JP2011199233A - Insulated substrate and process for production of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulated substrate and a process for production of the same which can provide a light-emitting element excellent in insulation and heat dissipation, and a light-emitting element using the same.SOLUTION: The insulated substrate has a metal substrate 33 and an insulation layer 32 formed on the surface of the metal substrate, wherein the metal substrate is a valve metal substrate, the insulation layer is an anodic oxidation film of a valve metal, and a porosity of the anodic oxidation film is 30% or less.

Description

  The present invention relates to an insulating substrate used for a light emitting element, and more particularly to an insulating substrate used for a light emitting diode (hereinafter referred to as “LED”) and a method for manufacturing the same.

In general, LEDs are said to have a power consumption of 1/100 and a lifespan of 40 times (40000 hours) compared to fluorescent lamps. Such a feature of power saving and long life is an important factor in adopting LEDs in an environment-oriented flow.
In particular, white LEDs are excellent in color rendering properties and have a merit that a power supply circuit is simpler than fluorescent lamps, and therefore, expectations for light sources for illumination are increasing.
In recent years, white LEDs (30 to 150 lm / W) with high luminous efficiency, which are required as a light source for illumination, have appeared one after another, and the fluorescent lamp (20 to 110 lm / W) has been reversed in terms of light use efficiency in practical use. is doing.
As a result, the flow of practical use of white LEDs instead of fluorescent lamps is rapidly increasing, and the number of cases in which white LEDs are employed as backlights or illumination light sources for liquid crystal display devices is increasing.

By the way, if a large amount of current is passed through the LED chip in order to achieve high brightness, the amount of generated heat increases, and the deterioration of the wavelength-supporting phosphor-supporting resin material is promoted over time. The problem of becoming.
In fact, in the conventional LED, when the LED is driven for a long time or driven at a high current in order to increase the light emission luminance, there is a problem that the LED chip remarkably generates heat and becomes a high temperature state, resulting in thermal deterioration.

  In order to solve such a problem, an insulating substrate in which the surface of an aluminum substrate is coated with an anodized film has been proposed (see, for example, Patent Documents 1 to 7). Since the substrate has high thermal conductivity, it is expected that good heat dissipation can be obtained.

JP 2007-250315 A Japanese Utility Model Publication No. 55-154564 JP-A-6-45515 JP 7-14938 A Japanese National Patent Publication No. 11-504387 JP 2006-344978 A JP 2009-164583 A

  As a result of studying the insulating substrates described in Patent Documents 1 to 7, the present inventor results in a decrease in heat dissipation when the thickness of the anodized film is increased from the viewpoint of further improvement in insulation (voltage resistance). It became clear that it was difficult to achieve both excellent insulation and heat dissipation.

  Accordingly, an object of the present invention is to provide an insulating substrate that can provide a light-emitting element that is excellent in both insulation and heat dissipation, a manufacturing method thereof, and a light-emitting element using the same.

As a result of intensive studies to achieve the above object, the present inventor is able to achieve both excellent insulation and heat dissipation by using an insulating substrate having an insulating layer in which the porosity of the anodized film is not more than a predetermined value. The present invention was completed.
That is, the present invention provides the following (1) to (14).

(1) An insulating substrate having a metal substrate and an insulating layer provided on the surface of the metal substrate,
The metal substrate is a valve metal substrate,
The insulating layer is an anodized film of a valve metal,
An insulating substrate having a porosity of the anodized film of 30% or less.

  (2) The insulating substrate according to (1), wherein the surface of the anodized film has irregularities with an average pitch of 0.5 μm or less and an average diameter of 1 μm or more.

(3) The anodic oxide film has micropores,
The insulating substrate according to (1) or (2), wherein at least a part of the inside of the micropore is sealed with a substance different from the substance constituting the anodized film.

(4) The anodic oxide film has micropores,
The micropore is composed of a micropore in which at least a part of the inside thereof is sealed with a material different from the material constituting the anodized film, and a micropore in which the inside is not sealed with the different material. The insulating substrate according to any one of (1) to (3), which is configured.

  (5) The insulating substrate according to (3) or (4), wherein the different substance is insulating.

  (6) The valve metal according to (1) to (5), wherein the valve metal is at least one metal selected from the group consisting of aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth and antimony. An insulating substrate according to any one of the above.

  (7) The insulating substrate according to (6), wherein the valve metal is aluminum.

  (8) The insulating substrate according to any one of (1) to (7), wherein the insulating substrate is a substrate provided on a light emission observation surface side of the LED light emitting element.

(9) An insulating substrate manufacturing method for manufacturing the insulating substrate according to any one of (1) to (8) above,
Anodizing the surface of the valve metal substrate to form an anodized film of the valve metal on the valve metal substrate;
A method for manufacturing an insulating substrate, comprising: a sealing treatment step of performing a sealing treatment after the anodizing treatment step so that a porosity of the anodized film is 30% or less.

(10) By the anodization treatment, the anodized film having micropores is formed,
The method for producing an insulating substrate according to (9), wherein at least a part of the inside of the micropore is sealed with a material different from the material constituting the anodized film by the sealing treatment.

  (11) The method for manufacturing an insulating substrate according to (9) or (10), further including a through-hole forming step of forming a through-hole in the thickness direction of the valve metal substrate.

  (12) The method for manufacturing an insulating substrate according to (11), further including an individualization step that enables the valve metal substrate to be separated into a desired shape after the through-hole forming step.

  (13) A wiring substrate having the insulating substrate according to any one of (1) to (8) and a metal wiring layer provided on the insulating layer side of the insulating substrate.

  (14) The wiring board according to (13), a blue LED light emitting element provided on the metal wiring layer side of the wiring board, and a fluorescent light emitter provided on at least the blue LED light emitting element. A white LED light-emitting element provided.

  As will be described below, according to the present invention, it is possible to provide an insulating substrate capable of providing a light emitting element excellent in both insulation and heat dissipation, a method for manufacturing the same, and a light emitting element using the same. .

FIG. 1 is a schematic cross-sectional view showing a sealing mode of different substances in a micropore. FIG. 2 is a schematic view of an anodizing apparatus used for anodizing in the production of the insulating substrate of the present invention. FIG. 3 is a schematic cross-sectional view showing a configuration example of the white LED light emitting element of the present invention. FIG. 4 is a schematic cross-sectional view showing another configuration example of the white LED light emitting element of the present invention. FIG. 5 is a schematic cross-sectional view showing another configuration example of the white LED light emitting element of the present invention.

[Insulated substrate]
Hereinafter, the insulating substrate of the present invention will be described in detail.
The insulating substrate of the present invention is an insulating substrate having a metal substrate and an insulating layer provided on the surface of the metal substrate, wherein the metal substrate is a valve metal substrate, and the insulating layer is an anodized film of a valve metal. And an insulating substrate having a porosity of 30% or less of the anodized film.
Next, the metal substrate (valve metal substrate) and the insulating layer (valve metal anodized film) constituting the insulating substrate of the present invention will be described.

[Metal substrate]
The metal substrate used for the insulating substrate of the present invention is a substrate made of a valve metal.
Here, the valve metal has a characteristic that the metal surface is covered with an oxide film of the metal by anodic oxidation, and the oxide film flows only in one direction and flows very much in the reverse direction. It is a metal having difficult characteristics, and specific examples thereof include aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony and the like.
Of these, an aluminum substrate is preferred because the light source has good light-transmitting properties and excellent workability and strength.

<Aluminum substrate>
As the aluminum substrate suitably used for the insulating substrate of the present invention, a known aluminum substrate can be used. In addition to a pure aluminum substrate, an alloy plate containing aluminum as a main component and a small amount of foreign elements; low-purity aluminum (for example, , Recycled materials), substrates with high-purity aluminum deposited thereon; substrates coated with high-purity aluminum on the surface of silicon wafers, quartz, glass, etc. by a method such as vapor deposition or sputtering; resin substrates with aluminum laminated; You can also
Here, the foreign elements that may be included in the alloy plate include silicon, iron, copper, manganese, magnesium, chromium, zinc, bismuth, nickel, titanium, etc., and the content of the foreign elements in the alloy is It is preferably 10% by mass or less.

  Thus, the composition of the aluminum substrate suitably used for the insulating substrate of the present invention is not specified. For example, a conventionally known aluminum substrate described in Aluminum Handbook 4th Edition (1990, published by Light Metal Association) A material, for example, an Al-Mn based aluminum substrate such as JIS A1050, JIS A1100, JIS A1070, JIS A3004 containing Mn, and internationally registered alloy 3103A can be appropriately used. For the purpose of increasing the tensile strength, 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. Furthermore, an Al—Zr alloy or an Al—Si alloy containing Zr or Si can also be used. Furthermore, an Al—Mg—Si based alloy can also be used.

  Regarding JIS 1050 materials, JP-A-59-153861, JP-A-61-51395, JP-A-62-146694, JP-A-60-215725, JP-A-60-215726, JP-A-60- No. 215727, JP-A-60-216728, JP-A-61-272367, JP-A-58-11759, JP-A-58-42493, JP-A-58-212254, JP-A-62-148295 JP-A-4-254545, JP-A-4-165541, JP-B-3-68939, JP-A-3-234594, JP-B-1-47545, JP-A-62-140894, JP-B-1-35910 And Japanese Patent Publication No. 55-28874.

  Regarding the JIS 1070 material, each of 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.

  Regarding Al-Mg alloys, 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, 61-274993, JP 62-23794, JP 63-47347, JP 63-47348, JP 63-47349, JP 64-1293, JP-A 63-135294, JP-A 63-87288, JP 4-73392, JP 7-100904, JP 62-149856, JP 4-73394, JP 62-62 181911, JP-B-5-76530, JP-A-63-30294, JP-B-6-37116, JP-A-2-215599, and JP-A-61-201747 It has been.

  Regarding Al-Mn alloys, JP-A-60-230951, JP-A-1-306288, JP-A-2-293189, JP-B-54-42284, JP-B-4-19290, JP-B-4-19291 JP-B-4-19292, JP-A-61-35995, JP-A-64-51992, and JP-A-4-226394, US Pat. No. 5,009,722, No. 028,276 and the like.

  Regarding Al-Mn-Mg alloys, JP-A-62-86143, JP-A-3-222796, 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.

  Al-Zr alloys are described in JP-B 63-15978, JP-A 61-51395, JP-A 63-143234, JP-A 63-143235, and the like.

  The Al—Mg—Si alloy is described in British Patent 1,421,710.

In order to use an aluminum alloy as a plate material, for example, the following method can be employed.
First, a molten aluminum alloy adjusted to a predetermined alloy component content is subjected to a cleaning process and cast according to a conventional method. In the 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 performed in order to prevent defects caused by foreign matters such as non-metallic inclusions and oxides in the molten metal and defects caused by gas dissolved in the molten metal. Regarding 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, JP-A-5-311261 6-136466 and the like. Further, the degassing of the molten metal is described in JP-A-5-51659, Japanese Utility Model Laid-Open No. 5-49148, and the like. The present applicant has also proposed a technique relating to degassing of molten metal in Japanese Patent Application Laid-Open No. 7-40017.

Next, casting is performed using the molten metal that has been subjected to the cleaning treatment as described above. As for 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.
In 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. When DC casting is performed, an ingot having a thickness of 300 to 800 mm can be manufactured. 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. Before and after that, soaking treatment is performed as necessary. When performing a soaking treatment, 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.

  Thereafter, hot rolling and cold rolling are performed to obtain a rolled plate of an aluminum substrate. An appropriate 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 substrate 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 substrate is cut into a sheet, but in order to improve the productivity, it is preferable to perform it in a continuous coil state. Further, a slitter line may be used for processing into a predetermined plate width. Moreover, in order to prevent the generation | occurrence | production of the damage | wound by friction between aluminum substrates, you may provide a thin oil film on the surface of an aluminum substrate. As the oil film, a volatile or non-volatile film is appropriately used as necessary.

  On the other hand, as 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. When the continuous casting method is used, it 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. Regarding the continuous casting method, the techniques proposed by the present applicant are disclosed in 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 and JP-A-6-26308.

  When continuous casting is performed, for example, if a method using a cooling roll such as a Hunter method is used, a cast plate having a thickness of 1 to 10 mm can be directly cast continuously, and the hot rolling step is omitted. The advantage of being able to In addition, when a method using a cooling belt such as the Husley method is used, a cast plate having a thickness of 10 to 50 mm can be cast. Generally, a hot rolling roll is arranged immediately after casting and continuously rolled. Thus, a continuous cast and rolled plate having a thickness of 1 to 10 mm is obtained.

  These continuous cast and rolled plates are subjected to processes such as cold rolling, intermediate annealing, improvement of flatness, slits, and the like in the same manner as described for DC casting. Finished to a thickness of 5 mm. Regarding the intermediate annealing condition and the cold rolling condition when using the continuous casting method, the techniques proposed by the present applicant are disclosed in JP-A-6-220593, JP-A-6-210308, JP-A-7-54111, It is described in JP-A-8-92709.

  The crystal structure of the aluminum substrate may cause poor surface quality when the surface of the aluminum substrate is subjected to chemical or electrochemical surface roughening. It is preferably not too coarse. The crystal structure on the surface of the aluminum substrate preferably has a width of 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, and the length of the crystal structure is 5000 μm or less. Is preferably 1000 μm or less, and more preferably 500 μm or less. With regard to these, techniques proposed by the present applicant are described in JP-A-6-218495, JP-A-7-39906, JP-A-7-124609, and the like.

  The distribution of alloy components on the aluminum substrate may cause poor surface quality due to non-uniform distribution of alloy components on the surface of the aluminum substrate when chemical or electrochemical surface roughening is performed. Therefore, it is preferable that the surface is not very uneven. With regard to these, the techniques proposed by the present applicant are described in Japanese Patent Laid-Open Nos. 6-48058, 5-301478, and 7-132589.

  As for the intermetallic compound of the aluminum substrate, the size and density of the intermetallic compound may affect the chemical roughening treatment or the electrochemical roughening treatment. With respect to these, techniques proposed by the present applicant are described in Japanese Patent Laid-Open Nos. 7-138687 and 4-254545.

  In the present invention, an aluminum substrate as shown above can be used by forming irregularities by lamination rolling, transfer or the like in the final rolling step or the like.

The aluminum substrate suitably used for the insulating substrate of the present invention may be an aluminum web or a sheet-like sheet.
In the case of an aluminum web, for example, the packing form of aluminum is, for example, laying a 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. Moreover, a polyethylene film can be used as the packaging material, and a needle felt or a hard board can be used as the cushioning material. There are various other forms, but 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 substrate suitably used for the insulating substrate of the present invention is about 0.1 to 2.0 mm, preferably 0.15 to 1.5 mm, and preferably 0.2 to 1.0 mm. Is more preferable. This thickness can be appropriately changed according to the user's wishes or the like.

[Insulating layer]
The insulating layer used in the insulating substrate of the present invention is a layer provided on the surface of the metal substrate (valve metal substrate) and is the above-described anodized film of the valve metal.
The insulating layer may be an anodized film of a valve metal substrate different from the valve metal substrate, but from the viewpoint of preventing formation defects of the insulating layer, a part (surface) of the valve metal substrate will be described later. An anodized film formed on the valve metal substrate by performing an anodizing treatment is preferable.

In the present invention, the porosity of the anodic oxide film is 30% or less, preferably 15% or less, and more preferably 5% or less.
Here, the porosity of the anodized film refers to a value calculated by the following formula. In the following formula, the density (g / cm ³ ) of the valve metal oxide refers to the density described in the chemical handbook, for example, 3.98 for aluminum oxide and 4 for titanium oxide. .23.
Porosity (%) = [1- (oxide film density / valve metal oxide density)] × 100
(In the formula, the oxide film density (g / cm ³ ) represents “oxide film mass per unit area / oxide film thickness”.)

By using an anodic oxide film having such a porosity for the insulating layer, a light-emitting element that is excellent in both insulation and heat dissipation can be provided.
This reduces the amount of air present in the voids of the anodized film without affecting the composition and film thickness of the anodized film, resulting in thermal conductivity while maintaining the excellent insulating properties of the anodized film. It is thought that it was possible to raise the price.

In the present invention, from the viewpoint of improving the insulation, at least a part of the inside of the micropore 2 included in the anodized film 1 constitutes the anodized film 1 as shown in FIG. It is preferably sealed with a substance 3 different from the substance (see FIG. 1 (A)), and from the viewpoint of improving the adhesion to the metal wiring layer described later, the micropores of the anodic oxide film 1 are included. However, at least a part of the inside of the micropore 2a is sealed with a substance 3 different from the substance constituting the anodic oxide film 1, and the micropore 2b is not sealed with the different substance. Is more preferable (see FIG. 1B).
Here, the substance different from the substance constituting the anodized film is preferably insulative, and as a specific example, when the anodized film is an aluminum anodized film (aluminum oxide), Specifically, examples thereof include aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, tantalum oxide, niobium oxide, zirconium oxide, and hydrates thereof, and these may be used alone. Two or more kinds may be used in combination.
Of these, aluminum hydroxide and its hydrates have a refractive index that is close to that of aluminum oxide, and because the light source has good light-transmitting properties and because of its excellent adsorptivity and insulation with aluminum oxide. Is preferred.

  Furthermore, in this invention, according to the use of a light emitting element, the said insulating layer may be provided in both surfaces of the said metal substrate, and may be provided in the end surface of the said metal substrate.

The surface of the metal substrate and the insulating layer constituting the insulating substrate of the present invention is provided with a predetermined surface shape from the viewpoint of increasing the diffuse reflection component of light, particularly when used as an insulating substrate for a white LED. Can do.
The surface shape is preferably a shape having irregularities with an average wavelength of 0.01 to 100 μm, and may be a shape in which irregularities with different wavelengths are superimposed.
With such a surface shape, it is presumed that the light diffusion effect is improved, and the light emission absorption effect and the interference effect (effects that can cause loss as reflection) can be suppressed.
The treatment for providing such a surface shape is performed under various mechanical / electrical / chemical treatment conditions as described in, for example, paragraphs [0049] to [0076] of Japanese Patent Application Laid-Open No. 2007-245116. Is preferred.

In particular, the surface of the insulating layer (anodized film) constituting the insulating substrate of the present invention has good adhesion with a metal wiring layer (described later) provided in consideration of LED mounting, and the reflection characteristics of the non-wiring portion are deteriorated. Therefore, it is preferable to have irregularities having an average pitch of 0.5 μm or less and an average diameter of 1 μm or more.
In the present invention, the irregularities can also be formed by sealing the different substances in a part (for example, about 80 to 90%) of the micropores of the anodized film.

[Insulating substrate manufacturing method]
Below, the manufacturing method of the insulated substrate of this invention is demonstrated in detail.
The manufacturing method of the insulating substrate of the present invention is a method of manufacturing the above-described insulating substrate of the present invention,
Anodizing the surface of the valve metal substrate to form an anodized film of the valve metal on the valve metal substrate;
After the said anodizing process, it is a manufacturing method of an insulating substrate which performs a sealing process and has the sealing process process which makes the porosity of the said anodized film 30% or less.
Next, the anodizing process and the sealing process will be described.

[Anodizing treatment process]
The anodizing process is a process for forming an insulating layer having a porous or non-porous portion on the surface of the metal substrate by anodizing the surface of the metal substrate.

The anodizing treatment in the oxidation treatment step can be performed by a conventional method performed in the production of a lithographic printing plate support or the like.
Specifically, as a solution used for anodizing treatment, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid, malonic acid, citric acid, tartaric acid, boric acid, etc. Alkali metal / alkaline earth metal hydroxides such as sodium hydroxide, magnesium hydroxide, potassium hydroxide and calcium hydroxide can be used alone or in combination of two or more.
At this time, at least a component usually contained in an aluminum substrate, an electrode, tap water, ground water, or the like may be contained in the electrolytic solution. Furthermore, the 2nd, 3rd component may be added. Examples of 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.

In addition, the conditions of the anodizing treatment in the anodizing treatment step vary depending on the electrolyte used, and thus cannot be determined unconditionally. In general, however, the electrolyte concentration is 1 to 80% by mass, and the solution temperature is 5 to 70. ° C., a current density of 0.5 to 60 a / dm ^2, voltage 1～600V, is suitably an electrolysis time of 15 seconds to 20 hours, is adjusted to obtain the desired anodized layer weight.

  Further, the anodizing treatment in the first anodizing treatment step is disclosed in JP-A-54-81133, JP-A-57-47894, JP-A-57-51289, JP-A-57-51290, JP-A-57. JP-A-54300, JP-A-57-136596, JP-A-58-107498, JP-A-60-2000025, JP-A-62-136596, JP-A-63-176494, JP-A-4-17697. JP-A-4-280997, JP-A-6-207299, JP-A-5-24377, JP-A-5-32083, JP-A-5-125597, JP-A-5-195291, etc. You can also use this method.

  Of these, as described in JP-A-54-12853 and JP-A-48-45303, it is preferable to use a 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, and 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.

In the anodizing treatment step, when anodizing is performed in an electrolytic solution containing sulfuric acid, direct current may be applied between the aluminum substrate and the counter electrode, or alternating current may be applied.
When a direct current is applied to the aluminum substrate, the current density is preferably from 1 to 60 A / dm ^2, and more preferably 5 to 40 A / dm ^2.

In addition, when the anodizing treatment in the anodizing treatment step is continuously performed, the initial anodizing treatment is performed so that current is concentrated on a part of the aluminum substrate and so-called “burning” does not occur. It is preferable to increase the current density to 30 to 50 A / dm ² or higher as the anodic oxidation process proceeds with a current flowing at a low current density of 10 A / dm ² . In the case where the anodizing process 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 substrate through an electrolytic solution.

When the anodized film is porous, the average pore diameter of the micropores is about 5 to 1000 nm, and the average pore density is about 1 × 10 ⁶ to 1 × 10 ¹⁰ / mm ² . Further, the porosity of the anodic oxide film that approximates the proportion of the micropores in the anodic oxide film is preferably 1 to 90%, more preferably 5 to 80%, from the viewpoint of facilitating the sealing treatment described later. Preferably, 10 to 70% is particularly preferable. The method for calculating the porosity is as described above.

  The thickness of the anodized film is preferably 1 to 200 μm. If the thickness is less than 1 μm, the insulation is poor and the withstand voltage is lowered. The thickness of the anodized film is more preferably 2 to 100 μm, still more preferably 10 to 50 μm.

  As the electrolysis apparatus used for the anodizing treatment, those described in JP-A-48-26638, JP-A-47-18739, JP-B-58-24517, and the like can be used. Among these, the apparatus shown in FIG. 2 is preferably used. FIG. 2 is a schematic view showing an example of an apparatus for anodizing the surface of an aluminum substrate. In the anodizing apparatus 410, the aluminum substrate 416 is transported as indicated by arrows in FIG. The aluminum substrate 416 is charged (+) by the power supply electrode 420 in the power supply tank 412 in which the electrolytic solution 418 is stored. Then, the aluminum substrate 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 substrate 416 is charged to (−) by the electrolytic electrode 430 to form an anodized film on the surface thereof, and the aluminum substrate 416 exiting the electrolytic treatment tank 414 is transported to a subsequent process. In the anodizing apparatus 410, the roller 422, the nip roller 424 and the roller 428 constitute a direction changing means, and the aluminum substrate 416 is disposed between the power supply tank 412 and the electrolytic treatment tank 414 between the rollers 422, 424 and 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. 2 is that the power supply tank 412 and the electrolytic treatment tank 414 are partitioned by a single tank wall 432, and the aluminum substrate 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 substrate 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. Further, by transporting the aluminum substrate 416 in a mountain shape and an inverted U shape, it is not necessary to form an opening for allowing the aluminum substrate 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.

  In addition, the anodizing treatment in the anodizing treatment step may be performed alone under a certain treatment condition, but the shape of the anodized film, such as the shape depending on the location or the shape in the depth direction, is desired to be controlled. In some cases, two or more anodizing treatments under different conditions may be sequentially combined.

Further, from the viewpoint of suppressing variation in sealing in the sealing processing step described later, for example, Japanese Patent No. 3,714,507, Japanese Patent Application Laid-Open No. 2002-285382, Japanese Patent Application Laid-Open No. 2006-124827, and Japanese Patent Application Laid-Open No. 2007-2007. Anodizing treatment for forming micropores arranged in a honeycomb shape by a method described in Japanese Patent No. 231339, Japanese Patent Application Laid-Open No. 2007-231405, Japanese Patent Application Laid-Open No. 2007-231340, Japanese Patent Application Laid-Open No. 2007-238988, or the like is preferable. .
These processes are preferably the processes described in the processing conditions of each patent and publication.

[Sealing process]
The sealing treatment step is a step of obtaining an insulating substrate of the present invention by performing sealing treatment after the anodizing treatment step so that the porosity of the anodized film is 30% or less.

  The sealing treatment in the sealing treatment step 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. For example, even if the sealing treatment is carried out by the apparatus and method described in JP-B-56-12518, JP-A-4-4194, JP-A-5-20296, JP-A-5-179482, etc. Good.

  In the present invention, when the anodized film has micropores, from the viewpoint of reducing the porosity of the anodized film and improving heat dissipation, not only the surface of the anodized film, It is preferable to infiltrate a treatment liquid such as boiling water treatment, hot water treatment, or sodium silicate treatment into the inside of the micropore.

In the present invention, when the anodic oxide film has micropores, as described above, the anodic oxide film is sealed with a substance different from the substance constituting the anodic oxide film as described above. Preferably it is perforated.
As the sealing treatment for sealing such different substances, for example, the inner wall of the micropore can be obtained by infiltrating the inside of the micropore with a treatment liquid such as the boiling water treatment, the hot water treatment, and the sodium silicate treatment. May be a method of altering a substance (for example, aluminum oxide or the like) constituting the material (for example, altering to aluminum hydroxide or the like), but described in paragraphs [0016] to [0035] of JP-A-6-35174. A sealing treatment by a sol-gel method as described above is also preferable.
Here, the sol-gel method is a method in which a sol composed of a metal alkoxide is generally used as a gel that loses fluidity by hydrolysis and polycondensation reaction, and this gel is heated to form an oxide.
The metal alkoxide is not particularly limited, but Al (O—R) n, Ba (O—R) n, B (O—R) n, Bi from the viewpoint of easy sealing inside the micropore. (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 and the like are preferably exemplified. In the above examples, R represents a linear, branched or cyclic hydrocarbon group which may have a substituent, or a hydrogen atom, and n represents an arbitrary natural number.
Among these, when the insulating layer is an aluminum anodic oxide film, titanium oxide and silicon oxide-based metal alkoxides that are excellent in reactivity with aluminum oxide and excellent in sol-gel formation are preferable.
The method for forming the sol-gel inside the micropore is not particularly limited, but from the viewpoint of easy sealing inside the micropore, a method of applying and heating the sol solution 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.
Moreover, in order to reduce a porosity, you may process repeatedly repeatedly.

On the other hand, as another sealing treatment for sealing such a different substance, the inside of the micropore may be filled with insulating particles having a size that can enter the micropore of the anodic oxide film.
As such insulating particles, colloidal silica is preferable from the viewpoint of dispersibility and size.
Colloidal silica can be prepared and used by a sol-gel method, and a commercially available product can also be used. For preparation by the sol-gel method, Werner Stober et al; Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D .; Badley et al; Lang muir 6, 792-801 (1990), Color Material Association Journal, 61 [9] 488-493 (1988), and the like.
Colloidal silica is a dispersion of water or a water-soluble solvent of silica having silicon dioxide as a basic unit, and the particle diameter is preferably 1 to 400 nm, more preferably 1 to 100 nm. It is especially preferable that it is ˜50 nm. When the particle size is smaller than 1 nm, the storage stability of the coating liquid is poor, and when it is larger than 400 nm, the filling properties into the micropores are poor.
Colloidal silica having a particle size in the above range can be used in the state of an aqueous dispersion, whether acidic or basic, and can be appropriately selected depending on the stable region of the aqueous dispersion to be mixed. .
Examples of acidic colloidal silica using water as a dispersion medium include, for example, Snowtex (registered trademark; the same shall apply hereinafter) -O, Snowtex-OL, manufactured by Nissan Chemical Industries, and Adelite (registered trademark) manufactured by Asahi Denka Kogyo Co., Ltd. The same shall apply hereinafter.) Commercially available products such as AT-20Q, Clevosol (registered trademark, the same applies hereinafter) manufactured by Clariant Japan Co., Ltd., 20H12, clebosol 30CAL25 and the like can be used.

  Examples of basic colloidal silica include silica stabilized by the addition of alkali metal ions, ammonium ions, and amines. For example, SNOWTEX-20, SNOWTEX-30, SNOWTEX-C, and SNOWTEX-C manufactured by Nissan Chemical Industries, Ltd. Tex-C30, Snotex-CM40, Snotex-N, Snotex-N30, Snotex-K, Snotex-XL, Snotex-YL, Snotex-ZL, Snotex PS-M, Snotex PS-L Asahi Denka Kogyo's Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-40, Adelite AT-50; Clariant Japan Made of clebozo 30R9, Kurebozoru 30R50, Kurebozoru 50R50; DuPont Ludox (TM forth..) HS-40, Ludox HS-30, Ludox LS, Ludox SM-30; and the like can be used commercially available products.

Examples of colloidal silica using a water-soluble solvent as a dispersion medium include MA-ST-M (particle diameter: 20 to 25 nm, methanol dispersion type), IPA-ST (particle diameter: 10 to 10) manufactured by Nissan Chemical Industries, Ltd. 15 nm, isopropyl alcohol dispersion type), EG-ST (particle diameter: 10 to 15 nm, ethylene glycol dispersion type), EG-ST-ZL (particle diameter: 70 to 100 nm, ethylene glycol dispersion type), NPC-ST (particle diameter) : Commercial products such as 10-15 nm, ethylene glycol monopropyl ether dispersion type) can be used.
These colloidal silicas may be used alone or in combination of two or more, and may contain alumina, sodium aluminate or the like as a minor component.
Colloidal silica may contain an inorganic base (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia) or an organic base (such as tetramethylammonium) as a stabilizer.

In the present invention, in the sealing treatment, when a substance different from the substance constituting the anodic oxide film is sealed in the micropore, the anodic oxide film is within a limit not exceeding 30%. It is preferable to remove the different substances present in the vicinity of the surface layer (surface).
By removing the different substances present in the vicinity of the surface layer, it becomes easy to form irregularities having an average pitch of 0.5 μm or less and an average diameter of 1 μm or more on the surface of the anodized film. Adhesion with a metal wiring layer to be described later is improved.
Further, the method for removing the different substances present in the vicinity of the surface layer is not particularly limited. For example, in addition to enzyme plasma treatment and immersion treatment with an aqueous sodium hydroxide solution shown in the examples described later, mechanical polishing treatment and chemical machinery A method of removing only the surface layer portion by polishing (CMP: Chemical Mechanical Polishing) or the like is preferable.

[Through-hole formation process / individualization process]
In the manufacturing method of the insulated substrate of this invention, you may provide the through-hole formation process. The through hole forming step is a step of forming the through hole in the thickness direction of the metal substrate.
Moreover, in the manufacturing method of the insulated substrate of this invention, you may provide the singulation process. When the singulation step includes the through-hole formation step, the metal substrate is divided into pieces having a desired shape (for example, a processing product added to the finished product) after the through-hole formation step. This process is also called routing processing.
These processes may be performed before or after the anodizing process described above. If it is performed before the anodizing treatment step, it is possible to prevent cracks in the insulating layer formed by the anodizing treatment, and to maintain the insulating property to the substrate end face portion generated by these steps. If it is performed after the anodizing treatment step, the efficiency of the anodizing treatment can be increased, and the final product can be processed accurately.

  The shape of the through-hole formed by the through-hole forming step is not particularly limited as long as it has a length between a plurality of layers where wiring is required and has a size (diameter) that can secure the necessary wiring by placing it therein. However, considering the final chip size and more reliable wiring formation, it is preferably circular, specifically 0.01 to 2 mmφ, more preferably 0.05 to 1 mmφ, and 0. .1 to 0.8 mmφ is particularly preferable.

In addition, the size to be singulated in the singulation process needs to consider the size and shape of the final chip, but when assuming a rectangular chip, from the viewpoint of compactness and workability of the chip, One side is preferably 0.1 to 50 mm, more preferably 0.2 to 40 mm, and particularly preferably 0.4 to 30 mm. In particular, when a reflection substrate for a main package is assumed, it is preferable to route to a size such as 3.2 mm × 2.8 mm, 1.6 mm × 0.8 mm, which is an example of the current shape standard.
Further, in the case where the anodizing process described above is performed on the chip part after singulation after the singulation process, in order to provide an insulating layer by anodizing process, electrical conductivity to the chip part is applied. It is preferable to process into a shape. Suitable methods include, but are not limited to, a method of performing routing processing with a conductive portion provided, a method of connecting the chip portion with a conductive wire, and the like.

  In the present invention, suitable methods for performing the through-hole forming step and the singulation step include, but are not limited to, drilling, pressing with a die, dicing with a dicer, laser processing, and the like.

[Protection treatment]
Furthermore, in the method for manufacturing an insulating substrate according to the present invention, the above-described through-hole forming step, individualizing step, metal wiring layer forming processing for electric signal transmission to the LED described later, and metal layer forming on the LED mounting portion are performed. In order to cope with various solvents used in processing or the like, protection treatment can be performed.
Specifically, as the protection treatment, for example, as described in JP 2008-93652 A, JP 2009-68076 A, etc., the hydrophilic / hydrophobic (philic / oleophobic) surface of the anodized film surface is used. In addition to being able to change the properties as appropriate, methods for imparting resistance to acids / alkalis can also be used as appropriate.

[Other processing]
Furthermore, in the method for manufacturing an insulating substrate of the present invention, various treatments can be applied to the surface of the insulating substrate as necessary.
For example, in order to improve the whiteness of the reflective substrate, 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.
In addition to the white color described above, a desired color can be colored on the insulating layer made of aluminum oxide, for example, by electrodeposition. Specifically, “Anodizing” Metal Surface Technology Association. Colored ionic species such as those described in Metal Surface Technology Course B (1969 PP. 195-207), “New Anodized Theory”, Karos Publishing (1997 PP. 95-96), specifically 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, As ion, etc. are mixed in the electrolytic solution and electrolysis is performed. By processing, it can color.

[Wiring board]
Below, the wiring board of this invention is demonstrated in detail.
The wiring substrate of the present invention is a wiring substrate having the above-described insulating substrate of the present invention and a wiring layer provided on the insulating layer side of the insulating substrate.

The material of the metal wiring layer is not particularly limited as long as it is a material that conducts electricity. Specific examples thereof include gold (Au), silver (Ag), copper (Cu), aluminum (Al), and magnesium (Mg). , Nickel (Ni), and the like. These may be used alone or in combination of two or more.
Of these, Cu is preferably used because of its low electrical resistance. Note that an Au layer or a Ni / Au layer may be provided on the surface layer of the wiring layer made of Cu from the viewpoint of improving the ease of wire bonding.

  The thickness of the metal wiring layer is preferably 0.5 to 1000 μm, more preferably 1 to 500 μm, and particularly preferably 5 to 250 μm, from the viewpoint of conduction reliability and package compactness.

As a method of forming the metal wiring layer, in addition to 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 pasting process of a metal foil, and an adhesion layer are provided. Processing and the like.
Among these, from the viewpoint of high heat resistance, the metal-only layer formation is preferable, and from the viewpoint of thick film / uniform formation and high adhesion, layer formation by plating is particularly preferable.

Since the plating process is a plating process for a non-conductive substance (insulating substrate), a method of forming a thick metal layer using the metal layer after providing a reduced metal layer called a seed layer is used. preferable.
For the formation of the seed layer, electroless plating is preferably used. As a plating solution, a main component (for example, a metal salt, a reducing agent, etc.) and an auxiliary component (for example, a pH adjusting agent, a buffering agent, a complex, etc.) are used. It is preferable to use a solution composed of an agent, accelerator, stabilizer, improver, etc. In addition, as a plating solution, SE-650 * 666 * 680, SEK-670 * 797, SFK-63 (all manufactured by Nippon Kanisen Co., Ltd.), Melplate NI-4128, Enplate NI-433, Enplate NI-411 Commercial products such as those manufactured by Meltex can be used as appropriate.
Further, when copper is used as the material of the metal wiring layer, various electrolytic solutions containing sulfuric acid, copper sulfate, hydrochloric acid, polyethylene glycol and a surfactant as main components and other various additives can be used.

The metal wiring layer thus formed is patterned by a known method according to the LED mounting design. In addition, a metal layer (including solder) is again provided at a location where the LED is actually mounted, and can be appropriately processed for easy connection by thermocompression bonding, flip chip, wire bonding, or the like.
As a suitable metal layer, a metal material such as solder or gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni) is preferable. From the viewpoint of mounting reliability, a method of providing Au or Ag via solder or Ni is preferable from the viewpoint of connection reliability.

Specifically, as a method of forming gold (Au) via nickel (Ni) on a copper (Cu) wiring on which a pattern is formed, Ni strike plating is performed, and then Au plating is performed. Can be mentioned.
Here, the Ni strike plating is performed for the purpose of removing the surface oxide layer of the Cu wiring layer and ensuring adhesion of the Au layer.
For Ni strike plating, a general Ni / hydrochloric acid mixed solution may be used, or a commercially available product such as NIPS-100 (manufactured by Hitachi Chemical Co., Ltd.) may be used.
On the other hand, Au plating is performed for the purpose of improving wire bonding and solder wettability after performing Ni strike plating.
The Au plating is preferably generated by electroless plating, such as HGS-5400 (manufactured by Hitachi Chemical Co., Ltd.), microfab Au series, galvanomister GB series, precious hub IG series (all manufactured by Tanaka Kikinzoku). A commercially available processing solution can be used.

[White LED light emitting element]
Hereinafter, the white LED light emitting element of the present invention will be described in detail.
The white LED light emitting element of the present invention is provided at least above the wiring board of the present invention described above, a blue LED light emitting element provided on the metal wiring layer side of the wiring board, and the blue LED light emitting element. A white LED light emitting device comprising a fluorescent light emitter.
Note that the above-described wiring board of the present invention is not limited to the shape of the light emitting element to be used, the type of LED, and the like, and can be used for various applications.
Next, the configuration of the white LED light emitting element of the present invention will be described with reference to the drawings.

FIG. 3 is a schematic cross-sectional view showing an example of a preferred embodiment of the white LED light-emitting element of the present invention.
Here, in the white LED light emitting device 100 shown in FIG. 3, the blue LED 110 is molded with a transparent resin 160 mixed with YAG-based fluorescent particles 150, and the light excited by the YAG-based fluorescent particles 150 and the blue LED 110. White light is emitted by the afterglow, and the blue LED 110 is face-down bonded to the wiring substrate 140 of the present invention having the metal wiring layers 120 and 130 that also serve as external connection electrodes. .

Moreover, FIG. 4 is typical sectional drawing which shows an example of the suitable embodiment of the white type LED light emitting element of this invention.
Here, the white LED light emitting element 100 shown in FIG. 4 is configured as a phosphor-mixed white LED light emitting element, and has the insulating layer 32, the metal substrate 33, and the metal wiring layer 34. A substrate, a blue LED light emitting element 22 provided on the metal wiring layer 34 side of the wiring board, and a fluorescent light emitter 26 provided at least on the blue LED light emitting element 22 are provided.
As shown in FIG. 4, in the white LED light-emitting element of the present invention, it is preferable that the blue LED light-emitting element 22 is sealed with a resin 24.
In the present invention, as the fluorescent light emitter 26, the fluorescent light emitting units described in Japanese Patent Application Nos. 2009-134007 and 2009-139261 can be used.

FIG. 5 is a schematic cross-sectional view showing another configuration example of the white LED light emitting element of the present invention.
Here, in the white LED light emitting element 100 shown in FIG. 5, similarly to the white LED light emitting element shown in FIG. 3, the blue LED 37 is molded with a transparent resin 160 mixed with YAG fluorescent particles 150. However, it is face-down bonded to the wiring board of the present invention having the metal wiring layers 120 and 130 that also serve as external connection electrodes.
As shown in FIG. 5, the wiring board of the present invention is provided with a through hole 35, and the metal substrate 33 positioned below the blue LED 37 is molded into a shape thicker than the other substrate portions to form a heat sink 39. Also good.
Although not clearly shown in FIG. 5, the inside of the through hole 35 in the insulating layer 32 is preferably an insulating layer that has been anodized.

Here, in the blue LED shown in FIGS. 3 and 5, a semiconductor such as GaAlN, ZnS, ZnSe, SiC, GaP, GaAlAs, AlN, InN, AlInGaP, InGaN, GaN, and AlInGaN is formed on the substrate as a light emitting layer. Things are used.
Examples of the 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.

Moreover, the material of the transparent resin shown in FIGS. 3 and 5 is preferably a thermosetting resin.
Among 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.
Further, the transparent resin is preferably hard to protect the blue LED.
Moreover, it is preferable to use resin excellent in heat resistance, a weather resistance, and light resistance for transparent resin.
The transparent resin 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 so as to have a predetermined function. it can.

Furthermore, the fluorescent particles shown in FIG. 3 and FIG. 5 may be anything that absorbs light from the blue LED and converts the wavelength into light of a different wavelength.
Specific examples of the fluorescent particles include nitride-based phosphors, oxynitride-based phosphors, sialon-based phosphors, and β-sialon-based phosphors that are mainly activated by lanthanoid elements such as Eu and Ce. An alkaline earth halogen apatite phosphor, an alkaline earth metal borate phosphor, an alkaline earth metal aluminate phosphor mainly activated by a lanthanoid group such as Eu, or a transition metal group element such as Mn; Alkaline earth silicate phosphor, alkaline earth sulfide phosphor, alkaline earth thiogallate phosphor, alkaline earth silicon nitride phosphor, germanate phosphor; mainly activated by lanthanoid elements such as Ce Rare earth aluminate phosphors, rare earth silicate phosphors, organic complexes mainly activated by lanthanoid elements such as Eu, etc., and these may be used alone, It may be used in combination with more species.

On the other hand, the wiring board of the present invention can also be used as a wiring board for phosphor mixed color white LED light emitting elements using ultraviolet to blue LEDs and a fluorescent light emitting material that absorbs the LEDs and emits fluorescence in the visible light region.
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 above-described method is a so-called “pseudo white light emission type” in which a blue LED light source chip and one kind of yellow phosphor are combined. In addition, for example, an ultraviolet to near-ultraviolet LED light source chip and red / green / blue fluorescence. A substrate of a light-emitting element of a light-emitting unit using a known light-emitting method such as “ultraviolet to near-ultraviolet light source type” in which several kinds of bodies are combined, and “RGB light source type” that emits white light with three red / green / blue light sources The wiring board of the present invention can be used.

The method of mounting the LED element on the wiring board of the present invention involves mounting by heating, but in the thermocompression bonding including solder reflow and the mounting method by flip chip, the highest temperature is achieved from the viewpoint of uniform and reliable mounting. Is preferably 220 to 350 ° C, more preferably 240 to 320 ° C, and particularly preferably 260 to 300 ° C.
The time for maintaining these maximum temperatures is preferably from 2 seconds to 10 minutes, more preferably from 5 seconds to 5 minutes, and particularly preferably from 10 seconds to 3 minutes.
Also, from the viewpoint of suppressing cracks generated in the anodized film due to the difference in thermal expansion coefficient between the metal substrate and the anodized film, the desired constant temperature is reached for 5 seconds to reach the maximum temperature. A method of performing a heat treatment for 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.

  Moreover, as temperature at the time of mounting by wire bonding, from a viewpoint of performing reliable mounting, 80-300 degreeC is preferable, 90-250 degreeC is more preferable, and 100-200 degreeC is especially preferable. 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.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.
(Examples 1-8)
<Preparation of aluminum substrate>
Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.005 mass%, Mn: 0.001 mass%, Mg: 0.001 mass%, Zn: 0.001 mass%, Ti: Containing 0.03% by mass, the balance is prepared using Al and an inevitable impurity aluminum alloy, and after performing the molten metal treatment and filtration, an ingot having a thickness of 500 mm and a width of 1200 mm is obtained by a DC casting method. Created.
Next, the surface was shaved with a chamfering machine with an average thickness of 10 mm, soaked at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., the thickness was 2.7 mm using a hot rolling mill. A rolled plate was used.
Furthermore, after performing heat processing at 500 degreeC using a continuous annealing machine, it finished by cold rolling to 0.24 mm in thickness, and obtained the aluminum substrate of JIS1050 material.
The aluminum substrate was made to have a width of 1030 mm and then subjected to the following anodic oxidation treatment and sealing treatment.

<Anodizing treatment>
The aluminum substrate produced above was anodized using an anodizing apparatus having a structure shown in FIG. The electrolytic solution conditions, voltage, and thickness of the formed anodic oxide film are shown in Table 1 below. The thickness of the anodized film was obtained from observation at a magnification of 1000 to 5000 times by SEM from the cross-sectional direction.

<Sealing treatment>
Any of the sealing treatments (1) to (6) described later was applied to the insulating layer made of the anodized film obtained above to produce an insulating substrate. In addition, the kind of sealing process performed in each Example is as showing in the following Table 1.

Sealing treatment (1):
An aluminum substrate having an insulating layer made of an anodized film was immersed in pure water at 80 ° C. for 1 minute, and then heated in an atmosphere at 110 ° C. for 10 minutes in the immersed state.

Sealing treatment (2):
An aluminum substrate having an insulating layer made of an anodized film was immersed in pure water at 60 ° C. for 1 minute, and then heated in an atmosphere at 130 ° C. for 25 minutes.

Sealing treatment (3):
An aluminum substrate having an insulating layer made of an anodized film was immersed in a 5% aqueous solution of lithium chloride at 80 ° C. for 1 minute, and then heated in an atmosphere at 110 ° C. for 10 minutes.

Sealing treatment (4):
The aluminum substrate which has the insulating layer which consists of an anodic oxide film was processed to expose to 100 degreeC / 500kPa water vapor for 1 minute.

Sealing treatment (5):
An aluminum substrate having an insulating layer made of an anodized film was immersed in a treatment liquid A (see below) at 25 ° C. for 15 minutes, and then heat-treated at 500 ° C. for 1 minute.
(Processing liquid A)
・ Titanium tetraisopropoxide 50.00g
・ Concentrated nitric acid 0.05g
・ Pure water 21.60g
・ Methanol 10.80 g

Sealing treatment (6):
An aluminum substrate having an insulating layer made of an anodized film was immersed in a treatment liquid B (see below) at 25 ° C. for 1 hour.
(Processing liquid B)
・ 20 nm diameter colloidal silica (Nissan Chemical Industries, Ltd. MA-ST-M) 0.01 g
・ Ethanol 100.00g

Sealing treatment (7):
An aluminum substrate having an insulating layer made of an anodized film was immersed in a treatment liquid B (see [0103]) at 25 ° C. for 3 hours.

(Comparative Examples 1-3)
Insulating substrates of Comparative Examples 1, 2, and 3 were produced in the same manner as in Examples 1, 3, and 6 except that the sealing treatment was not performed.

<Porosity>
About each produced insulating substrate, the porosity of the anodic oxide film was computed from the following formula. The results are shown in Table 1 below.
Porosity (%) = [1- (oxide film density / 3.98)] × 100
(In the formula, the oxide film density (g / cm ³ ) represents “oxide film mass per unit area / oxide film thickness”, and 3.98 represents the density of aluminum oxide (g / cm ³ ).)

<Thermal conductivity>
About each produced insulation board | substrate, thermal diffusivity was computed according to the t1 / 2 method using TC-9000 / laser flash type thermal diffusivity measuring apparatus by ULVAC-RIKO, and the thermal conductivity was computed from the following formula. The results are shown in Table 1.
Thermal conductivity λ = α × Cp × ρ
(In the formula, α represents thermal diffusivity, Cp represents specific heat, and ρ represents density.)

<Dielectric breakdown voltage>
With respect to the obtained insulating substrate, the dielectric breakdown voltage was measured according to the method of the JISC2110 standard. The results are shown in Table 1.

<Measurement of total reflectance>
About the obtained insulating substrate, 400-700 nm total reflectance was measured using SP64 by X-Rite. The measurement was performed every 10 nm, and the average value was calculated. The results are shown in Table 1.

From the results shown in Table 1, first, comparing Comparative Example 1 and Comparative Example 2, if the anodic oxide film is thickened from the viewpoint of improving insulation (withstand voltage), the heat dissipation (thermal conductivity) is reduced. I understood.
On the other hand, the insulating substrate (Examples 1 to 8) in which the porosity of the anodic oxide film is 30% or less by performing the sealing treatment suppresses the reduction in heat dissipation even when the anodic oxide film is thick. It was found that both insulation and heat dissipation were excellent.
In particular, when Example 1 and Comparative Example 1 in which the formation conditions and film thickness of the anodized film are the same values are compared, the sealing treatment is performed to reduce the porosity of the anodized film to 30% or less. It was found that the thermal conductivity can be improved while maintaining the voltage and average reflectance. The same can be seen from the comparison between Example 3 and Comparative Example 2 and the comparison between Example 6 and Comparative Example 3.

Example 9
The insulating substrate manufactured in Example 3 (porosity: 5%) was further subjected to oxygen plasma treatment while controlling the pressure, whereby the insulating substrate of Example 9 was manufactured.
The oxygen plasma treatment was performed using a plasma reactor PR300 manufactured by Yamato Scientific Co., Ltd. for 4 minutes under a condition of 100 W while flowing oxygen at 80 mL / min and adjusting the pressure to be −0.1 MPa.
By the oxygen plasma treatment, the hydroxyl group of aluminum hydroxide sealed inside the micropore by the sealing treatment reacts with ionized oxygen and is desorbed as water, and the aluminum hydroxide present in the surface layer is It changed to aluminum oxide and was removed by volume shrinkage.
After the oxygen plasma treatment, the surface of the insulating substrate was observed with an SEM. As a result, alteration from the surface to about 2 μm was observed, and then 5 μm square was measured with an AFM in a tapping mode. As a result, the average depth was 1.8 μm. It was found that the recesses exist with an average pitch of 110 nm. In addition, when the surface of the insulating substrate produced in Example 3 was measured by AFM, a recess having a depth exceeding 0.3 μm was not observed, and a clear pitch could not be detected.
Moreover, when the porosity of the anodic oxide film after the oxygen plasma treatment was calculated by the method described above, the porosity was 9%.

(Example 10)
The insulating substrate produced in Example 3 (porosity: 5%) was further subjected to alkali treatment for 1 minute using a 1% NaOH solution (liquid temperature: 10 ° C.) to produce the insulating substrate of Example 10.
After the alkali treatment, the substrate was washed with water for 10 minutes and dried, and then the surface of the insulating substrate was observed with an SEM. As a result, alteration from the surface to about 10 μm was observed. As a result of measurement, it was found that recesses having an average depth of 2 μm exist with a period of an average pitch of 100 nm.
Moreover, when the porosity of the anodized film after alkali treatment was calculated by the method described above, the porosity was 12%.

With respect to the produced insulating substrates of Examples 1 to 10 and Comparative Examples 1 to 3, a wiring substrate in which a metal wiring layer provided for mounting was formed by the following method was prepared.
(1) Formation of Ni seed layer First, 25 g of nickel sulfate hexahydrate and 500 mL of pure water were put into a 1000 mL beaker to dissolve nickel sulfate hexahydrate, and then 20 g of sodium hypophosphite and 10 g of sodium acetate. And 10 g of sodium citrate was added and stirred.
Subsequently, pure water was added to make the total volume 1000 mL, the pH was adjusted to 5 with sulfuric acid, and the bath temperature was maintained at 83 ° C. while stirring.
The Ni seed layer was formed by immersing each insulating substrate in this solution for 1 minute.
(2) Formation of Cu plating layer In the electrolyte prepared sulfuric acid, copper sulfate, hydrochloric acid, polyethylene glycol and sodium lauryl sulfate, the substrate on which the Ni seed layer was formed was immersed, electrolyzed under a constant voltage, thickness A 20 μm Cu plating layer was formed.
(3) Formation of metal wiring The substrate on which the Cu plating layer was formed was immersed in a resist solution (DSR330P, manufactured by Tamura Kaken Co., Ltd.) at 25 ° C. for 5 minutes, followed by a drying temperature of 80 ° C. and a drying time. Dry in 10 minutes.
Next, using FL-3S (manufactured by Ushio Lighting Co., Ltd.), exposure is performed using a mask on which a wiring pattern is formed, and development is performed for 90 seconds at 30 ° C. using a 1% aqueous sodium carbonate solution. The resist layer was removed.
Next, the substrate on which the pattern was formed by the above method was immersed in a hydrogen peroxide solution and subjected to an etching treatment to peel off the Cu layer and the Ni seed layer in the non-wiring portion.
Next, the remaining resist layer was removed to produce a wiring board on which Cu wiring was formed.
(4) Formation of Au plating layer Ni strike plating was performed on the wiring board on which the Cu wiring was formed in order to impart wire bonding suitability, and an Au plating layer was further provided on the Ni strike plating layer.
The Ni strike plating was processed for 5 minutes using a Ni / hydrochloric acid mixture.
After that, an Au plating layer was formed by immersing the precious hub ACG2000 (manufactured by Tanaka Kikinzoku Co., Ltd.) and a reducing solution at a ratio of 10: 0.4 for 10 minutes at 50 ° C.

In the case of using the insulating substrate produced in Comparative Examples 1 to 3 that has not been subjected to the sealing treatment, in the steps shown in the above (3) and (4), during the etching process of the Cu layer of the non-wiring portion, The Ni seed layer could not be peeled off, the reflectance of the non-wiring portion was lowered, and Au was plated on the entire surface when the Au plating layer was formed.
On the other hand, when the insulating substrates produced in Examples 1 to 8 were used, the above-mentioned problems did not occur, but the results were slightly inferior in adhesion with the thin wire portion of the formed Cu wiring.
Moreover, when the insulated substrate produced in Example 9 and 10 was used, it turned out that the above problems do not generate | occur | produce and it is excellent also in the adhesiveness with the thin wire | line part of formed Cu wiring. This is presumably because the anchoring effect with the Cu wiring is caused by the uneven shape of the surface of the insulating substrate produced in Examples 9 and 10.

(Example 11)
First, a water-repellent material (perfluorohexylethylmethoxysilane [CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH) is applied to the insulating substrate (unsealed pores, porosity: 36%) prepared in Comparative Example 2). ₃ ) ₃ ] (manufactured by Gelest)) was used as it was without being purified, and was projected and adhered in a wiring shape using an ink jet apparatus (DMT-2831, manufactured by Dimatix), and then dried.
Then, the sealing process similar to the sealing process (1) mentioned above was performed. In addition, when the porosity of the anodized film was calculated by the method described above, the porosity was 18%.
Next, dissolution treatment with an alkali (1% NaOH solution, liquid temperature: 30 ° C., treatment time: 20 seconds) was performed to remove a substantially monolayer fluorine (fluoroalkylsilane) film.
Ni was vapor-deposited in this state, and a Ni seed layer was formed on the entire surface.
Subsequently, a Cu wiring substrate was produced by the same method as the steps shown in the above (2) to (4).
Here, in the step shown in the above (3), the non-wiring portion that has been subjected to the sealing treatment can easily dissolve the Ni seed layer, and the Ni strike plating applied in the step shown in the above (4) and Also in Au plating, metal deposition on the non-wiring portion was not observed.

1 Anodized film 2, 2a, 2b Micropore 3 Different materials 22 Blue LED
24 Resin 26 Fluorescent light emitting unit 32 Insulating layer 33 Metal substrate 34 Metal wiring layer 35 Through hole 37 Blue LED
39 Heat Sink 100 Light Emitting Element 110 Blue LED
120, 130 Metal wiring layer (electrode)
DESCRIPTION OF SYMBOLS 140 Wiring board 150 Fluorescent particle 160 Transparent resin 410 Anodizing apparatus 412 Power supply tank 414 Electrolytic processing tank 416 Aluminum substrate 418, 426 Electrolytic solution 420 Power supply electrode 422, 428 Roller 424 Nip roller 430 Electrolytic electrode 432 Tank wall 434 DC power supply

Claims (14)

An insulating substrate having a metal substrate and an insulating layer provided on the surface of the metal substrate,
The metal substrate is a valve metal substrate;
The insulating layer is an anodized film of a valve metal;
An insulating substrate having a porosity of the anodized film of 30% or less.   The insulating substrate according to claim 1, wherein the surface of the anodized film has irregularities having an average pitch of 0.5 μm or less and an average diameter of 1 μm or more. The anodized film has micropores;
The insulating substrate according to claim 1, wherein at least a part of the inside of the micropore is sealed with a material different from a material constituting the anodized film. The anodized film has micropores;
The micropore includes a micropore in which at least a part of the inside thereof is sealed with a material different from the material constituting the anodized film, and a micropore in which the inside is not sealed with the different material. The insulating substrate according to claim 1, which is configured.   The insulating substrate according to claim 3, wherein the different substance is insulating.   The insulation according to any one of claims 1 to 5, wherein the valve metal is at least one metal selected from the group consisting of aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth and antimony. substrate.   The insulating substrate according to claim 6, wherein the valve metal is aluminum.   The insulating substrate according to claim 1, wherein the insulating substrate is a substrate provided on a light emission observation surface side of the LED light emitting element. An insulating substrate manufacturing method for manufacturing the insulating substrate according to claim 1,
Anodizing the surface of the valve metal substrate to form an anodized film of the valve metal on the valve metal substrate;
A method for manufacturing an insulating substrate, comprising: a sealing treatment step of performing a sealing treatment after the anodizing treatment step so that a porosity of the anodized film is 30% or less. By the anodizing treatment, the anodized film having micropores is formed,
The method for manufacturing an insulating substrate according to claim 9, wherein at least a part of the inside of the micropore is sealed with a material different from a material constituting the anodized film by the sealing treatment.   The method for manufacturing an insulating substrate according to claim 9, further comprising a through-hole forming step of forming a through-hole in a thickness direction of the valve metal substrate.   The method for manufacturing an insulating substrate according to claim 11, further comprising a step of dividing the valve metal substrate into a desired shape after the through-hole forming step.   A wiring substrate comprising the insulating substrate according to claim 1 and a metal wiring layer provided on an upper portion of the insulating substrate on the insulating layer side.   14. A white system comprising: the wiring board according to claim 13; a blue LED light emitting element provided on an upper portion of the wiring board on the metal wiring layer side; and a fluorescent light emitter provided at least on the blue LED light emitting element. LED light emitting element.