陽極酸化皮膜を形成した。
上記で得られた実施例7の基板の陽極酸化皮膜上に、(k)酸化物層形成処理として、更に以下記載の塗布液(A)を塗布厚1μmとなるように塗布し、100℃で1分間加熱処理を施しゾルゲル層を形成した。
塗布液(A)
・テトラエチルオルソシリケート 50.00g
・濃硝酸 0.05g
・純水 21.60g
・メタノール 10.80g
上記で得られた実施例7の基板の陽極酸化皮膜上に、(k)酸化物層形成処理として、更に以下記載の塗布液(B)を塗布厚1μmとなるように塗布し、100℃で1分間加熱処理を施しゾルゲル層を形成した。
塗布液(B)
・テトラエチルオルソシリケート 50.00g
・濃硝酸 0.05g
・酸化チタン 1.00g
・純水 21.60g
・メタノール 10.80g
実施例1で用いたアルミニウム板を用い、(j)の陽極酸化処理のみを行った。
上記で得られた光反射基板の表面の凹凸について、下記(1)~(3)の測定を行い、大波構造、中波構造および小波構造の各平均波長を算出した。
結果を第1表に示す。なお、第1表中、「-」は、該当する平均波長の凹凸がなかったことを示す。
触針式粗さ計(sufcom575、東京精密社製)で2次元粗さ測定を行い、ISO4287に規定されている平均山間隔Smを5回測定し、その平均値を平均波長とした。
2次元粗さ測定は、以下の条件で行った。
<測定条件>
カットオフ値0.8mm、傾斜補正FLAT-ML、測定長3mm、縦倍率10000倍、走査速度0.3mm/sec、触針先端径2μm
高分解能SEMを用いて多孔質アルミナ担体の表面を真上から倍率50000倍で撮影し、得られたSEM写真において小波構造の凹凸を50個抽出し、その直径を読み取って波長とし、平均波長を算出した。
上記で得られた多孔質アルミナの表面についてΔSを求めるために、原子間力顕微鏡(SP13700、セイコー電子工業社製)により表面形状を測定し、3次元データを求めた。以下、具体的な手順を説明する。
多孔質アルミナを1cm角の大きさで、ピエゾスキャナー上の水平な試料台にセットし、カンチレバーを試料表面にアプローチし、原子間力が働く領域に達したところで、XY方向にスキャンし、その際、試料の凹凸をZ方向のピエゾの変位でとらえた。ピエゾスキャナーは、XY方向について150μm、Z方向について10μm、走査可能なものを使用した。カンチレバーは共振周波数120~150kHz、バネ定数12~20N/mのもの(SI-DF20、NANOPROBE社製)を用い、DFMモード(DynamicForce Mode)で測定した。また、求めた3次元データを最小二乗近似することにより試料のわずかな傾きを補正し基準面を求めた。
計測の際は、表面の50μm□を512×512点測定した。XY方向の分解能は1.9μm、Z方向の分解能は1nm、スキャン速度は60μm/secとした。
上記で求められた3次元データ(f(x,y))を用い、隣り合う3点を抽出し、その3点で形成される微小三角形の面積の総和を求め、実面積Sxとした。表面積差ΔSは、得られた実面積Sxと幾何学的測定面積S0(50μm×50μm)とから、上記式(1)により求めた。
結果を第1表(その2)に示す。
得られた実施例、比較例の光反射基板は、300~700nmの全反射率を計測するため、エックスライト社製SP60を用いて10nm毎に計測した。結果を図6および図8に示す。
上記のようにして得られた実施例、比較例の光反射基板を用いて、以下のようにして、蛍光体混色型の白色系LED発光ユニットの輝度評価を行なった。
すなわち、図5に示す発光ユニット100の青色LED110に接する形で、各実施例、比較例の光反射基板を、光反射基板140として設け、青色LED110を6Vで駆動させた際の各発光ユニットの輝度を比較した。
その結果、実施例1の微細構造体を光反射基板として用いた発光ユニットは、比較例1の基板を用いた発光ユニットと比較して、1.1~1.3倍の輝度向上効果が得られた。
上記5と同様に、得られた実施例、比較例の光反射基板を用いて、蛍光体混色型の白色系LED発光ユニットを製造し、光反射基板の光指向性評価を行った。すなわち、マルチ分光ゴニオフォトメータを用いて、反射光測定視野角を175度、および、120度とした際の400~700nmの反射率の平均を求めた。結果を表3に示す。一般にLED発光部材は、発光面に対し、垂直方向への指向性を高める設計が求められており、本発明の実施例の光反射基板を用いた発光ユニットは、視野角度依存性が小さく(視野角で反射率の差が小さい)光反射特性に優れている。
6.LED実装用(下層)基板とスルーホール(上層)基板とを作成し2枚の基板を重ねたLED素子実装ユニットの作成
LED実装用(下層)基板としては実施例1で製造した光反射基板を用いた。
スルーホール(上層)基板は、予めアルミニウム板に、ドリル加工によりスルーホール形成加工を行った以外は実施例1と同様の表面処理および陽極酸化処理を行ってスルーホール(上層)基板とした。具体的には、炭化タングステン素材のドリルを用い、1500rpm、加工時間20秒で厚さ0.24mmのアルミ材に0.5mmφのスルーホールを形成した。
上記で得た、2枚のアルミニウム光反射基板を、エポキシ系接着剤にて貼り合せた、その後、上記0.5mmφのスルーホールを中心に、3.2×2.8mmとなるようにダイシング処理により切り出し、キャビティ構造の実装基板を作成した。
上記キャビティ構造の実装基板のスルーホール内に0.3mm□の青色LED、及びこのLEDに電気信号を送付するための100μm幅の電気配線を設け、ワイヤボンディングにより接続し、LED素子実装ユニットを得た。
2、4 ローラ状ブラシ
3 研磨スラリー液
5、6、7、8 支持ローラ
12 ラジアルドラムローラ
13a、13b 主極
14 電解処理液
15 電解液供給口
16 スリット
17 電解液通路
18 補助陽極
19a、19b サイリスタ
20 交流電源
22 青色LED
24 樹脂
26 蛍光発光ユニット
30、301、303 光反射基板
32、321 絶縁層
33、331 金属層
34 窪み(キャビティ)
35 スルーホール
36 金型
37 素子
39 ヒートシンク
40 主電解槽
41 チップ
42 連結部
43 切り離し部
45 切り離し跡
50 補助陽極槽
410 陽極酸化処理装置
412 給電槽
414 電解処理槽
416 アルミニウム板
418、426 電解液
420 給電電極
422、428 ローラ
424 ニップローラ
430 電解電極
432 槽壁
434 直流電源
100 発光ユニット
110 青色LED
120,130 電極
140 光反射基板
150 蛍光粒子
160 透明樹脂
Claims (12)
- 少なくとも、絶縁層と、該絶縁層と接して設けられる金属層とを有する光反射基板において、320nm超~700nm波長光の全反射率が50%以上であって、且つ、300nm~320nm波長光の全反射率が60%以上であることを特徴とする、光反射基板。
- 前記光反射基板の表面が、平均波長0.01~100μmの凹凸を有する請求項1に記載の光反射基板。
- 原子間力顕微鏡を用いて、前記光反射基板の前記表面の50μm×50μmの範囲を512×512点測定して得られる3次元データから近似三点法により求められる実面積Sxと、幾何学的測定面積S0とから、下記式(1)により求められる表面積差ΔSが5%以上90%以下である、請求項1または2に記載の光反射基板。
ΔS=[(Sx-S0)/S0]×100(%) (1) - 前記金属層がアルミニウムであり、前記絶縁層が該アルミニウムの陽極酸化皮膜である請求項1~3のいずれかに記載の光反射基板。
- 前記光反射基板が、発光素子の発光を発光観測面側に反射する光反射基板である請求項1~4のいずれかに記載の光反射基板。
- 前記金属層が窪みを持つ形状であり、前記絶縁層が窪みを持つ形状の表面に設けられている請求項1~5のいずれかに記載の光反射基板。
- 前記請求項1~6のいずれかに記載の光反射基板の製造方法であって、
アルミニウム板を用意し、
該アルミニウム板の表面を粗面化し、
該粗面化した表面を陽極酸化処理して絶縁層を形成する、
光反射基板の製造方法。 - 前記請求項1~6のいずれかに記載の光反射基板の製造方法であって、少なくとも、
アルミニウム板を用意し、
該アルミニウム板の表面を粗面化した後、以下の(a)および(b)工程を任意の順序で行う、
(a)発光素子を設けるための配線用スルーホールを形成し、および、基板をチップ化するためのルーティング加工を施す工程、
(b)粗面化した表面を陽極酸化処理して絶縁層を形成する工程、
を有する光反射基板の製造方法。 - 一方のアルミニウム基板は、少なくとも1つのスルーホールが形成され、他方のアルミニウム基板はスルーホールが形成されていない、請求項1~4のいずれかに記載の光反射基板を少なくとも2枚重ねることにより形成される請求項6に記載の光反射基板。
- 前記ルーティング加工において、複数のチップの周りにチップを個別に切り離すための切り離し部を設け、切り離し部の一部に複数のチップをアルミニウム板に連結する連結部を有するように加工する際に、予めアルミニウム板の連結部になる部分をチップとなる部分より板厚を薄く設計して、ルーティング加工でアルミニウム板に連結部を残して切り離し部を切り欠いて、その後アルミニウム板を陽極酸化処理した後に連結部を切り離して、切り離した後の個別のチップの厚さ方向に連結部が切り離された後に形成されるアルミニウム部分の面積を小さくし、または無くした、個別のチップを得るルーティング加工を有する請求項8に記載の光反射基板の製造方法。
- 請求項8または10に記載の工程を経た後、以下の(c)および(d)工程を任意の順序で行う、請求項8または10に記載の光反射基板の製造方法:
(c)発光素子への電気信号伝送のための金属配線層を形成し、上記金属配線層をパターン化する工程と、
(d)発光素子を実装する部分に相当する電極部に再度金属層を設ける加工を施す工程。 - 請求項1~6のいずれかまたは9に記載の光反射基板の上層に青色発光素子を有し、その周りおよび/または上部に蛍光発光体を備える白色系発光ダイオード装置。
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- 2010-06-23 WO PCT/JP2010/060629 patent/WO2010150810A1/ja active Application Filing
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- 2010-06-23 CN CN2010800282351A patent/CN102460749A/zh active Pending
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JPH0135910B2 (ja) | 1982-10-12 | 1989-07-27 | Kobe Seikosho Kk | |
JPS6360824B2 (ja) | 1983-01-20 | 1988-11-25 | ||
JPS6360823B2 (ja) | 1983-01-20 | 1988-11-25 | ||
JPS59153861A (ja) | 1983-02-22 | 1984-09-01 | Fuji Photo Film Co Ltd | 平版印刷版用支持体 |
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JPH0361753B2 (ja) | 1983-06-22 | 1991-09-20 | Furukawa Aruminiumu Kogyo Kk | |
JPS6036195A (ja) | 1983-08-09 | 1985-02-25 | Mitsubishi Chem Ind Ltd | 平版印刷版用支持体 |
JPH0419292B2 (ja) | 1983-09-16 | 1992-03-30 | Kobe Seikosho Kk | |
JPH0419290B2 (ja) | 1983-09-16 | 1992-03-30 | Kobe Seikosho Kk | |
JPH0419291B2 (ja) | 1983-09-16 | 1992-03-30 | Kobe Seikosho Kk | |
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JPS60215727A (ja) | 1984-04-06 | 1985-10-29 | Sukai Alum Kk | 印刷用アルミニウム合金素板 |
JPS60215725A (ja) | 1984-04-06 | 1985-10-29 | Sukai Alum Kk | 印刷用アルミニウム合金素板 |
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JP2016080864A (ja) * | 2014-10-16 | 2016-05-16 | 富士フイルム株式会社 | 反射防止フィルムの製造方法 |
Also Published As
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TW201107797A (en) | 2011-03-01 |
EP2448024A1 (en) | 2012-05-02 |
KR20120101290A (ko) | 2012-09-13 |
US20120091495A1 (en) | 2012-04-19 |
CN102460749A (zh) | 2012-05-16 |
JP2011205051A (ja) | 2011-10-13 |
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