TWI552375B - An optical semiconductor device and a method for manufacturing the same, and a silver surface treatment agent and a light emitting device - Google Patents

Description

Optical semiconductor device, method of manufacturing the same, and surface treatment agent for silver and illuminating device

The present invention relates to an optical semiconductor device to which a light-emitting diode is bonded, a method of manufacturing the same, and a surface treatment agent for silver and a light-emitting device.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a surface treatment agent for silver, and more particularly to a surface treatment agent for preventing discoloration (corrosion) of various silver or silver alloys, particularly for preventing silver or silver alloys, particularly silver steaming. A surface treatment agent for discoloration (corrosion) of a plating surface, which is used for an illumination device such as an electronic component or a light-emitting diode.

The present invention relates to a light-emitting device, and more particularly to a light-emitting device comprising a substrate having a silver or a silver alloy and a light-emitting diode.

An optical semiconductor device disclosed in Patent Document 1 is known as an optical semiconductor device in which an LED (Light Emitting Diode) is mounted. In the optical semiconductor device described in Patent Document 1, a blue LED is bonded to a molded body, and the molded body is stood up as a reflector for reflecting light emitted by the blue LED in a manner of surrounding the blue LED, and is filled therein. The blue LED is sealed by a transparent sealing portion containing a phosphor.

Silver and silver alloys, as precious metals, have been used as decorations, currency, food, and electronic materials since ancient times due to their excellent optical and electrochemical properties. Materials, lighting equipment, and dental materials are used. In recent years, the demand for reflective materials for light-emitting diodes (LEDs) is rapidly increasing. The light-emitting diode is used as a light source for a fluorescent lamp or an incandescent light bulb, and is used for a lighting device, an automobile lamp, or the like. In such a light-emitting device, a light-reflecting film such as a silver plating layer is provided on the substrate to enhance the light. The efficiency of the extraction.

However, since silver and silver alloys are chemically very unstable, they are easily reacted with oxygen, moisture, hydrogen sulfide, sulfurous acid gas, etc. in the air to form silver oxide or silver sulfide, and thus the surface of the silver is discolored (corroded). The disadvantage of black.

For the method of preventing such discoloration (corrosion) of silver, for example, an organic rust preventive agent has been proposed (for example, refer to Patent Documents 2 to 3). Further, in Patent Document 4 below, a surface treatment agent containing silver in a layered tannic acid compound is proposed.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: International Publication No. 2007/015426

Patent Document 2: Japanese Patent Laid-Open No. Hei 10-158572

Patent Document 3: Japanese Laid-Open Patent Publication No. 2004-238658

Patent Document 4: International Publication No. 2013/108773

In recent years, such an optical semiconductor device has been gradually adopted as an LED illumination such as illumination or a street lamp. However, after actually trying to use it, The illumination of the LED illumination is reduced in a shorter time than the guaranteed time of the LED. This is caused by the formation of a silver plating layer on the electrodes of the optical semiconductor device, and the silver plating layer is discolored. That is, for the transparent sealing portion, since a gas or a resin having high water permeability is generally used, gas or moisture penetrating through the transparent sealing portion may cause corrosion and discoloration of the silver plating layer. In particular, if the silver plating layer is vulcanized due to hydrogen sulfide gas, the electrode is discolored to black, and the illuminance is remarkably lowered.

Further, conventionally, a thermoplastic resin is used as a reflector, and the yellowing speed of the reflector is faster than the vulcanization rate of the silver plating layer, so that the illuminance reduction due to vulcanization of the silver plating layer is less noticeable. . However, recently, a thermosetting resin has been used as a reflector, and since the rate of vulcanization of the silver plating layer is slower than the rate of vulcanization of the silver plating layer, the illuminance caused by vulcanization of the silver plating layer is lowered. More eye-catching. Further, when the LED illumination is increased in power, the temperature of the silver plating layer rises due to the high heat generation temperature of the blue LED, and thus the vulcanization of the silver plating layer is promoted.

Further, in view of the problem of vulcanization of the silver plating layer, there is an operation of normalizing the evaluation of the hydrogen sulfide gas resistance of the optical semiconductor device used for LED illumination.

Therefore, after in-depth discussion, the inventors of the present invention obtained the insight that instead of improving the gas permeability of the transparent sealing portion, the anti-vulcanization film having gas barrier properties derived from clay is used to cover the silver plating layer. This can effectively suppress the vulcanization of the silver plating layer.

Further, the inventor of the present invention discovered that the adhesive force of the clay to the reflector is not so high when manufacturing the optical semiconductor device based on such findings. Therefore, the problem that the transparent sealing portion is peeled off from the optical semiconductor device is high.

Accordingly, a first object of the present invention is to provide an optical semiconductor device capable of suppressing vulcanization of a silver plating layer and suppressing peeling of a transparent sealing portion.

The inventors of the present invention conducted intensive investigations and found that it is possible to effectively suppress the silver plating layer by providing a gas barrier layer having a gas barrier property derived from clay instead of improving the gas permeability of the transparent sealing portion. By vulcanization, the gas barrier properties of the gas barrier layer can be improved by homogenizing the layer thickness of the gas barrier layer.

Accordingly, a second object of the present invention is to provide an optical semiconductor device capable of suppressing vulcanization of a silver plating layer and improving gas barrier properties, and a method of manufacturing the same.

The organic rust preventive agent has a drawback that it is low in resistance to ultraviolet rays and causes ultraviolet ray exposure over a long period of time to cause discoloration. Among the light-emitting diodes used in lighting equipment and automotive applications, these organic rust inhibitors are difficult to apply due to the use of near-ultraviolet light.

Further, when a surface treatment agent is applied to the surface of the silver plating layer, the sealing material or the like provided thereon may be easily peeled off.

The present invention has been made in view of the above circumstances, and a third object of the present invention is to provide a light-emitting device which has an anti-tarnish film excellent in discoloration resistance to a silver plating layer and which is not easily peeled off; and a surface treatment for silver The agent is excellent in discoloration resistance (corrosion) to silver, and can impart excellent discoloration resistance to the surface of silver, and can reduce the influence on the sealing material and the like.

The inventor of the present invention found that if the substrate of the light-emitting device is provided, When a layer containing a layered citric acid compound is subjected to electrochemical migration, the electrode may be discolored. In order to maintain sufficient luminous intensity for a long period of time, the light-emitting device is required to have insulation reliability that does not easily migrate.

A fourth object of the present invention is to provide a light-emitting device having a color-resistant film which is excellent in both discoloration resistance and insulation reliability of a silver plating layer.

An optical semiconductor device according to an aspect of the present invention includes: a substrate having a silver plating layer formed on a surface thereof; a light emitting diode bonded to the silver plating layer; and a light reflecting portion surrounding the light emitting diode a light reflecting surface forming an inner space for accommodating the light emitting diode; an anti-silver vulcanized film covering the silver plating layer; and a transparent sealing portion filled in the inner space to seal the light emitting diode; wherein the silver sulfide is resistant The film has a gas barrier layer having gas barrier properties derived from clay, and an undercoat layer disposed on the lower layer of the gas barrier layer and having adhesiveness; and the transparent seal portion is in contact with the undercoat layer.

According to the optical semiconductor device of one aspect of the present invention, since the silver plating layer is covered by the gas barrier layer having gas barrier properties derived from clay, vulcanization of the silver plating layer can be suppressed. Thereby, it is possible to greatly suppress the decrease in the illuminance of the optical semiconductor device caused by the blackening of the silver plating layer. Further, in the case of the anti-silver vulcanization film, the undercoat layer having the adhesive property is disposed in the lower layer of the gas barrier property, and the transparent sealing portion is brought into contact with the undercoat layer, and the undercoat layer is applied or the primer is not applied. When the layer is not in contact with the transparent sealing resin, peeling of the transparent sealing portion can be suppressed.

As an embodiment, the undercoat layer is formed on the light reflecting surface, and the gas The body barrier layer is laminated on the light reflecting surface to a portion of the undercoat layer, and the transparent sealing portion is in contact with the undercoat layer at a position where the gas barrier layer on the light reflecting surface is not laminated to the undercoat layer. The silver-resistant vulcanization film may be coated with a solute of the solvent-diluted gas barrier layer and the undercoat layer into the inner space of the light-reflecting portion, and then the solvent may be dried. get on. However, since the inner space is small, it is difficult to drip or spread the diluent only to the silver plating layer. Thus, since the silver-resistant vulcanization film is allowed to cover the light-reflecting surface, the silver-plated film can be easily covered with the anti-silver vulcanization film. Further, even in this case, since the gas barrier layer on the light reflecting surface is not laminated on the undercoat layer, the transparent sealing portion comes into contact with the undercoat layer, and peeling of the transparent sealing portion can be suppressed.

Further, as an embodiment, the light emitting diode may be a blue LED that emits blue light. The light reflecting surface reflects the light emitted from the light emitting diode and is output from the optical semiconductor device. However, since the gas barrier layer having gas barrier properties derived from clay has an effect of increasing the frequency band of the blue light, the gas is utilized. The barrier layer covers the light reflecting surface and can increase the reflection efficiency of the blue light emitted by the blue LED.

Further, as an embodiment, the gas barrier layer may not be laminated on the undercoat layer on the light reflecting surface. In this manner, since the gas barrier layer is not laminated on the undercoat layer on the light-reflecting surface, the contact area between the transparent sealing portion and the undercoat layer can be increased, so that the peeling of the transparent sealing portion can be further suppressed.

Moreover, as an embodiment, the undercoat layer is formed on the light reflecting surface, and the gas barrier layer is laminated on the undercoat layer on the light reflecting surface, and the transparent sealing portion may also be associated with the undercoat layer extending along the light reflecting surface. Leading edge contact. So that is When the gas barrier layer is formed on the light-reflecting surface, the leading edge surface of the undercoat layer extending along the light-reflecting surface is brought into contact with the transparent resin, whereby peeling of the transparent sealing portion can be further suppressed.

Further, in one embodiment, a top surface is formed in the light reflecting portion, the top surface is adjacent to the light reflecting surface and located outside the inner space; the undercoat layer is formed on at least a portion of the top surface, and the gas barrier layer is reflected in the light The surface is laminated on the undercoat layer, and the transparent sealing portion can also be in contact with the undercoat layer on the top surface. The silver-resistant vulcanization film may be coated with a solute of the solvent-diluted gas barrier layer and the undercoat layer into the inner space of the light-reflecting portion, and then the solvent may be dried. Implemented. However, since the inner space of the light reflecting portion is small, it is difficult to drip or spread the diluent only to the silver plating layer. Therefore, since the silver-resistant vulcanization film is allowed to cover the entire light-reflecting surface, the silver-resistant vulcanization film can be more easily covered with the silver-plated layer. Further, even in this case, since the transparent sealing portion is in contact with the undercoat layer on the top surface of the light reflecting portion, peeling of the transparent sealing portion can be suppressed.

An optical semiconductor device according to an aspect of the present invention includes: a substrate having a silver plating layer formed on a surface thereof; a light emitting diode bonded to the silver plating layer; and a light reflecting portion surrounding the light emitting diode a light reflecting surface forming an inner space for accommodating the light emitting diode; a transparent sealing portion filling the inner space to seal the light emitting diode; and a gas blocking layer formed at a position away from the substrate and having a source Gas barrier properties in clay.

According to the optical semiconductor device of one aspect of the present invention, since the gas barrier layer having gas barrier properties derived from clay is formed, vulcanization of the silver plating layer can be suppressed. Thereby, the blackening of the silver plating layer can be greatly suppressed. The illuminance of the optical semiconductor device is lowered. Incidentally, the gas barrier layer having gas barrier properties derived from clay is improved in gas barrier properties by homogenizing the layer thickness. On the other hand, since the surface of the substrate on which the silver plating layer is formed is uneven, it is difficult to homogenize the layer thickness of the gas barrier layer when the gas barrier layer is formed on the surface of the substrate. Thus, the layer thickness of the gas barrier layer can be made uniform by forming the gas barrier layer at a position away from the substrate. Thereby, the gas barrier property of the gas barrier layer can be improved.

As an embodiment, a transparent sealing portion may be disposed between the gas barrier layer and the substrate. In this manner, by arranging the transparent sealing portion between the gas barrier layer and the substrate, since the gas barrier layer becomes distant from the substrate, migration between the gas barrier layer and the substrate can be prevented.

Further, as an embodiment, the gas barrier layer may be buried in the transparent sealing portion. In this way, since the gas barrier layer is buried in the transparent sealing portion, peeling of the gas barrier layer can be prevented.

Further, as an embodiment, the gas barrier layer may be formed on the surface of the transparent sealing portion. In this way, since the gas barrier layer is formed on the surface of the transparent sealing portion, the transparent sealing portion and the gas barrier layer can be easily formed.

Further, as an embodiment, an undercoat layer may be further provided on the substrate and the light reflecting surface, and a gas barrier layer may be laminated. In this manner, since the undercoat layer is formed between the substrate and the gas barrier layer, the transparent sealing portion can be not filled between the substrate and the gas barrier layer, and the gas barrier layer can be disposed at a position away from the substrate. Further, in the case where the gas barrier layer is formed directly on the substrate, the surface on which the gas barrier layer is to be formed is planarized by the undercoat layer, and the layer thickness of the gas barrier layer can be made uniform. Thereby being able to Improve the gas barrier properties of the gas barrier layer.

Further, as an embodiment, a second gas barrier layer may be further formed on the surface of the silver plating layer and has gas barrier properties derived from clay. In this way, since the second gas barrier layer is formed on the surface of the silver plating layer, the gas barrier layer can be easily multilayered. Thereby, the gas barrier property can be further improved.

Further, as an embodiment, a bonding wire bonded to the substrate and the LED may be further provided, and the second gas barrier layer covers the bonding wire. In this way, since the bonding wire is covered by the second gas barrier layer, when the material of the bonding wire is made of silver, vulcanization of the bonding wire can be suppressed.

Further, as an embodiment, the second gas barrier layer may cover the light reflecting surface. As a result, since the light reflecting surface is covered by the second gas barrier layer, oxidation of the light reflecting surface can be suppressed. Thereby, it is possible to greatly suppress a decrease in illuminance of the optical semiconductor device due to discoloration of the light reflecting surface.

A method of manufacturing an optical semiconductor device according to an aspect of the present invention includes the following steps: a preparation step of preparing an intermediate part; and a transparent sealing portion sealing step of filling a transparent sealing portion in an inner space and sealing the light with a transparent sealing portion And a gas barrier layer forming step of forming a gas barrier layer having a gas barrier property derived from clay at a position away from the substrate; wherein the intermediate portion is provided with a substrate, and the surface is formed with silver plating a layer, and a light emitting diode is bonded to the silver plating layer; the light emitting diode is bonded to the silver plating layer; and the light reflecting portion is formed to receive the light emitting diode by surrounding the light reflecting surface of the light emitting diode The inner space of the body.

According to the method of manufacturing an optical semiconductor device according to an aspect of the present invention, since the gas barrier layer having gas barrier properties derived from clay is formed, vulcanization of the silver plating layer can be suppressed. Thereby, it is possible to greatly suppress the decrease in the illuminance of the optical semiconductor device caused by the blackening of the silver plating layer. Incidentally, the gas barrier layer having gas barrier properties derived from clay is improved in gas barrier properties by homogenizing the layer thickness. On the other hand, since the surface of the substrate on which the silver plating layer is formed is uneven, it is difficult to homogenize the layer thickness of the gas barrier layer when the gas barrier layer is formed on the surface of the substrate. Thus, the layer thickness of the gas barrier layer can be made uniform by forming the gas barrier layer at a position away from the substrate. Thereby, the gas barrier property of the gas barrier layer can be improved.

In one embodiment, an undercoat layer forming step may be further provided to form an undercoat layer on which a gas barrier layer is to be laminated on the substrate and the light reflecting surface. In this way, by forming an undercoat layer between the substrate and the gas barrier layer, the transparent barrier portion is not filled between the substrate and the gas barrier layer, and the gas barrier layer can be formed at a position away from the substrate. Further, in the case where the gas barrier layer is formed directly on the substrate, the surface on which the gas barrier layer is to be formed is planarized by the undercoat layer, and the layer thickness of the gas barrier layer can be made uniform. Thereby, the gas barrier property of the gas barrier layer can be improved.

Further, as an embodiment, a second gas barrier layer forming step may be further provided to form a second gas barrier layer having gas barrier properties derived from clay on the surface of the silver plating layer. In this way, since the second gas barrier layer is formed on the surface of the silver plating layer, the gas barrier layer can be easily multilayered. Thereby, the gas barrier property can be further improved.

An illumination device according to an aspect of the present invention includes: a silver plating layer a substrate, a light-emitting diode mounted on the substrate, and a multi-layer film (two or more layers) covering at least a surface of the silver plating layer; wherein the multi-layer film has a first layer containing a layered tannic acid a compound; and a second layer comprising a second phthalic acid compound other than the layered citric acid compound.

In the light-emitting device according to the aspect of the invention, it is possible to exhibit gas shielding properties against a gas such as hydrogen sulfide according to the first layer, and to provide excellent discoloration resistance to the surface of the silver plating layer. Further, according to the second layer, the water resistance of the first layer and the adhesion to silver can be improved, and the adhesion to the transparent sealing resin used for covering and sealing the light-emitting device can be improved. Thereby, it is possible to realize a light-emitting device which has a color-resistant film excellent in discoloration resistance to a silver plating layer and which is not easily peeled off. Further, the above-mentioned multi-layer film can have sufficient light transmittance, and can suppress discoloration of the silver plating layer without impairing the light-emitting characteristics of the light-emitting device.

In a light-emitting device according to an aspect of the invention, it is preferable that the second layer and the first layer are sequentially provided on a surface of the silver plating layer.

The above light-emitting device may also be covered or sealed with a transparent sealing resin.

A surface treatment agent for silver according to the present invention comprises: a liquid A comprising a layered citric acid compound; and a liquid B containing a second phthalic acid compound other than the layered citric acid compound.

According to the silver surface treatment agent of the present invention, it is possible to form a multi-layer film having the first layer formed of the A liquid and the second layer formed of the B liquid, whereby the silver is resistant to discoloration ( It is excellent in corrosion resistance, and can provide excellent discoloration resistance on the surface of silver, and can reduce the influence on a sealing material etc. Moreover, according to one aspect of the surface treatment agent for silver according to the present invention, When a light-resistant device having excellent transparency and adhesion is formed, when it is applied to a light-emitting device having a silver-plated layer, it is possible to form an anti-tarnish that can sufficiently suppress the discoloration of the silver-plated layer without impairing the light-emitting characteristics of the light-emitting device. membrane.

In the surface treatment agent for silver according to an aspect of the invention, the second phthalic acid compound is preferably a polyfluorene-based resin or an inorganic glass.

Moreover, the average long side length of the layered tannic acid compound is preferably 30 nm or more and 50,000 nm or less. By using a layered tantalum compound having an average long side length in such a range, discoloration of silver can be more sufficiently suppressed.

An aspect of the invention provides a hair-emitting device comprising: a substrate having a silver-plated layer; a light-emitting diode mounted on the substrate; and a multi-layer film covering at least a surface of the silver plating layer; wherein the multi-layer film has: The first layer contains an oxygen permeability of 0.0001 to 10 cc/m ² . 24h. a compound of atm; and, layer 2, which has a volume resistivity of 10 ¹⁰ ~ 10 ¹⁶ Ω. Cm compound.

According to the light-emitting device of the aspect of the invention, the multi-layer film can exhibit the function of the anti-tarnish film which is excellent in both the discoloration resistance and the insulation reliability of the silver plating layer, and can maintain sufficient luminous intensity for a long period of time. .

In a light-emitting device according to an aspect of the invention, it is preferable that the second layer and the first layer are sequentially provided on a surface of the silver plating layer.

The above light-emitting device may also be covered or sealed with a transparent sealing resin. In this case, since the adhesion between the above-mentioned multi-layer film and the transparent sealing resin is excellent, the problem of peeling off of the sealing resin is less likely to occur.

According to the present invention, it is possible to provide an optical semiconductor device capable of suppressing vulcanization of a silver plating layer and suppressing peeling of a transparent sealing portion.

According to the present invention, it is possible to provide an optical semiconductor device capable of suppressing vulcanization of a silver plating layer and improving gas barrier properties.

According to the present invention, it is possible to provide a light-emitting device which has an anti-tarnish film excellent in discoloration resistance to a silver plating layer and which is not easily peeled off by a sealing material; and a surface treatment agent for silver which is resistant to discoloration (corrosion) of silver It is excellent in the ability to impart excellent discoloration resistance on the surface of silver, and it is possible to reduce the influence on the sealing material and the like.

According to the silver surface treatment agent of the present invention, it is possible to prevent, for example, silver used in an illumination device such as an electronic component or a light-emitting diode, in particular, discoloration (corrosion) of the silver vapor deposition surface.

According to the present invention, it is possible to provide a light-emitting device having an anti-tarnish film excellent in both discoloration resistance and insulation reliability of a silver-plated layer.

1, 2, 3, 4‧‧‧ Optical semiconductor devices

10‧‧‧Substrate

10a‧‧‧ surface

12‧‧‧ base

14‧‧‧copper plate

16‧‧‧Silver plating

20‧‧‧Reflector (light reflection part)

20a‧‧‧Light reflecting surface

20b‧‧‧ top surface

20c‧‧‧ outer perimeter

20d‧‧‧Upper end

22‧‧‧ inside space

30‧‧‧Blu-ray diode

32‧‧‧Grain joints

34‧‧‧bonding leads

40‧‧‧Transparent seal

42‧‧‧Fluorite

44‧‧‧Transparent sealing resin

50, 52, 53, 54‧ ‧ gas barrier

60, 63, 64‧‧‧ undercoat

60a, 63a, 64a‧‧‧ undercoat reflective face

63b‧‧‧ front face

64b‧‧‧Undercoat top surface

70, 72, 73, 74‧‧‧ anti-silver vulcanized film

H‧‧‧thickness

L‧‧‧Clay dilution, length

M‧‧‧ primer dilution

U‧‧‧Exposed Department

101, 102, 103, 104, 105, 106‧‧‧ optical semiconductor devices

108‧‧‧Intermediate parts

110‧‧‧Substrate

110a‧‧‧ surface

112‧‧‧ base

114‧‧‧copper plate

116‧‧‧Silver plating

120‧‧‧ reflector (light reflection part)

120a‧‧‧Light reflecting surface

120b‧‧‧ top surface

120c‧‧‧ outer perimeter

122‧‧‧ inside space

124‧‧‧ openings

130‧‧‧Blue LED (Light Emitting Diode)

132‧‧‧Grain joints

134‧‧‧bonding leads

140‧‧‧Transparent seal

142‧‧‧Fluorite

150, 151, 155‧ ‧ gas barrier

152, 153, 154‧‧‧ second gas barrier

153a, 154a‧‧‧Light reflecting surface covering

153b, 154b‧‧‧ Bonded lead cover

160‧‧‧Undercoat

L‧‧‧Clay Diluent

201‧‧‧Lighting device

210‧‧‧Substrate

210a‧‧‧ surface of the substrate

212‧‧‧ base

214‧‧‧copper plate

216‧‧‧ Silver plating

220‧‧‧ reflector (light reflection part)

220a‧‧‧ inner circumference (light reflection surface)

220b‧‧‧ top surface

220c‧‧‧ outer perimeter

222‧‧‧ inside space

230‧‧‧Blue LED (Blu-ray diode)

232‧‧‧die joints

234‧‧‧bonding leads

240‧‧‧Transparent sealing resin (transparent sealing part)

242‧‧‧Fertior

250‧‧‧Layer 2 (primer coating)

252‧‧‧1st layer (gas barrier)

260‧‧‧Multilayer film (anti-tarnish film)

300‧‧‧ particles

310‧‧‧External rectangle

M‧‧‧B liquid

D‧‧‧thickness

L, Lmax‧‧‧ length

Fig. 1 is a cross-sectional view showing an optical semiconductor device according to a first embodiment.

Fig. 2 is a plan view showing the optical semiconductor device shown in Fig. 1.

Fig. 3 is a conceptual diagram for explaining the constitution of a vulcanization resistant film using montmorillonite.

Fig. 4 is a view for explaining a method of forming an undercoat layer.

Fig. 5 is a view for explaining a method of covering a gas barrier layer.

Fig. 6 is a cross-sectional view showing an optical semiconductor device according to a second embodiment.

Fig. 7 is a view for explaining a method of covering a gas barrier layer.

Fig. 8 is a cross-sectional view showing an optical semiconductor device according to a third embodiment.

Fig. 9 is a cross-sectional view showing an optical semiconductor device according to a fourth embodiment.

Fig. 10 is a cross-sectional view showing an optical semiconductor device according to a fifth embodiment.

Fig. 11 is a plan view showing the optical semiconductor device shown in Fig. 10.

Fig. 12 is a conceptual diagram for explaining the constitution of a vulcanization resistant film using montmorillonite.

Fig. 13 is a flow chart showing a method of manufacturing the optical semiconductor device according to the fifth embodiment.

Fig. 14 is a view showing a manufacturing procedure of the optical semiconductor device of the fifth embodiment.

Fig. 15 is a view showing a manufacturing procedure of the optical semiconductor device of the fifth embodiment.

Figure 16 is a cross-sectional view showing an optical semiconductor device according to a sixth embodiment.

Fig. 17 is a flow chart showing a method of manufacturing the optical semiconductor device according to the sixth embodiment.

Figure 18 is a cross-sectional view showing an optical semiconductor device according to a seventh embodiment.

Fig. 19 is a flow chart showing a method of manufacturing the optical semiconductor device according to the seventh embodiment.

Figure 20 is a cross-sectional view showing an optical semiconductor device according to an eighth embodiment.

Fig. 21 is a flow chart showing a method of manufacturing the optical semiconductor device according to the eighth embodiment.

Figure 22 is a cross-sectional view showing an optical semiconductor device according to a ninth embodiment.

Figure 23 is a cross-sectional view showing an optical semiconductor device according to a tenth embodiment.

Fig. 24 is a flow chart showing a method of manufacturing the optical semiconductor device according to the tenth embodiment.

Figure 25 is a cross-sectional view of the light-emitting device.

Figure 26 is a plan view showing the light-emitting device shown in Figure 25.

Fig. 27 is a schematic view showing an example of a layered citric acid compound.

Fig. 28 is a flow chart showing a method of manufacturing the light-emitting device of the eleventh and twelfth embodiments.

Fig. 29 is a cross-sectional view showing a light-emitting device after the coating step of the silver surface treatment agent of the embodiment.

Figure 30 is a cross-sectional view of the light-emitting device after the drying step.

Figure 31 is a cross-sectional view of the light-emitting device after the step of filling the transparent sealing resin.

Fig. 32 is a conceptual view for explaining the configuration of the anti-tarnish film formed of the surface treatment agent for silver of the embodiment.

Fig. 33 is a flow chart showing a method of manufacturing the light-emitting device of the thirteenth and fourteenth embodiments.

Figure 34 is a cross-sectional view showing a light-emitting device manufactured by the manufacturing method of Figure 33.

Fig. 35 is a flow chart showing a method of manufacturing the light-emitting device of the fifteenth and sixteenth embodiments.

Figure 36 is a cross-sectional view showing a light-emitting device manufactured by the manufacturing method of Figure 35.

Fig. 37 is a cross-sectional transmission electron micrograph taken for an example of an anti-tarnish film formed by using a surface treatment agent for silver in the examples.

Hereinafter, a preferred embodiment of an optical semiconductor device according to an aspect of the present invention will be described in detail with reference to the drawings. In addition, in all the drawings, The same symbols will be given to the same or equivalent parts.

[First Embodiment]

Fig. 1 is a cross-sectional view showing an optical semiconductor device according to a first embodiment. Fig. 2 is a plan view showing the optical semiconductor device shown in Fig. 1. As shown in FIG. 1 and FIG. 2, the optical semiconductor device 1 of this embodiment is generally classified into a "surface mount type (surface mount type)". The optical semiconductor device 1 includes a substrate 10, a blue LED 30 bonded to the surface of the substrate 10, a reflector 20 disposed on the surface of the substrate 10 so as to surround the blue LED, and being filled in the reflector The transparent sealing portion 40 which seals the blue LED 32 and the silver-resistant vulcanization film 70 covering the silver plating layer 16 are provided. In addition, in FIG. 2, illustration of the transparent sealing part 40 is abbreviate|omitted.

In the substrate 10, the copper plate 14 is wired on the surface of the insulating base 12, and the silver plating layer 16 is formed on the surface of the copper plate 14. The silver plating layer 16 is disposed on the surface of the substrate 10 to be an electrode that is electrically connected to the blue LED 30. Further, the silver plating layer 16 may be any composition as long as it is a plating layer containing silver. For example, the silver plating layer 16 may be formed by plating only silver, or the silver plating layer 16 may be formed by plating in the order of nickel and silver. The copper plate 14 and the silver plating layer 16 are insulated on the anode side and the cathode side. The insulation between the copper plate 14 and the silver plating layer 16 on the anode side and the copper plating plate 14 and the silver plating layer 16 on the cathode side can be plated, for example, by the copper plating plate 14 on the anode side and the silver plating layer 16 and the cathode side. The copper plate 14 and the silver plating layer 16 are isolated, and an insulating layer such as a resin or a ceramic is interposed therebetween.

The blue LED 30 is a die bonded to the anode side and the cathode side. The silver plating layer 16 of either side is electrically connected to the silver plating layer 16 via the die bonding material 32. Further, the blue LED 30 is a silver plating layer 16 which is wire-bonded to any one of the anode side and the cathode side, and is electrically connected to the silver plating layer 16 via the bonding wires 34.

The reflector 20 is a light reflecting portion filled with a transparent sealing portion 40 for sealing the blue LED 30, and reflects light emitted from the blue diode 30 to the surface side of the optical semiconductor device 1. The reflector 20 is erected on the surface of the substrate 10 in such a manner as to surround the blue LED 30, and an inner space 22 accommodating the blue diode 30 is formed inside. Further, the reflector 20 includes a light reflecting surface 20a, a top surface 20b, and an outer circumferential surface 20c. The light reflecting surface 20a is formed in a circular shape in a plan view (see FIG. 2), and an inner space 22 accommodating the blue LED body 30 is formed around the blue LED body 30. In other words, by surrounding the light reflecting surface 20a of the blue LED 30, the inner space 22 accommodating the blue diode 30 is formed. The top surface 20b is located outside the inner space 22 adjacent to the light reflecting surface 20a, and extends from the front edge of the light reflecting surface 20a toward the opposite side of the inner space 22. The outer peripheral surface 20c has a rectangular shape in plan view (see FIG. 2), and rises from the surface 10a of the substrate 10 to the outer edge of the top surface 20b. The shape of the light reflecting surface 20a and the outer peripheral surface 20c is not particularly limited. However, from the viewpoint of enhancing the illuminance of the optical semiconductor device 1, the light reflecting surface 20a preferably has a truncated cone shape (funnel shape) which is away from the substrate. The diameter is increased by 10, and from the viewpoint of increasing the degree of accumulation of the optical semiconductor device 1, the outer peripheral surface 20c preferably has a rectangular shape facing the substrate 10. Further, as an example of formation of the light reflecting surface 20a, the lower portion on the substrate 10 side is perpendicular to the substrate 10 in the drawing, and the upper portion on the opposite side of the substrate 10 is away from the substrate 10. Expand the diameter.

The reflector 20 is composed of a cured product of a thermosetting resin composition containing a white pigment. From the viewpoint of ease of formation of the reflector 20, the thermosetting resin composition is preferably one which can be press-formed at room temperature (25 ° C) before thermal curing.

As the thermosetting resin contained in the thermosetting resin composition, various resins such as an epoxy resin, a polyoxyxylene resin, an amine ester resin, and a cyanate resin can be used. In particular, an epoxy resin is preferred because of its excellent adhesion to various materials.

As the white pigment, alumina, magnesia, cerium oxide, titanium oxide, zirconium oxide or the like can be used. Among these, titanium oxide is preferred from the viewpoint of light reflectivity. Inorganic hollow particles can also be used as the white pigment. Specific examples of the inorganic hollow particles include sodium citrate glass, aluminum silicate glass, sodium borosilicate glass, and white sand (Shirasu).

The transparent sealing portion 40 is filled in the inner space 22 formed by the light reflecting surface 20a of the reflector 20 to seal the blue LED 30. This transparent sealing portion 40 is composed of a transparent sealing resin having light transmissivity. Among the transparent sealing resins, in addition to the completely transparent resin, a translucent resin is also included. In the case of the transparent sealing resin, the modulus of elasticity is preferably 1 MPa or less at room temperature (25 ° C). In particular, from the viewpoint of transparency, a polyoxyxylene resin or an acrylic resin is preferably used. The transparent sealing resin may further contain an inorganic filler or a phosphor 42 that diffuses light, and the phosphor 42 causes blue light emitted from the blue diode 30 as an excitation source to become white light.

The anti-silver vulcanization film 70 has a gas barrier layer 50, which has a source The gas barrier property of the clay; and the undercoat layer 60 disposed on the lower layer of the gas barrier layer 50 and having adhesiveness.

The gas barrier layer 50 suppresses vulcanization of the silver plating layer 16 by covering the silver plating layer 16. The gas barrier layer 50 is a layer containing clay. As the clay constituting the gas barrier layer 50, any of natural clay and synthetic clay can be used, for example, stevensite, hectorite, saponite, montmorillonite can be used. Any one or more of (montmorillonite) and beidelite. In particular, as shown in Fig. 3, when the thickness H is 1 nm or less and the length L is 10 nm or more and 400 nm or less, the gas path is long, and the gas barrier property is excellent. .

The film thickness of the gas barrier layer 50 is preferably 0.01 μm or more and 1000 μm or less, more preferably 0.03 μm or more and 500 μm or less, and still more preferably 0.05 μm or more and 100 μm or less. It is preferably 0.05 μm or more and 10 μm or less, and more preferably 0.05 μm or more and 1 μm or less. By setting the film thickness of the gas barrier layer 50 to 0.01 μm or more and 1000 μm or less, the gas barrier properties to the silver plating layer 16 and the transparency of the gas barrier layer 50 can be achieved. In this case, the film thickness of the gas barrier layer 50 is set to 0.03 μm or more and 500 μm or less, 0.05 μm or more and 100 μm or less, 0.05 μm or more, 10 μm or less, and 0.05 μm or more. Below 1 μm , this effect can be further improved.

The undercoat layer 60 is disposed between the reflector 20 and the transparent sealing portion 40 to suppress peeling of the reflector 20 by the transparent sealing portion 40. The undercoat layer 60 is preferably a layer having adhesiveness and insulating properties, and for example, a layer containing a phthalic acid compound can be used. As the phthalic acid compound, for example, polyfluorene oxide rubber Polyoxyphthalic resin and inorganic glass.

The tantalum acid compound used in the present embodiment has a linear expansion coefficient of preferably from 180 ppm to 450 ppm from the viewpoint of obtaining adhesiveness by flexibility. When the coefficient of linear expansion is 180 ppm or more, it is easier to ensure adhesiveness derived from softness, and on the other hand, deformation can be suppressed by a linear expansion coefficient of 450 ppm or less, for example, by a transparent sealing resin for covering or sealing. Occurs in the base coat. The tannic acid compound is more preferably a linear expansion coefficient of from 200 ppm to 450 ppm from the viewpoint of improving the adhesion due to flexibility, from the viewpoint of improving the reliability with respect to the transparent sealing resin for covering or sealing. More preferably, it is 200ppm~350ppm.

The niobic acid compound used in the present embodiment has a volume resistivity of preferably 10 ¹⁰ to 10 ¹⁶ Ω from the viewpoint of ensuring insulation. Cm, more preferably 10 ¹² ~ 10 ¹⁶ Ω from the viewpoint of improving insulation. Cm, and more preferably 10 ¹³ ~ 10 ¹⁶ Ω. Cm. In addition, the volume resistivity of the citric acid compound is a value measured by a volume resistivity measurement test piece according to JIS C2139, and the volume resistivity measurement test piece is a substrate in which 3 g of a phthalic acid compound is applied to a copper-attached electrode. It was obtained by drying at 150 ° C for 3 hours.

The film thickness of the undercoat layer 60 is preferably from 10 nm to 1000 nm from the viewpoint of adhesion, and more preferably from 30 nm to 1000 nm from the viewpoint of water resistance, from the viewpoint of effectively exhibiting gas barrier properties of the gas barrier layer 50. More preferably, it is 30 to 500 nm.

The gas barrier layer 50 can be formed by diluting or dispersing a clay obtained by diluting the clay with a solvent into the inner space 22 of the reflector 20, removing the solvent, and/or hardening.

The undercoat layer 60 can be formed by dropping or dispersing a primer which is obtained by diluting the above-described citric acid compound with a solvent into the inner space 22 of the reflector 20, removing the solvent, and/or hardening.

Then, by laminating the gas barrier layer 50 on the undercoat layer 60, it is possible to suppress the water resistance of the anti-silver vulcanization film 70 and the adhesion to the silver plating layer 16 as the transparency can be ensured and the adhesion to the silver plating layer 16 can be improved. Peeling between the covered or sealed transparent sealing portion 40 and the light reflecting surface 20a.

The specific configuration of the gas barrier layer 50 and the undercoat layer 60 is as follows. The undercoat layer 60 is formed on the entire surface of the silver plating layer 16 and the light reflecting surface 20a, and the gas barrier layer 50 covers a portion of the silver plating layer 16 and the light reflecting surface 20a. Among the undercoat layers 60, a portion formed on the light reflecting surface 20a is referred to as an undercoat reflecting surface portion 60a. The undercoat layer reflects the surface portion 60a to form a cover portion on which the gas barrier layer 50 is laminated, and an exposed portion U which is not laminated with the gas barrier layer 50, and the exposed portion U of the undercoat layer 60 contacts the transparent seal portion 40. In addition, the gas barrier layer 50 may be covered with the silver plating layer 16, regardless of whether or not the blue LED body 30 is covered.

The ratio of the area of the exposed portion U to the undercoat reflection surface portion 60a (hereinafter referred to as the "area ratio of the exposed portion U") is not particularly limited, but is preferably 1 to 99%, more preferably 5 to 95. %, especially good is set to 10~90%. By setting the area ratio of the exposed portion U to 1% or more, the bonding strength between the undercoat layer 60 and the transparent sealing portion 40 can be ensured. Further, by setting the area ratio of the exposed portion U to 5% or more and further setting it to 10% or more, this effect can be further enhanced. By setting the area ratio of the exposed portion U to 99% or less, the gas barrier layer 50 can be easily covered. And by the surface of the exposed portion U The product ratio is set below 95%, and further set below 90%, which can further enhance this effect.

Incidentally, the gas barrier layer 50 using the above-described clay has sufficient light transmittance as long as it has a film thickness of 0.01 μm or more and 1000 μm or less. Therefore, even if the light reflecting surface 20a is covered with the gas barrier layer 50, it does not have much influence on the reflection characteristics of the reflector 20. Moreover, natural clay is also a film of montmorillonite, which has the effect of increasing the frequency band of blue light. Therefore, the reflection efficiency of the blue light emitted by the blue LED 30 is increased by covering the light reflecting surface 20a with the gas barrier layer 50 using natural clay, that is, montmorillonite.

Next, a method of forming the silver-resistant vulcanization film 70 and a method of filling the transparent sealing portion 40 in the method of manufacturing the optical semiconductor device 1 will be described with reference to FIGS. 4, 5, and 1 . Fig. 4 is a view for explaining a method of forming an undercoat layer. Fig. 5 is a view for explaining a method of covering a gas barrier layer.

First, as shown in (a) of Fig. 4, the primer dilution liquid M is dropped or dispersed into the inner space 22 of the reflector 20. At this time, as shown in (a) of Fig. 4, the amount or amount of dripping of the primer D is adjusted, and the entire surface of the light reflecting surface 20a is covered with the primer D. Thereafter, the solvent of the primer D is dried. Then, as shown in Fig. 4(b), the entire surface of the range covered with the primer D, in other words, the entire surface of the silver plating layer 16, the blue LED 30, and the light reflecting surface 20a. An undercoat layer 60 is formed.

After the undercoat layer 60 is formed, as shown in (a) of FIG. 5, the clay diluent L is dropped or dispersed into the inner space 22 of the reflector 20. at this time, The silver plating layer 16 is entirely covered with the clay diluent L, and a part of the light reflecting surface 20a is covered with the clay diluent L (a part of the light reflecting surface 20a is not covered with the clay diluent L), and the clay diluent is adjusted. The amount of instillation or the amount of dispersion of L. Thereafter, the solvent of the clay diluent L is dried. Then, as shown in (b) of Fig. 5, in the entire surface of the range covered with the clay diluent L, in other words, a part of the silver plating layer 16, the blue LED 30, and the undercoat reflection surface 60a. The gas barrier layer 50 is laminated on the undercoat layer 60.

After the gas barrier layer 50 is formed, as shown in Fig. 1, the transparent sealing portion 40 including the phosphor 42 is filled in the inner space 22, and the transparent sealing portion 40 seals the blue diode 30. At this time, as shown in FIG. 5(b), since the gas barrier layer 50 is not laminated on the exposed portion U, the transparent sealing portion 40 is in contact with the exposed portion U in the undercoat reflection surface portion 60a. Thereby, a part of the light reflecting surface 20a, that is, the optical semiconductor device 1 in which the exposed portion U and the transparent sealing portion 40 are joined is obtained.

As described above, according to the optical semiconductor device 1 of the present embodiment, since the silver plating layer 16 is covered with the gas barrier layer 50 having gas barrier properties derived from clay, vulcanization of the silver plating layer 16 can be suppressed. Thereby, the silver plating layer 16 can greatly suppress the decrease in the illuminance of the optical semiconductor device 1 due to blackening. Then, in the anti-silver vulcanization film 70, by disposing the adhesive undercoat layer on the lower layer of the gas barrier layer 50 and bringing the transparent sealing portion 40 into contact with the undercoat layer 60, there is no undercoating. In the case of the layer 60 or in the case where the undercoat layer 60 is not in contact with the transparent sealing resin, peeling of the transparent sealing portion 40 can be suppressed.

Moreover, since the inner space 22 is small, it is difficult to make the clay diluent L and the bottom. The coating diluent M is only dropped or dispersed on the silver plating layer 16. Therefore, when the gas barrier layer 50 and the undercoat layer 60 are allowed to cover the light reflecting surface 20a, the gas barrier layer 50 and the undercoat layer 60 can be easily covered with the silver plating layer 16. Further, even in this case, since the transparent sealing portion 40 is in contact with the undercoat layer 60 on the exposed portion U of the undercoat reflective surface portion 60a, peeling of the transparent sealing portion 40 can be suppressed.

Further, the light reflecting surface 20a reflects the light emitted from the blue LED 30 and is output from the optical semiconductor device 1. However, since the gas barrier layer 50 having gas barrier properties derived from clay has an increase in the frequency band of the blue light. By covering the light reflecting surface 20a with the gas barrier layer 50, the reflection efficiency of the blue light emitted by the blue LED 30 can be increased.

[Second Embodiment]

Next, the second embodiment will be described. The second embodiment is basically the same as the first embodiment, and only the position at which the gas barrier layer is formed is different from that of the first embodiment. Therefore, in the following description, only the differences from the first embodiment will be described, and the same description as the first embodiment will be omitted.

Fig. 6 is a cross-sectional view showing an optical semiconductor device according to a second embodiment. As shown in Fig. 6, the optical semiconductor device 2 of the second embodiment is provided with an anti-silver vulcanization film 72 instead of the anti-silver vulcanization film 70 of the first embodiment.

The silver-resistant vulcanization film 72 is provided with a gas barrier layer 52 and an undercoat layer 60. The gas barrier layer 52 is substantially the same as the gas barrier layer 50, but is different from the gas barrier layer 50 in that it does not cover the light reflecting surface 20a. In other words, the gas barrier layer 52 is not laminated to the undercoat reflective surface 60a, and the undercoat layer is reversed. The emitting surface portion 60a exposes the entire surface of the gas barrier layer 52. Therefore, the transparent sealing portion 40 is in contact with the entire surface of the undercoat reflection surface portion 60a. In addition, the gas barrier layer 52 may be covered with the silver plating layer 16, regardless of whether or not the blue LED body 30 is covered.

Fig. 7 is a view for explaining a method of covering a gas barrier layer. As shown in (a) of FIG. 7, after the undercoat layer 60 is formed, the clay diluent L is dropped or dispersed into the inner space 22 of the reflector 20. At this time, the entire surface of the silver plating layer 16 is covered with the clay diluent L, but the light reflecting surface 20a and the undercoat reflecting surface portion 60a are not covered with the clay diluent L, and the amount or dispersion of the clay diluent L is adjusted. the amount. Thereafter, the solvent of the clay diluent L is dried. Then, as shown in (b) of Fig. 7, on the entire surface of the range covered with the clay diluent L, in other words, on the entire surface of the silver plating layer 16 and the blue LED 30, the gas barrier layer 52 is stacked. The layer is on the undercoat layer 60.

According to the second embodiment, since the gas barrier layer 52 is not laminated on the undercoat layer 60 on the light reflecting surface 20a, the contact area between the transparent sealing portion 40 and the undercoat layer 60 can be increased. The peeling of the transparent sealing portion 40 can be further suppressed.

[Third embodiment]

Next, the third embodiment will be described. The third embodiment is basically the same as the first embodiment, and only the positions at which the undercoat layer and the gas barrier layer are formed are different from those of the first embodiment. Therefore, in the following description, only the differences from the first embodiment will be described, and the same description as the first embodiment will be omitted.

Fig. 8 is a cross-sectional view showing an optical semiconductor device according to a third embodiment. As shown in Fig. 8, the optical semiconductor device 3 of the third embodiment is provided with an anti-silver vulcanization film 73 instead of the anti-silver vulcanization film 70 of the first embodiment.

The silver-resistant vulcanization film 73 is provided with an undercoat layer 63 and a gas barrier layer 53.

The undercoat layer 63 is substantially the same as the undercoat layer 60, but is different from the undercoat layer 60 in that it is not formed on the light reflecting surface 20a of the entire surface. In the undercoat layer 63, a portion formed on the light reflecting surface 20a is referred to as an undercoat reflecting surface portion 63a. Further, in the light reflecting surface 20a, the end on the top surface 20b side is referred to as an upper end portion 20d. Then, in the light reflecting surface 20a, the undercoat layer 63 is formed only at a portion other than the upper end portion 20d, and the undercoat layer 63 is not formed on the upper end portion 20d. In other words, the undercoat reflection surface portion 63a extends from the silver plating layer 16 along the light reflection surface 20a to the front side of the top surface 20b.

The gas barrier layer 53 is substantially the same as the gas barrier layer 50, but is different from the gas barrier layer 50 on the light-reflecting surface 20a which is laminated on the substantially entire undercoat reflection surface 63a. Then, the leading edge surface 63b of the undercoat layer reflecting surface portion 63a extending along the light reflecting surface 20a, in other words, the leading edge surface 63b on the top surface 20b side of the undercoat layer reflecting surface portion 63a, is exposed from the gas barrier layer 53 The front edge surface 63b is in contact with the transparent sealing portion 40.

As a method of exposing the leading edge surface 63b of the undercoat reflection surface portion 63a from the gas barrier layer 53, for example, a method in which the undercoat layer 63 is formed and the clay diluent L is not covered before To the extent of the rim surface 63b, the clay diluent L is dropped or dispersed into the inner space 22, and the solvent of the clay diluent L is dried.

In this way, according to the third embodiment, even the gas barrier layer The base layer reflection surface portion 63a is formed by laminating a substantially entire base, and the front edge surface 63b of the undercoat reflection surface portion 63a extending along the light reflection surface 20a is in contact with the transparent sealing resin, whereby peeling of the transparent sealing portion 40 can be suppressed. .

[Fourth embodiment]

Next, the fourth embodiment will be described. The fourth embodiment is basically the same as the first embodiment except that the positions at which the undercoat layer, the gas barrier layer, and the transparent sealing resin are formed are different from those of the first embodiment. Therefore, in the following description, only the differences from the first embodiment will be described, and the same description as the first embodiment will be omitted.

Fig. 9 is a cross-sectional view showing an optical semiconductor device according to a fourth embodiment. As shown in FIG. 9, the optical semiconductor device 4 of the fourth embodiment includes the undercoat layer 64, the gas barrier layer 54, and the transparent sealing resin 44 instead of the undercoat layer 60 and the gas barrier layer 50 of the first embodiment. Transparent sealing portion 40.

The undercoat layer 64 is substantially the same as the undercoat layer 60, but is different from the undercoat layer 60 in that it is formed beyond the light reflecting surface 20a up to the top surface 20b. In the undercoat layer 64, a portion formed on the light reflecting surface 20a is referred to as an undercoat reflecting surface portion 64a, and a portion formed on the top surface 20b is referred to as an undercoat top portion 64b.

The gas barrier layer 54 is substantially the same as the gas barrier layer 50, but is different from the gas barrier layer 50 in that it is laminated on the entire undercoat reflection surface 64a. However, the gas barrier layer 54 does not cover the undercoat top surface portion 64b. Therefore, the undercoat top surface portion 64b is exposed from the gas barrier layer 54.

The transparent sealing resin 44 is substantially the same as the transparent sealing portion 40, but exceeds the inner space of the reflector 20 to reach the top surface 20b. Then, the transparent seal tree The grease 44 seals the undercoat top surface portion 64b in a state of being in contact with the undercoat top surface portion 64b.

As described above, according to the fourth embodiment, even if the gas barrier layer 54 is laminated on the entirety of the undercoat reflection surface portion 64a, since the undercoat top surface portion 64b is formed, the undercoat top surface portion 64b and the transparent seal are formed. The resin 44 is in contact with each other, and peeling of the transparent sealing resin 44 can be suppressed.

Further, since the inner space 22 is small, it is difficult to drip or spread the clay diluent L and the primer dilution liquid M only on the silver plating layer 16. Therefore, when the gas barrier layer 54 and the undercoat layer 64 are allowed to cover the entire surface of the light reflecting surface 20a, the gas barrier layer 54 and the undercoat layer 64 can be easily covered with the silver plating layer 16. Further, even in this case, since the transparent sealing portion 40 is in contact with the undercoat top surface portion 64b, peeling of the transparent sealing portion 40 can be suppressed.

The above is a description of a preferred embodiment of the present invention, but the present invention is not limited to the above embodiment.

For example, in the above embodiment, the base 12 and the reflector 20 are described as individual members, but they may be integrally formed.

Further, in the above-described embodiment, the light-emitting diode to be bonded to the optical semiconductor device 1 is described by using the blue diode 30 that emits blue light, but a light-emitting diode that emits light other than blue may be used. body.

Hereinafter, a preferred embodiment of the optical semiconductor device and the method of manufacturing the same according to the embodiment will be described in detail with reference to the drawings. In addition, the same symbols will be given to the same or corresponding parts throughout the drawings.

[Fifth Embodiment]

As shown in FIGS. 10 and 11, the optical semiconductor device 101 of this embodiment is generally classified into a "surface structure type". The optical semiconductor device 101 includes a substrate 110, a blue LED 130 bonded to the surface of the substrate 110, and a reflector 120 disposed on the surface of the substrate 110 so as to surround the blue LED 130. The transparent sealing portion 140 of the device 120 and the blue LED 130 is sealed, and the gas barrier layer 150 covering the silver plating layer 116. In addition, in FIG. 11, the illustration of the transparent sealing part 140 is abbreviate|omitted. In the present embodiment, "covering the silver plating layer 116" means directly or indirectly covering the silver plating layer 116. Intermittently covering the silver-plated layer 116 means, for example, between the silver-plated layer 116 and the other member.

In the substrate 110, the copper plate 114 is wired on the surface of the insulating base 112, and the silver plating layer 116 is formed on the surface of the copper plate 114. However, the configuration of the substrate 110 is not limited thereto, and can be appropriately changed. The silver plating layer 116 is disposed on the surface of the substrate 110 and serves as an electrode that is electrically connected to the blue LED 130. Further, the silver plating layer 116 may be any composition as long as it is a plating layer containing silver. For example, the silver plating layer 116 may be formed by plating only silver, or the silver plating layer 116 may be formed by plating in the order of nickel and silver. The copper plate 114 and the silver plating layer 116 are insulated on the anode side and the cathode side. The insulation between the copper plating plate 114 and the silver plating layer 116 on the anode side and the copper plating plate 114 and the silver plating layer 116 on the cathode side can be plated, for example, by the copper plating plate 114 and the silver plating layer 116 on the anode side and the cathode side. The copper plate 114 and the silver plating layer 116 are separated, and an insulating layer such as a resin or a ceramic is interposed therebetween.

The blue LED 130 is a silver plating layer 116 bonded to either one of the anode side and the cathode side, and is bonded to the silver plating layer 116 via the die bonding material 132. Conducted. Further, the blue LED 130 is a silver plating layer 116 which is wire-bonded to any one of the anode side and the cathode side, and is electrically connected to the silver plating layer 116 via the bonding wires 134.

The reflector 120 is a light reflecting portion filled with a transparent sealing portion 140 for sealing the blue LED 130, and reflects light emitted from the blue diode 130 to the surface side of the optical semiconductor device 101. The reflector 120 is erected on the surface of the substrate 110 in such a manner as to surround the blue LED 130, and an inner space 122 accommodating the blue diode 130 is formed inside. Therefore, on the opposite side of the substrate 110 in the inner space 122, the opening 124 of the inner space 122 is formed. Further, the reflector 120 includes a light reflecting surface 120a, a top surface 120b, and an outer circumferential surface 120c. The light reflecting surface 120a is formed in a circular shape in plan view (refer to FIG. 11), and an inner space 122 accommodating the blue LED 130 is formed around the blue LED 130. In other words, the inner space 122 accommodating the blue LED 130 is formed by surrounding the light reflecting surface 120a of the blue LED 130. The top surface 120b is located outside the inner space 122 adjacent to the light reflecting surface 120a, and extends from the front edge of the light reflecting surface 120a toward the opposite side of the inner space 122. The outer peripheral surface 120c is formed in a rectangular shape in plan view (see FIG. 11), and rises from the surface 110a of the substrate 110 to the outer edge of the top surface 120b. The shape of the light reflecting surface 120a and the outer peripheral surface 120c is not particularly limited. However, from the viewpoint of enhancing the illuminance of the optical semiconductor device 101, the light reflecting surface 120a preferably has a truncated cone shape (funnel shape) which is away from the substrate 110. Further, from the viewpoint of increasing the degree of accumulation of the optical semiconductor device 101, the outer peripheral surface 120c preferably forms a vertical quadrangle facing the substrate 110. In addition, as an example of formation of the light reflecting surface 120a, the figure is shown below the substrate 110 side in the drawing. The portion is perpendicular to the substrate 110, and the upper portion on the opposite side of the substrate 110 is expanded in diameter as it moves away from the substrate 110.

The reflector 120 is composed of a cured product of a thermosetting resin composition containing a white pigment. From the viewpoint of ease of formation of the reflector 120, the thermosetting resin composition is preferably one which can be press-formed at room temperature (25 ° C) before thermal curing.

As the thermosetting resin contained in the thermosetting resin composition, various resins such as an epoxy resin, a polyoxyxylene resin, an amine ester resin, and a cyanate resin can be used. In particular, an epoxy resin is preferred because of its excellent adhesion to various materials.

As the white pigment, alumina, magnesia, cerium oxide, titanium oxide, zirconium oxide or the like can be used. Among these, titanium oxide is preferred from the viewpoint of light reflectivity. Inorganic hollow particles can also be used as the white pigment. Specific examples of the inorganic hollow particles include sodium citrate glass, aluminum silicate glass, sodium borosilicate glass, white sand, and the like.

The transparent sealing portion 140 is filled in the inner space 122 formed by the light reflecting surface 120a of the reflector 120 to seal the blue LED 130. This transparent sealing portion 140 is made of a transparent sealing resin having light transmissivity. Among the transparent sealing resins, in addition to the completely transparent resin, a translucent resin is also included. In the case of the transparent sealing resin, the modulus of elasticity is preferably 1 MPa or less at room temperature (25 ° C). In particular, from the viewpoint of transparency, a polyoxyxylene resin or an acrylic resin is preferably used. The transparent sealing resin may further contain an inorganic filler or a phosphor 142 that diffuses light, and the phosphor 142 converts the blue light emitted by the blue diode 130 as an excitation source to become white light.

The gas barrier layer 150 is a gas barrier layer having gas barrier properties derived from clay, and suppresses vulcanization of the silver plating layer 116 by covering the silver plating layer 116. The gas barrier layer 150 is disposed at a position away from the substrate 110, and covers the silver plating layer 116 from the opening 124 side of the inner space 122. The gas barrier layer 150 is buried in the transparent sealing portion 140, and the front surface of the gas barrier layer 150 is sealed by the transparent sealing portion 140. Further, the gas barrier layer 150 is connected to the light reflecting surface 120a which surrounds the inner space 122 for a whole circumference, and the transparent sealing portion 140 is divided into a portion on the side of the substrate 110 and a portion on the side of the opening 124 by the gas barrier layer 150. Therefore, on the silver plating layer 116, the transparent sealing portion 140, the gas barrier layer 150, and the transparent sealing portion 140 are sequentially laminated toward the opening 124.

The gas barrier layer 150 is a layer containing clay. As the clay constituting the gas barrier layer 150, any of natural clay and synthetic clay can be used, and for example, any one of Stevenstone, hectorite, saponite, montmorillonite, and beide stone can be used. the above. In particular, as shown in Fig. 12, when the thickness H is 1 nm or less and the length L is 10 nm or more and 400 nm or less, the gas path has a long path ratio and is excellent in gas barrier properties.

The layer thickness of the gas barrier layer 150 is preferably 0.01 μm or more and 1000 μm or less, more preferably 0.03 μm or more and 500 μm or less, and still more preferably 0.05 μm or more and 100 μm or less. It is preferably 0.05 μm or more and 10 μm or less, and more preferably 0.05 μm or more and 1 μm or less. By setting the layer thickness of the gas barrier layer 150 to 0.01 μm or more and 1000 μm or less, it is possible to achieve both the gas barrier properties to the silver plating layer 116 and the transparency of the gas barrier layer 150. In this case, the layer thickness of the gas barrier layer 150 is set to 0.03 μm or more and 500 μm or less, 0.05 μm or more and 100 μm or less, 0.05 μm or more, 10 μm or less, and 0.05 μm or more. Below 1 μm , this effect can be further improved.

Incidentally, the gas barrier layer 150 using the above clay has sufficient light transmittance as long as it has a layer thickness of 0.01 μm or more and 1000 μm or less. Therefore, even if the light reflecting surface 120a is covered with the gas barrier layer 150, it does not have much influence on the reflection characteristics of the reflector 120. Moreover, natural clay is also a film of montmorillonite, which has the effect of increasing the frequency band of blue light. Therefore, the reflection efficiency of the blue light emitted by the blue LED 130 is increased by covering the light reflecting surface 120a with the gas barrier layer 150 using natural clay, that is, montmorillonite.

Next, a method of manufacturing the optical semiconductor device 101 will be described with reference to FIGS. 13 to 15 and FIG. Fig. 13 is a flow chart showing a method of manufacturing the optical semiconductor device according to the fifth embodiment. Fig. 14 and Fig. 15 are views showing a manufacturing procedure of the optical semiconductor device according to the fifth embodiment.

First, as shown in FIG. 13 and FIG. 14(a), a preparation step (S111) for preparing the intermediate member 108 is provided. The intermediate member 108 is provided with a substrate 110 having a silver plating layer 116 formed on the surface thereof; The polar body 130 is bonded to the silver plating layer 116; and the reflector 120 forms an inner space 122 accommodating the blue LED 130 by surrounding the light reflecting surface 120a of the blue LED 130.

Next, as shown in FIG. 13 and FIG. 14(b), a transparent sealing portion sealing step (S112) is performed in which the transparent sealing portion 140 including the phosphor 142 is filled in the inner space 122, thereby being transparent. Sealing portion 140 will be blue The step of sealing the photodiode 130. At this time, the filling amount of the transparent sealing portion 140 is adjusted such that the transparent sealing portion 140 is filled to the inner space 122 by half. In this case, whether or not the bonding wires 134 are sealed by the transparent sealing portion 140 may be used. Thereafter, the transparent sealing portion 140 is dried by being dried or the like.

Next, as shown in Fig. 13 and Fig. 15(a), a gas barrier layer forming step (S113) is performed which is a step of forming the gas barrier layer 150 at a position away from the substrate 110. In the gas barrier layer forming step, first, the clay diluent L is dropped or dispersed into the inner space 122 filled with the transparent sealing portion 140. At this time, the amount of dripping or the amount of dispersion of the clay diluent L is adjusted so that the entire surface of the transparent sealing portion 140 covers the entire surface of the transparent sealing portion 140 and contacts the light reflecting surface 120a surrounding the inner space 122. Thereafter, the solvent of the clay diluent L is dried. Then, on the entire surface of the transparent sealing portion 140, a gas barrier layer 150 which is connected to the light reflecting surface 120a for an entire circumference is formed. Thereby, the silver plating layer 116 is covered with the gas barrier layer 150 from the opening 124 side via the transparent sealing portion 140.

Next, as shown in FIGS. 13 and 10, a gas barrier layer embedding step (S114) is performed in which the transparent sealing portion 140 including the phosphor 142 is filled into the inner space 122 formed by the gas barrier layer 150. The step of completely filling the inner space 122. Thereby, the gas barrier layer 150 is embedded in the transparent sealing portion 140, and the transparent sealing portion 140, the gas barrier layer 150, and the transparent sealing portion 140 are sequentially laminated on the top surface of the silver plating layer 116.

As described above, according to the optical semiconductor device 101 of the present embodiment, since the silver plating layer 116 is blocked by gas having gas barrier properties derived from clay. The layer 150 is covered, so that the vulcanization of the silver plating layer 116 can be suppressed. Thereby, the silver plating layer 116 can greatly suppress the decrease in the illuminance of the optical semiconductor device 101 due to blackening. Incidentally, the gas barrier layer having gas barrier properties derived from clay is improved in gas barrier properties by homogenizing the layer thickness. On the other hand, since the surface of the substrate 110 on which the silver plating layer 116 is formed becomes uneven, it is difficult to homogenize the layer thickness of the gas barrier layer if a gas barrier layer is formed on the surface of the substrate 110. Then, by arranging the gas barrier layer 150 at a position away from the substrate 110, the layer thickness of the gas barrier layer 150 can be made uniform. Thereby, the gas barrier property of the gas barrier layer 150 can be improved.

Moreover, by arranging the transparent sealing portion 140 between the gas barrier layer 150 and the substrate 110, since the gas barrier layer 150 is away from the substrate 110, migration between the gas barrier layer 150 and the substrate 110 can be prevented.

Further, since the gas barrier layer 150 is embedded in the transparent sealing portion 140, peeling of the gas barrier layer 150 can be prevented.

[Sixth embodiment]

Next, the sixth embodiment will be described. The sixth embodiment is basically the same as the fifth embodiment, and is different from the fifth embodiment only in the position at which the gas barrier layer is formed. Therefore, in the following description, only the differences from the fifth embodiment will be described, and the same description as the fifth embodiment will be omitted.

Figure 16 is a cross-sectional view showing an optical semiconductor device according to a sixth embodiment. As shown in Fig. 16, the optical semiconductor device 102 of the sixth embodiment includes a gas barrier layer 151 formed on the surface of the transparent sealing portion 140 instead of the gas barrier layer 150 of the fifth embodiment.

Similarly to the gas barrier layer 150 of the fifth embodiment, the gas barrier layer 151 is a gas barrier layer having gas barrier properties derived from clay, and the silver plating layer 116 is covered to suppress vulcanization of the silver plating layer 116. The gas barrier layer 151 is disposed at a position away from the substrate 110, and covers the silver plating layer 116 from the opening 124 side of the inner space 122. Then, the gas barrier layer 151 is formed on the surface of the transparent sealing portion 140 and the top surface 120b of the reflector 120, and is connected to the top surface 120b surrounding the inner space 122 for a whole week so as to cover the entire inner space 122. Therefore, on the silver plating layer 116, the transparent sealing portion 140 and the gas barrier layer 151 are sequentially laminated toward the opening 124. The material, structure, layer thickness and the like of the gas barrier layer 151 are the same as those of the gas barrier layer 150 of the fifth embodiment.

Next, a method of manufacturing the optical semiconductor device 102 will be described with reference to FIGS. 16 and 17. Fig. 17 is a flow chart showing a method of manufacturing the optical semiconductor device according to the sixth embodiment.

As shown in Figs. 16 and 17, first, the same preparation steps as in the fifth embodiment (S121) are performed.

Next, a transparent sealing portion sealing step (S122) is performed in which the transparent sealing portion 140 including the phosphor 142 is filled in the inner space 122, and the transparent sealing portion 140 seals the blue LED 130. At this time, the filling amount of the transparent sealing portion 140 is adjusted so that the transparent sealing portion 140 is filled in the entire inner space 122.

Next, a gas barrier layer forming step (S123) is performed which is a step of forming the gas barrier layer 151 at a position away from the substrate 110. In the gas barrier layer forming step, first, the clay is diluted or dropped into the surface of the transparent sealing portion 140 and the top surface 120b of the reflector 120. At this time, in clay The dilution covers the entire surface of the transparent sealing portion 140 and contacts the top surface 120b surrounding the inner space 122 for a whole week, and adjusts the amount or amount of dispersion of the clay diluent. Thereafter, the solvent of the clay diluent is dried. Then, on the entire surface of the transparent sealing portion 140, a gas barrier layer 151 which is connected to the top surface 120b for an entire circumference is formed. Thereby, the silver plating layer 116 is covered with the gas barrier layer 151 from the opening 124 side via the transparent sealing portion 140.

As described above, according to the optical semiconductor device 102 of the present embodiment, since the gas barrier layer 151 is formed on the surface of the transparent sealing portion 140, the transparent sealing portion 140 and the gas barrier layer 151 can be easily formed.

[Seventh embodiment]

Next, the seventh embodiment will be described. The seventh embodiment is basically the same as the fifth embodiment, and is different from the fifth embodiment only in that a second gas barrier layer is newly provided. Therefore, in the following description, only the differences from the fifth embodiment will be described, and the same description as the fifth embodiment will be omitted.

Figure 18 is a cross-sectional view showing an optical semiconductor device according to a seventh embodiment. As shown in FIG. 18, in the optical semiconductor device 103 of the seventh embodiment, the second gas barrier layer 152 is newly provided in the optical semiconductor device 101 of the fifth embodiment.

Similarly to the gas barrier layer 150 of the fifth embodiment, the second gas barrier layer 152 is a gas barrier layer having gas barrier properties derived from clay, and the silver plating layer 116 is covered to suppress vulcanization of the silver plating layer 116. The second gas barrier layer 152 is formed on the surface of the substrate 110 (silver plating layer 116), and is hollow from the inside. The side of the opening 124 of the space 122 covers the silver plating layer 116. Therefore, the second gas barrier layer 152 is directly laminated on the silver plating layer 116. Then, on the silver plating layer 116, the second gas barrier layer 152, the transparent sealing portion 140, the gas barrier layer 150, and the transparent sealing portion 140 are sequentially laminated toward the opening 124. The material, configuration, layer thickness, and the like of the second gas barrier layer 152 are the same as those of the gas barrier layer 150 of the fifth embodiment.

Next, a method of manufacturing the optical semiconductor device 103 will be described with reference to FIGS. 18 and 19. Fig. 19 is a flow chart showing a method of manufacturing the optical semiconductor device according to the seventh embodiment.

As shown in FIGS. 18 and 19, first, a preparation step (S131) for preparing an intermediate member is provided. The intermediate member includes a substrate 110 having a silver plating layer 116 formed on the surface, and a blue LED 130 bonded thereto. The silver plating layer 116; and the reflector 120 form an inner space 122 for accommodating the blue LED 130 by surrounding the light reflecting surface 120a of the blue LED 130. Further, in the preparation step of the sixth embodiment, an intermediate member in which the blue LED 130 and the silver plating layer 116 are not yet subjected to wire bonding is prepared.

Next, a second gas barrier layer forming step (S132) is performed, which is a step of forming a second gas barrier layer 152 on the surface of the silver plating layer 116. In the second gas barrier layer forming step, first, the clay is diluted into or dispersed into the inner space 122. At this time, the amount of dripping or the amount of dispersion of the clay diluent is adjusted by covering the entire surface of the substrate 110 exposed to the inner space 122 with the clay diluent and contacting the light reflecting surface 120a surrounding the inner space 122 for a whole week. Thereafter, the solvent of the clay diluent is dried. Thus, on the entire surface of the substrate 110 exposed to the inner space 122, the first The second gas barrier layer 152 is connected to the light reflecting surface 120a surrounding the inner space 122 for a whole week. Thereby, the silver plating layer 116 is in a state of being covered by the second gas barrier layer 152 from the opening 124 side.

Next, a connecting step (S133) is performed, which is a step of wire bonding the silver plating layer 116 covered by the blue diode 130 and the second gas barrier layer 152 to electrically connect. A well-known person can be used for the wire bonding apparatus used for this connection step. The wire bonding apparatus includes a capillary (not shown) into which the bonding wire 134 is inserted. The capillary is moved to a fixed position and then lowered, and the bonding wire 134 is fixed by pushing the bonding wire 134 to the blue diode 130 or the silver plating layer 116 on which the second gas barrier layer 152 is formed. At this time, in order to enable the bonding wire 134 to be fixed to the blue LED 130 or the silver plating layer 116, the conditions exemplified below can be set. In other words, a load of 60 g or more and 150 gf or less is applied to the capillary, or the capillary is vibrated in a frequency band of 80 kHz or more and 160 kHz or less. Thereby, the blue LEDs 130 and the silver plating layer 116 are electrically connected to each other via the bonding wires 134.

Next, a transparent sealing portion sealing step (S134) is performed in which the transparent sealing portion 140 including the phosphor 142 is filled in the inner space 122 in which the second gas barrier layer 152 is formed, whereby the transparent sealing portion 140 is used for the blue light The step of sealing the polar body 130. At this time, the filling amount of the transparent sealing portion 140 is adjusted such that the transparent sealing portion 140 is filled to the inner space 122 by half. In this case, whether or not the bonding wires 134 are sealed by the transparent sealing portion 140 may be used. Thereafter, the transparent sealing portion 140 is dried by being dried or the like.

Next, a gas barrier layer forming step (S135) is performed, which is a step of forming the gas barrier layer 150 at a position away from the substrate 110. In gas In the barrier layer forming step, first, the clay is diluted or dropped into the inner space 122 filled by the transparent sealing portion 140. At this time, the dripping amount or the amount of dispersion of the clay diluent is adjusted so that the entire surface of the transparent sealing portion 140 is covered with the clay diluent and is in contact with the light reflecting surface 120a surrounding the inner space 122 for a whole week. Thereafter, the solvent of the clay diluent is dried. Thus, on the surface of the integral transparent sealing portion 140, a gas barrier layer 150 is formed which is connected to the light reflecting surface 120a which surrounds the inner space 122 for a whole week. Thereby, the gas barrier layer has a multilayer (two-layer) structure, and the silver-plated layer 116 is in a state of being covered by the second gas barrier layer 152 and the gas barrier layer 150 from the opening 124 side.

Next, the gas barrier layer embedding step (S136) similar to that of the fifth embodiment is performed. Thereby, the second gas barrier layer 152, the transparent sealing portion 140, the gas barrier layer 150, and the transparent sealing portion 140 are sequentially laminated on the top surface of the silver plating layer 116.

As described above, according to the optical semiconductor device 103 of the present embodiment, the gas barrier layer can be easily multilayered by forming the second gas barrier layer 152 on the surface of the silver plating layer 116. Thereby, the gas barrier property can be further improved.

[Eighth Embodiment]

Next, the eighth embodiment will be described. The eighth embodiment is basically the same as the seventh embodiment, and is different from the seventh embodiment only in that the shape of the second gas barrier layer is different. Therefore, in the following description, only the items different from the seventh embodiment will be described, and the same as the seventh embodiment will be omitted. Description.

Figure 20 is a cross-sectional view showing an optical semiconductor device according to an eighth embodiment. As shown in Fig. 20, the optical semiconductor device 104 of the eighth embodiment includes a second gas barrier layer 153 extending to the light reflecting surface 120a and covering the bonding wires 134 instead of the second gas barrier layer 152 of the seventh embodiment. .

The second gas barrier layer 153 is barrierd to the gas of the fifth embodiment Similarly to the second gas barrier layer 152 of the sixth embodiment, the layer 150 is a gas barrier layer having gas barrier properties derived from clay, and the silver plating layer 116 is covered to suppress vulcanization of the silver plating layer 116. The second gas barrier layer 153 is formed on the surface of the substrate 110 (silver plating layer 116) exposed to the inner space 122, and covers the silver plating layer 116 from the opening 124 side of the inner space 122. Therefore, the second gas barrier layer 153 is directly laminated on the silver plating layer 116.

Then, the second gas barrier layer 153 is also formed on the light reflecting surface 120a. The surface and the surface of the bonding wire 134. Among the second gas barrier layers 153, a portion formed on the light reflecting surface 120a is referred to as a light reflecting surface covering portion 153a, and a portion formed on the surface of the bonding wire 134 is referred to as a bonding wire covering portion 153b.

The light reflecting surface covering portion 153a may be formed on the entire surface of the light reflecting surface 120a, or may be formed only on a part of the light reflecting surface 120a. In addition, in FIG. 20, the light reflection surface covering portion 153a is formed on the entire surface of the light reflecting surface 120a.

The bonding wire covering portion 153b is formed on the entire surface of the bonding wire 134 with approximately the same layer thickness. Therefore, the bonding wire covering portion 153b extends from the blue LED 130 to the silver plating layer 116 along the bonding wire 134 in a ring shape, and the bonding wires 134 are also in the same substrate 110 and the blue LED 130. A gap is formed between them.

The material, structure, layer thickness, and the like of the second gas barrier layer 153 are the same as those of the gas barrier layer 150 of the fifth embodiment and the second gas barrier layer 152 of the sixth embodiment.

Next, a method of manufacturing the optical semiconductor device 104 will be described with reference to FIGS. 20 and 21. Fig. 21 is a flow chart showing a method of manufacturing the optical semiconductor device according to the eighth embodiment.

As shown in Fig. 20 and Fig. 21, first, a preparation step (S141) similar to that of the fifth embodiment is performed.

Next, a second gas barrier layer forming step (S142) is performed on the surface of the silver plating layer 116 to form a second gas barrier layer 153 covering the silver plating layer, the silver plating layer having a gas derived from clay Barrier. In the second gas barrier layer forming step, first, the clay is diluted into or dispersed into the inner space 122. At this time, a part or the entire surface of the light reflecting surface 120a is covered with the clay diluent, and the amount of the dripping or the amount of the clay diluent is adjusted to completely cover the bonding wire 134. In this case, when the light reflecting surface covering portion 153a is covered on the entire surface of the light reflecting surface 120a, the inner surface 122 is filled with the clay diluent, and the entire surface of the light reflecting surface 120a is covered with the clay diluent. Adjust the amount or amount of dispersion of the clay diluent. On the other hand, in a case where only a part of the light reflecting surface 120a covers the light reflecting surface covering portion 153a, the clay thinning liquid is not filled in the inner space 122, so that only a part of the light reflecting surface 120a is made of the clay diluent The way of covering, adjusting the amount of dripping or the amount of dispersion of the clay diluent. Thereafter, the solvent of the clay diluent is dried. Thus, the entire substrate 110 exposed to the inner space 122 On the surface of the body, a second gas barrier layer 153 is formed; on the surface of the light reflecting surface 120a, a light reflecting surface covering portion 153a of the second gas barrier layer 153 is formed; on the entire surface of the bonding wire 134, a first portion is formed The bonding barrier cover portion 153b of the second gas barrier layer 153 is bonded. Thereby, the silver plating layer 116 is in a state of being covered by the second gas barrier layer 153 from the opening 124 side.

Next, a transparent sealing portion sealing step (S143) is performed in which the transparent sealing portion 140 including the phosphor 142 is filled in the inner space 122 in which the second gas barrier layer 153 is formed, whereby the transparent sealing portion 140 converts the blue light The step of sealing the polar body 130. At this time, the filling amount of the transparent sealing portion 140 is adjusted such that the transparent sealing portion 140 is filled to the inner space 122 by half. In this case, whether or not the bonding wires 134 are sealed by the transparent sealing portion 140 may be used. Thereafter, the transparent sealing portion 140 is dried by being dried or the like.

Next, a gas barrier layer forming step (S144) is performed which is a step of forming the gas barrier layer 150 at a position away from the substrate 110. In the gas barrier layer forming step, first, the clay dilution is dropped or dispersed into the inner space 122 filled by the transparent sealing portion 140. At this time, in the case where the light reflecting surface covering portion 153a is covered by the transparent sealing portion 140, the clay thinning solution is covered so that the entire surface of the transparent sealing portion 140 is covered with the clay diluent and contacts the light reflecting surface covering portion 153a for a whole week. The amount of liquid to be dropped or the amount of dispersion. On the other hand, in the case where the light reflecting surface covering portion 153a is exposed from the transparent sealing portion 140, the clay thinning is covered by covering the entire surface of the transparent sealing portion 140 with the clay diluent and contacting the light reflecting surface 120 for a whole week. The amount of liquid to be dropped or the amount of dispersion. Thereafter, the solvent of the clay diluent is dried. Thus, on the surface of the integral transparent sealing portion 140, a gas barrier layer 150 is formed, the gas The barrier layer 150 is connected to the light reflecting surface 120a or the light reflecting surface covering portion 153a which surrounds the inner space 122 for a whole circumference. Thereby, the gas barrier layer has a multilayer (two-layer) structure, and the silver plating layer 116 is in a state of being covered by the second gas barrier layer 153 and the gas barrier layer 150 from the opening 124 side.

Next, a gas barrier layer embedding step (S145) similar to that of the fifth embodiment is performed. Thereby, the second gas barrier layer 153, the transparent sealing portion 140, the gas barrier layer 150, and the transparent sealing portion 140 are sequentially laminated on the top surface of the silver plating layer 116.

As described above, according to the optical semiconductor device 104 of the present embodiment, the light reflecting surface 120a is covered by the light reflecting surface covering portion 153a, and oxidation of the light reflecting surface 120a can be suppressed. Thereby, it is possible to greatly suppress the decrease in the illuminance of the optical semiconductor device 104 caused by the discoloration of the light reflecting surface 120a.

Moreover, when the bonding wire 134 is covered by the bonding wire covering portion 153b, when the material of the bonding wire 134 is made of silver, vulcanization of the bonding wire 134 can be suppressed.

[Ninth Embodiment]

Next, the ninth embodiment will be described. The ninth embodiment is basically the same as the eighth embodiment except that the shape of the bonding wire covering portion is different. Therefore, in the following description, only the differences from the eighth embodiment will be described, and the description similar to the eighth embodiment will be omitted.

Figure 22 is a cross-sectional view showing an optical semiconductor device according to a ninth embodiment. As shown in Fig. 22, the optical semiconductor device 105 of the ninth embodiment includes the first The second gas barrier layer 154 is substituted for the second gas barrier layer 153 of the eighth embodiment.

Similarly to the gas barrier layer 150 of the fifth embodiment and the second gas barrier layer 153 of the eighth embodiment, the second gas barrier layer 154 has a gas barrier layer derived from the gas barrier property of clay, and is covered with a silver plating layer. 116 to suppress vulcanization of the silver plating layer 116.

The second gas barrier layer 154 is formed on the surface of the substrate 110 (silver plating layer 116) exposed to the inner space 122, and covers the silver plating layer 116 from the opening 124 side of the inner space 122. Therefore, the second gas barrier layer 154 is directly laminated on the silver plating layer 116.

Then, the second gas barrier layer 154 includes a light reflecting surface covering portion 154a formed on the surface of the light reflecting surface 120a, and a bonding wire covering portion 154b formed on the surface of the bonding wire 134. The light reflecting surface covering portion 154a is the same as the light reflecting surface covering portion 153a of the eighth embodiment.

The bonding wire covering portion 154b is formed on the entire surface of the bonding wire 134 in the same manner as the bonding wire covering portion 153b of the eighth embodiment. However, unlike the bonding wire covering portion 153b of the eighth embodiment, the bonding wire covering portion 154b is filled between the substrate 110 and the blue LED 130 in a film shape.

The material, structure, layer thickness, and the like of the second gas barrier layer 154 are the same as those of the gas barrier layer 150 of the fifth embodiment and the second gas barrier layer 153 of the eighth embodiment.

Next, a method of manufacturing the optical semiconductor device 105 will be described.

The method of manufacturing the optical semiconductor device 105 is basically the same as the method of manufacturing the optical semiconductor device 104 of the eighth embodiment. But, to make the clay diluted When the solvent of the liquid is dried, the clay diluent is still held between the bonding wire 134 and the substrate 110 and the blue LED 130, and the clay diluent is dropped or dispersed to the inside for forming the second gas barrier layer 154. Space 122. Further, a method of holding the clay diluent between the bonding wire 134 and the substrate 110 and the blue LED 130 may, for example, be a method of delaying the drying rate of the solvent, or a method of increasing the concentration of the clay in the clay diluent. . Thereby, the bonding wire covering portion 154b which is filled in the film shape between the bonding wires 134 and the substrate 110 and the blue LEDs 130 is formed.

In the optical semiconductor device 105 of the present embodiment, the light reflecting surface 120a is covered by the light reflecting surface covering portion, and the bonding wire 134 is covered by the bonding wire covering portion 154b, so that the eighth embodiment can be achieved. The optical semiconductor device 104 has the same operational effects.

[10th embodiment]

Next, the tenth embodiment will be described. The tenth embodiment is basically the same as the seventh embodiment except that the structure of the gas barrier layer is different and the primer layer is newly provided. Therefore, in the following description, only the differences from the seventh embodiment will be described, and the same description as the seventh embodiment will be omitted.

Figure 23 is a cross-sectional view showing an optical semiconductor device according to a tenth embodiment. As shown in FIG. 23, in the optical semiconductor device 106 of the tenth embodiment, the undercoat layer 160 is newly provided in the optical semiconductor device 103 of the seventh embodiment, and the gas barrier layer 155 is provided instead of the gas barrier layer 150. And a second gas barrier layer 152.

The gas barrier layer 155 is basically the same as the second gas barrier layer 152 of the seventh embodiment, and is different from the second gas barrier layer 152 of the seventh embodiment only in that it is laminated on the undercoat layer 160.

The undercoat layer 160 is provided between the substrate 110 and the light reflecting surface 120a and the transparent sealing portion 140 to suppress peeling of the transparent sealing portion 140 from the substrate 110 and the light reflecting surface 120a. The undercoat layer 160 is formed on the substrate 110 and the light reflecting surface 120a exposed to the inner space 122, and a gas barrier layer 155 is laminated on the top surface thereof. As the undercoat layer 160, a layer having adhesiveness and insulating properties is preferable, and for example, a layer containing a phthalic acid compound can be used. Examples of the phthalic acid compound include a polyfluorene-based resin such as polyarylene oxide rubber and inorganic glass.

The tantalum acid compound used in the present embodiment has a linear expansion coefficient of preferably from 180 ppm to 450 ppm from the viewpoint of obtaining adhesiveness by flexibility. By having a linear expansion coefficient of 180 ppm or more, adhesion by softness can be easily ensured, and on the other hand, by a linear expansion coefficient of 450 ppm or less, for example, by a transparent sealing portion 140 for covering or sealing, it is possible to suppress the bottom. The deformation of the coating 160 occurs. From the viewpoint of improving the adhesion derived from softness, the tannic acid compound is more preferably a linear expansion coefficient of from 200 ppm to 450 ppm, from the viewpoint of improving the reliability with respect to the transparent sealing portion 140 for covering or sealing. More preferably, it is 200ppm~350ppm.

The niobic acid compound used in the present embodiment has a volume resistivity of preferably 10 ¹⁰ to 10 ¹⁶ Ω from the viewpoint of ensuring insulation. Cm, more preferably 10 ¹² ~ 10 ¹⁶ Ω from the viewpoint of improving insulation. Cm, and more preferably 10 ¹³ ~ 10 ¹⁶ Ω. Cm. In addition, the volume resistivity of the citric acid compound is a value measured by a volume resistivity measurement test piece according to JIS C2139, and the volume resistivity measurement test piece is a substrate in which 3 g of a phthalic acid compound is applied to a copper-attached electrode. It was obtained by drying at 150 ° C for 3 hours.

The layer thickness of the undercoat layer 160 is preferably from 10 nm to 1000 nm from the viewpoint of adhesion, and more preferably from 30 nm to 1000 nm from the viewpoint of water resistance, from the viewpoint of effectively exhibiting gas barrier properties of the gas barrier layer 155. More preferably, it is 30 to 500 nm.

Then, the undercoat layer 160 is formed on the substrate 110 (silver plating layer 116) and the light reflecting surface 120a exposed to the inner space 122, and the gas barrier layer 155 covers the silver plating layer 116 through the undercoat layer 160. Therefore, the gas barrier layer 155 is disposed at a position away from the substrate 110, and the undercoat layer 160, the gas barrier layer 155, and the transparent sealing portion 140 are sequentially laminated on the silver plating layer 116 toward the opening 124. Further, the undercoat layer 160 may be formed on the entire surface of the light reflecting surface 120a, or may be formed only on a part of the light reflecting surface 120a. Further, the gas barrier layer 155 may be covered with the substrate 110 exposed to the inner space 122, regardless of whether or not the blue diode 130 is covered.

Next, a method of manufacturing the optical semiconductor device 106 will be described with reference to FIGS. 23 and 24. Fig. 24 is a flow chart showing a method of manufacturing the optical semiconductor device according to the tenth embodiment.

As shown in Figs. 23 and 24, first, a preparation step (S161) similar to that of the seventh embodiment is performed. Further, in the preparation step of the tenth embodiment, as in the seventh embodiment, an intermediate member in which the blue LED 130 and the silver plating layer 116 are not yet wire bonded is prepared.

Next, an undercoat layer forming step (S162) of forming the undercoat layer 160 on the substrate 110 and the light reflecting surface 120a is performed. In the undercoat layer forming step, First, a primer diluted by diluting the above-mentioned citric acid compound with a solvent is dropped or dispersed into the inner space 122. At this time, the amount of the primer or the amount of dispersion of the primer solution is adjusted so that the entire surface or a part of the light-reflecting surface 120a is covered with the primer solution. Thereafter, the solvent of the primer solution is dried. Thus, the undercoat layer 160 is formed on the entire surface of the range covered with the primer solution, in other words, on the entire surface or a portion of the silver plating layer 116, the blue LED 130, and the light reflecting surface 120a.

Next, a gas barrier layer forming step (S163) is performed, which is a step of forming a gas barrier layer 155 on the surface of the undercoat layer 160. In the gas barrier layer forming step, first, the clay dilution is dropped or dispersed into the inner space 122. At this time, the clay diluent is used to cover the entire surface of the substrate 110 exposed to the inner space 122 through the undercoat layer 160, and the drip amount of the clay diluent is adjusted or the light reflection surface 120a surrounding the inner space 122 for a whole week. The amount of distribution. Thereafter, the solvent of the clay diluent is dried. Thereby, the silver plating layer 116 is in a state of being covered by the gas barrier layer 155 from the opening 124 side.

Next, a connecting step (S164) is performed, which is a step of electrically connecting the blue-polar diode 130 and the undercoat layer 160 and the silver-plated layer 116 covered by the gas barrier layer 155. This connection step is the same as the connection step (S133) of the seventh embodiment. Thereby, the blue LEDs 130 and the silver plating layer 116 are electrically connected to each other via the bonding wires 134.

Thereafter, in the same manner as in the seventh embodiment, the transparent sealing portion sealing step (S165) is performed to form the transparent sealing portion 140. Thereby, the undercoat layer 160, the gas barrier layer 155, and the transparent sealing portion 140 are sequentially laminated on the top surface of the silver plating layer 116.

According to the optical semiconductor device 106 of the present embodiment, the undercoat layer 160 is disposed between the substrate 110 and the gas barrier layer 155, so that the transparent sealing portion can be disposed between the substrate 110 and the gas barrier layer 155. 140, and the gas barrier layer 155 is disposed at a position away from the substrate 110. Further, as compared with the case where the gas barrier layer 155 is formed directly on the substrate 110, since the surface on which the gas barrier layer 155 is to be formed is planarized by the undercoat layer 160, the layer thickness of the gas barrier layer 155 can be made uniform. Chemical. Thereby, the gas barrier property of the gas barrier layer 155 can be improved.

Further, by laminating the gas barrier layer 155 on the undercoat layer 160, as the transparency can be ensured at the same time, the water resistance of the undercoat layer 160 and the gas barrier layer 155 and the adhesion to the silver plating layer 116 are improved. Peeling between the transparent sealing portion 140 for covering or sealing and the light reflecting surface 120a can be suppressed.

The above is a description of a preferred embodiment of the present invention, but the present invention is not limited to the above embodiment.

For example, each configuration of each of the above embodiments may be combined as appropriate. For example, the second gas barrier layer of the eighth or ninth embodiment may be replaced with the second gas barrier layer of the seventh or tenth embodiment. Further, the undercoat layer of the tenth embodiment can be applied to the fifth to ninth embodiments.

Further, in the seventh embodiment, the multilayer structure of the gas barrier layer is described as an example of a two-layer structure, but it may have a multilayer structure of three or more layers.

Further, in the above embodiment, the base and the reflector are described as individual members, but they may be integrally formed.

Moreover, in the above embodiment, as the bonding to the optical semiconductor device Although the light-emitting diode is described by using a blue light-emitting diode that emits blue light, a light-emitting diode that emits light other than blue may be used.

Hereinafter, a preferred embodiment of a light-emitting device according to another aspect of the present invention will be described in detail with reference to the drawings. In addition, the same symbols will be given to the same or corresponding parts throughout the drawings.

The light-emitting device according to the eleventh embodiment includes: a substrate having a silver plating layer, a light-emitting diode mounted on the substrate, and a multi-layer film covering at least a surface of the silver plating layer; wherein the multi-layer film has: first The layer contains a layered tannic acid compound; and the second layer contains a second tannic acid compound other than the layered tannic acid compound.

The light-emitting device according to the twelfth embodiment includes: a substrate having a silver plating layer, a light-emitting diode mounted on the substrate, and a multi-layer film covering at least a surface of the silver plating layer; wherein the multi-layer film has: first The layer contains an oxygen permeability of 0.0001 to 10 cc/m ² . 24h. a compound of atm; and, layer 1, which has a volume resistivity of 10 ¹⁰ ~ 10 ¹⁶ Ω. Cm compound.

[11th and twelfth embodiments]

The configuration of the light-emitting device of the eleventh and twelfth embodiments will be described with reference to Figs. 25 and 26. The parts common to the eleventh and twelfth embodiments will be described together.

Figure 25 is a cross-sectional view of the light-emitting device. Figure 26 is a plan view showing the light-emitting device shown in Figure 25. As shown in Figs. 25 and 26, the light-emitting device 201 of this embodiment is generally classified into a "surface structure type". The light-emitting device 201 includes a substrate 210 and is bonded to the surface of the substrate 210 as a hair The blue LED 230 of the optical element, the reflector 220 disposed on the surface of the substrate 210 in such a manner as to surround the blue LED 230, and the transparent sealing resin 240 filled in the reflector 220 and sealing the blue LED 230. In addition, in Fig. 26, the illustration of the transparent sealing resin 240 is omitted.

The substrate 210 is a copper plated plate 214 which is wired on the surface of the insulating base 212, and a silver plated layer 216 is formed on the surface of the copper plated plate 214. The silver plating layer 216 is disposed on the surface of the substrate 210 to become an electrode that is electrically connected to the blue LED 230. Further, the silver plating layer 216 may be any composition as long as it is a plating layer containing silver. For example, the silver plating layer 216 may be formed by plating only silver, or the silver plating layer 216 may be formed by plating in the order of nickel and silver. The copper plate 214 and the silver plating layer 216 are insulated on the anode side and the cathode side. The insulation between the copper plating plate 214 and the silver plating layer 216 on the anode side and the copper plating plate 214 on the cathode side and the silver plating layer 216 can be plated, for example, by the copper plating plate 214 on the anode side and the silver plating layer 216 and the cathode side. The copper plate 214 and the silver plating layer 216 are separated, and an insulating layer such as a resin or a ceramic is interposed therebetween.

The blue LED 230 is a silver plated layer 216 in which the die is bonded to either the anode side and the cathode side, and is electrically connected to the silver plating layer 216 via the die bonding material 232. Further, the blue LED 230 is a silver plating layer 216 which is wire-bonded to any one of the anode side and the cathode side, and is electrically connected to the silver plating layer 216 via a bonding wire.

The reflector 220 is filled with a transparent sealing resin 240 for sealing the blue LED 230 while reflecting light emitted from the blue LED 230 to the surface side of the light-emitting device 201. The reflector 220 is erected on the surface of the substrate 210 in such a manner as to surround the blue LED 230. That is, the reflector 220 is provided with: The inner peripheral surface 220a is formed from the surface 210a of the substrate 210 so as to surround the blue LED 230, and an inner space 222 for accommodating the blue LED 230 is formed inside, and a circular shape is formed in a plan view (refer to FIG. 26); The surface 220b is located outside the inner space 222 adjacent to the inner circumferential surface 220a, and extends from the front edge of the inner circumferential surface 220a toward the opposite side of the inner space 222; and the outer circumferential surface 220c is from the top surface 220b. The outer end edge is lowered to the surface 210a of the substrate 210, and a rectangular shape is formed in a plan view (see Fig. 26). The shape of the inner circumferential surface 220a and the outer circumferential surface 220c is not particularly limited. However, from the viewpoint of improving the illuminance of the light-emitting device 201, the inner circumferential surface 220a preferably has a truncated cone shape (funnel shape) which is away from the substrate 210. The diameter is increased, and from the viewpoint of increasing the degree of accumulation of the light-emitting device 201, the outer peripheral surface 220c preferably forms a vertical quadrangle facing the substrate 210. Further, as an example of the formation of the inner circumferential surface 220a, the lower portion on the substrate 210 side is perpendicular to the substrate 210 in the drawing, and the upper portion on the opposite side of the substrate 210 is expanded in diameter as it goes away from the substrate 210.

The reflector 220 is composed of a cured product of a thermosetting resin composition containing a white pigment. From the viewpoint of easy formation of the reflector 220, the thermosetting resin composition is preferably one which can be press-formed at room temperature (25 ° C) before thermal curing.

As the thermosetting resin contained in the thermosetting resin composition, various resins such as an epoxy resin, a polyoxymethylene resin, an amine ester resin, a cyanate resin, and a fluorine resin can be used. In particular, an epoxy resin is preferred because of its excellent adhesion to various materials.

As a white pigment, alumina, magnesia, cerium oxide, or the like can be used. Titanium oxide or zirconia. Among these, titanium oxide is preferred from the viewpoint of light reflectivity. Inorganic hollow particles can also be used as the white pigment. Specific examples of the inorganic hollow particles include sodium citrate glass, aluminum silicate glass, sodium borosilicate glass, white sand, and the like.

The transparent sealing resin 240 is filled in the inner space 222 formed by the inner peripheral surface 220a of the reflector 220, and the blue LED 230 is sealed. This transparent sealing resin 240 is composed of a transparent sealing resin having light transmissivity. Among the transparent sealing resins, in addition to the completely transparent resin, a translucent resin is also included. In the case of the transparent sealing resin, the modulus of elasticity is preferably 1 MPa or less at room temperature (25 ° C). In particular, from the viewpoint of transparency, a polyoxyxylene resin or an acrylic resin is preferably used. The transparent sealing resin may further contain an inorganic filler or a phosphor 242 that diffuses light, and the phosphor 242 converts blue light emitted from the blue diode 230 as an excitation source to become white light.

In the case of the light-emitting device of the eleventh embodiment, the silver-plated layer 216 of the light-emitting device 201 is covered by a multi-layer film, that is, the anti-tarnish film 260, which is composed of a layered tannic acid compound. One layer (gas barrier layer) 252 is formed of two layers of a second layer (primer layer) 250 containing a second tantalum compound other than the layered tannic acid compound, and the transparent sealing resin 240 is bonded to the reflector 220. together.

In the case of the light-emitting device of the twelfth embodiment, the silver-plated layer 216 of the light-emitting device 201 is covered by a multi-layer film, that is, the anti-tarnish film 260, which is composed of the first layer (gas barrier layer). 252, which is composed of two layers of the second layer (undercoat layer) 250, and the transparent sealing resin 240 is bonded to the reflector 220. The gas barrier layer 252 contains an oxygen permeability of 0.0001 to 10 cc/m ² . 24h. A compound of atm. The compound contained in the gas barrier layer 252 preferably has an oxygen permeability of from 0.0001 to 5 cc/m ² from the viewpoint of obtaining practical gas barrier properties (gas shielding properties). 24h. Atm, the oxygen permeability is preferably from 0.001 to 1 cc/m ² from the viewpoint of simultaneously taking out the degassing procedure for forming a gas barrier layer and obtaining excellent gas barrier properties. 24h. Atm.

In the twelfth embodiment, the oxygen permeability of the compound can be determined in accordance with JIS K7126-1 (GC method). Specifically, the oxygen permeability was measured for the sample for evaluation prepared as follows. First, the layered citric acid compound was 5% by mass, and the water was 95% by mass. The mixture was weighed and mixed, and the mixture was mixed at 2000 rpm using a planetary centrifugal mixer (ARE-310, manufactured by THINKY Co., Ltd.). In minutes, defoaming was carried out at 2,200 rpm for 10 minutes. Next, on a PET film (A4300-125) with an easy-to-adhere layer, a bar coater having a wet thickness of 100 μm was used, and a solution of a target of 5 mass% of the compound was applied. The solvent was removed by leaving at 22 ° C for 12 hours to prepare a PET film having the formed film on the surface, and this was used as a sample for evaluation.

In the case of the light-emitting device of the eleventh embodiment, the gas barrier layer 252 containing the layered tantalum compound in the anti-tarnish film 260 composed of two layers suppresses the silver plating layer 216 by covering the silver plating layer 216. The discoloration (for example, discoloration due to vulcanization) is formed by the liquid A of the first silver surface treatment agent of the present embodiment to be described later. The gas barrier layer 252 can form a film having a long path of gas and excellent gas barrier properties as shown in FIG. 32 by including a layered tantalum compound, and excellent gas barrier properties can be obtained. From the above In view of the above, when the thickness D of the layered tannic acid compound is from 1 nm to 30 nm and the length L is from 30 to 50,000, the dimensional ratio is preferably high.

In the case of the light-emitting device of the twelfth embodiment, in the anti-tarnish film 260 composed of two layers, the gas barrier layer 252 suppresses discoloration (for example, discoloration due to vulcanization) of the silver-plated layer 216, and can be described later. The second silver surface treatment agent of the present embodiment is formed of the liquid A.

The film thickness of the gas barrier layer 252 is preferably 0.01 μm or more and 1000 μm or less, more preferably 0.03 μm or more and 500 μm or less, still more preferably 0.05 μm or more and 100 μm or less. It is preferably 0.05 μm or more and 10 μm or less, and particularly preferably 0.05 μm or more and 1 μm or less. By setting the film thickness of the gas barrier layer 252 to 0.01 μm or more and 1000 μm or less, the discoloration resistance of the silver plating layer 216 and the transparency of the anti-tarnish film can be achieved. In this case, the film thickness of the gas barrier layer 252 is set to 0.03 μm or more and 500 μm or less, 0.05 μm or more and 100 μm or less, 0.05 μm or more, 10 μm or less, or 0.05 μm or more. And below 1 μm , this effect can be further improved. The anti-tarnish film of the present embodiment is formed of the liquid A and the liquid B of the first or second silver surface treatment agent of the present embodiment to be described later, and cracks are less likely to occur even in the above film thickness.

In the case of the light-emitting device of the eleventh embodiment, the film thickness can be adjusted by, for example, changing the content of the solvent in the surface treatment agent for silver and appropriately adjusting the concentration of the layered tannic acid compound. Moreover, the film thickness can be adjusted by the amount of the surface treatment agent for silver and the number of times of dripping.

In the case of the light-emitting device of the twelfth embodiment, the film thickness can be adjusted, for example, by changing the content of the solvent in the surface treatment agent for silver. The concentration of the above compound having a predetermined oxygen permeability is adjusted to carry out the above. Moreover, the film thickness can be adjusted by the amount of the surface treatment agent for silver and the number of times of dripping.

In the case of the light-emitting device of the eleventh embodiment, the gas barrier layer 252 preferably contains a layered tannic acid compound having the following oxygen permeability. The oxygen permeability of the layered citric acid compound is preferably from 0.0001 to 10 cc/m ² . 24h. From the viewpoint of obtaining practical gas barrier properties (gas shielding properties), atm is more preferably 0.0001 to 5 cc/m ² . 24h. Atm. The oxygen permeability is more preferably from 0.001 to 1 cc/m ² from the viewpoint of simultaneously obtaining a degassing procedure for forming a film containing a layered citric acid compound and obtaining excellent gas barrier properties. 24h. Atm.

The oxygen permeability of the layered tannic acid compound can be determined in accordance with JIS K7126-1 (GC method). The sample for evaluation was prepared as follows. First, the layered citric acid compound was 5% by mass, and the water was 95% by mass. The mixture was weighed and mixed, and the mixture was mixed at 2000 rpm for 10 minutes using a rotary revolution mixer (ARE-310, manufactured by THINKY Co., Ltd.) at 2,200 rpm. Defoam for 10 minutes. Next, on a PET film (A4300-125) having an easy-to-adhere layer, a solution having a thickness of 100 μm was applied to a solution of the above-mentioned layered citric acid compound of 5% by mass, The solvent was removed by leaving at 22 ° C for 12 hours to prepare a PET film having a layered tantalate film on the surface, and this was used as a sample for evaluation.

In the case of the light-emitting device of the eleventh embodiment, the content of the layered tannic acid compound in the gas barrier layer 252 is based on the total amount of the gas barrier layer from the viewpoint of improving the discoloration resistance of the anti-tarnish film. It is preferably 10% by mass or more, more preferably 50% by mass or more, and still more preferably 80% by mass or more. Very good is 100% by mass.

In the case of the light-emitting device of the twelfth embodiment, the content of the compound having the predetermined oxygen permeability in the gas barrier layer 252 is from the viewpoint of improving the discoloration resistance of the anti-tarnish film, and the total amount of the gas barrier layer is The basis of the standard is preferably 10% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, and particularly preferably 100% by mass.

In the twelfth embodiment, the compound having the predetermined oxygen gas permeability contained in the gas barrier layer 252 may, for example, be a layered tannic acid compound. When the gas barrier layer 252 contains a layered tantalum compound, a film having a long path of gas and excellent gas barrier properties as shown in Fig. 32 can be formed, and excellent gas barrier properties can be obtained. From the above viewpoint, when the layered tannic acid compound has a thickness D of from 1 nm to 30 nm and a length L of from 30 to 50,000, the size ratio is preferably high. Moreover, by containing a layered tannic acid compound, excellent gas barrier properties can be obtained without impeding the light-emitting characteristics of the light-emitting device.

In the case of the light-emitting device of the twelfth embodiment, the undercoat layer 250 has a volume resistivity of 10 ¹⁰ to 10 ¹⁶ Ω. Cm compound. The compound contained in the undercoat layer 250 has a volume resistivity of 10 ¹⁰ to 10 ¹⁶ Ω from the viewpoint of ensuring insulation. Cm, from the technical limit and practicality of the measurement of volume resistivity, the upper limit of volume resistivity can be set to 10 ¹⁶ Ω. Cm. The volume resistivity of the above compound is preferably from 10 ¹² to 10 ¹⁶ Ω from the viewpoint of improving the insulating property. Cm, more preferably 10 ¹³ ~ 10 ¹⁶ Ω. Cm. The volume resistivity of the compound is a value measured by a volume resistivity measurement test piece according to JIS C2139. The volume resistivity measurement test piece is a substrate on which a compound to be measured is applied to a substrate having a copper electrode, and is 150. It was obtained by drying at °C for 3 hours.

In the twelfth embodiment, the compound contained in the undercoat layer 250 preferably has a linear expansion coefficient of from 180 ppm to 450 ppm from the viewpoint of obtaining adhesiveness by flexibility. As the adhesion from the softness is ensured to be easy, by the transparent sealing resin for covering or sealing, it is possible to suppress the occurrence of deformation in the above compound. From the viewpoint of improving the adhesion derived from softness, the linear expansion coefficient of the above compound is more preferably from 200 ppm to 450 ppm, and from the viewpoint of improving the reliability of the transparent sealing resin for covering or sealing, Good is 200ppm~350ppm. The coefficient of linear expansion of the compound is a value measured by TMA (Thermal Mechanical Analysis) according to JIS K7197 "Testing Method for Measuring Linear Thermal Expansion Coefficient of Plastics by Thermomechanical Analysis".

In the twelfth embodiment, the compound contained in the undercoat layer 250 is converted into a bottom light at a central wavelength of 450 nm which is mainly used for illumination, from the viewpoint of light extraction efficiency. The coating 250 has a value of 1 mm thickness, preferably 80 to 100%. The light transmittance of the above compound is preferably from 85 to 100%, more preferably from 90 to 100%, from the viewpoint of applicability to a higher luminance light-emitting diode. The light transmittance of the above compound means a value obtained by measuring a phthalic acid compound coated on a PET film by a spectrophotometer (UV-Vis).

In the case of the light-emitting device of the eleventh embodiment, the undercoat layer 250 containing the second bismuth acid compound is preferably a layer having adhesiveness and insulating properties in the anti-tarnish film composed of two layers. The undercoat layer 250 can be formed of the liquid B of the first silver surface treatment agent of the present embodiment to be described later.

In the case of the light-emitting device of the twelfth embodiment, the structure is composed of two layers. In the anti-tarnish film, as the undercoat layer 250, a layer having adhesiveness and insulating properties is preferable. The undercoat layer 250 can be formed of the liquid B of the second silver surface treatment agent of the present embodiment to be described later.

The film thickness of the undercoat layer 250 is preferably from 10 nm to 1000 nm from the viewpoint of adhesion, and more preferably from 30 nm to 1000 nm from the viewpoint of water resistance. More preferably, it is 30 to 500 nm from the viewpoint of effectively exhibiting gas barrier properties of the gas barrier layer.

In the case of the light-emitting device of the twelfth embodiment, the film thickness can be adjusted by, for example, changing the concentration of the solvent in the surface treatment agent for silver and appropriately adjusting the concentration of the compound having a predetermined volume resistivity. Moreover, the film thickness can be adjusted by the amount of the surface treatment agent for silver and the number of times of dripping.

In the eleventh and twelfth embodiments, by laminating the gas barrier layer 252 on the undercoat layer 250, the water resistance of the anti-tarnish film 260 and the adhesion to the silver plating layer 216 can be improved while ensuring transparency. It is possible to suppress peeling between the transparent sealing portion 240 for covering or sealing and the inner circumferential surface 220a of the reflector 220.

Next, the surface treatment agent for silver of this embodiment is demonstrated.

The first silver surface treatment agent (hereinafter also referred to as "first silver surface treatment agent" according to the present embodiment) has the following two types of liquid: liquid A containing a layered tannic acid compound (hereinafter referred to as It is also called "A liquid"), and B liquid (hereinafter, also referred to as "B liquid") containing a second bismuth acid compound other than the layered citric acid compound.

The second silver surface treatment agent (hereinafter also referred to as "second silver surface treatment agent" according to the present embodiment) contains the following two types of liquids: oxygen gas permeability of 0.0001 to 10 cc/m. ² . 24h. A liquid of atm compound (hereinafter also referred to as "A liquid"); and, containing a volume resistivity of 10 ¹⁰ ~ 10 ¹⁶ Ω. The liquid B of the compound of cm (hereinafter also referred to as "liquid B").

The object of the surface treatment agent of this embodiment is silver, and also contains a silver alloy and silver plating.

According to the first silver surface treatment agent of the present embodiment, by forming the undercoat layer 250 on the surface of the silver with the B liquid, the gas barrier layer 252 is formed on the undercoat layer 250 with the liquid A, whereby the formation can be performed. The anti-tarnish film 260 composed of two layers is used. In the gas barrier layer 252, by laminating a layered tantalum compound having a flat plate-like shape, gas shielding properties against a gas such as hydrogen sulfide can be exhibited, and the surface of the silver, particularly silver, is vaporized. The plated surface can impart excellent discoloration resistance. Further, by forming the undercoat layer 250 containing the second bismuth acid compound as a primer layer of the gas barrier layer 252 on the surface of the silver plating layer, the water resistance of the anti-tarnish film 260 and the adhesion to silver can be improved. Further, it is possible to improve the adhesion to the transparent sealing resin for covering, sealing, and the like of the light-emitting device.

The reason why the inventors of the present invention thought that the above effects can be obtained is as follows. The layered tannic acid compound has a plate-like shape and has a property of being dispersed in a solvent by swelling with water or a mixed solvent of a solvent such as water and an alcohol. According to the silver surface treatment agent of the present embodiment, after the B liquid is applied onto the surface of the silver, the undercoat layer is formed by drying, and the layer A containing the layered tannic acid compound is applied thereon, and then removed. The solvent is capable of laminating particles of the layered tannic acid compound on the undercoat layer. The inventors of the present invention thought that it is possible to form a color change factor for silver, that is, a gas (for example, hydrogen sulfide gas) in the atmosphere. A film excellent in barrier properties, and the film is improved in water resistance, adhesion, and crack resistance by the undercoat layer.

According to the second silver surface treatment agent of the present embodiment, the gas barrier layer 252 is formed on the undercoat layer 250 by the liquid A by forming the undercoat layer 250 on the surface of the silver with the liquid B, whereby the gas barrier layer 252 can be formed on the undercoat layer 250. The anti-tarnish film 260 composed of two layers is used. The gas barrier layer 252 includes an oxygen permeability of 0.0001 to 10 cc/m ² . 24h. The compound of atm can exhibit gas shielding properties against a gas such as hydrogen sulfide, and can impart excellent discoloration resistance on the surface of silver, particularly on a silver vapor deposition surface. Also, by containing a volume resistivity of 10 ¹⁰ ~ 10 ¹⁶ Ω. The undercoat layer 250 of the compound of cm is formed as a primer for the gas barrier layer 252, and is formed on the surface of the silver plating layer, thereby improving the insulation reliability, water resistance and adhesion to the silver of the anti-tarnish film 260, and can also be improved. Adhesion to a transparent sealing resin for covering, sealing, etc. of a light-emitting device.

The gas barrier layer has an oxygen permeability of 0.0001~10cc/m ² . 24h. In the case of a compound of atm, in the case of a layered tannic acid compound, by laminating a layered tantalum compound having a flat plate-like shape, gas shielding properties can be more highly exhibited, and on the surface of silver, It is capable of imparting excellent discoloration resistance on a silver vapor deposition surface.

The reason why the inventors of the present invention thought that the above effects can be obtained is as follows. The layered tannic acid compound has a plate-like shape and has a property of being dispersed in a solvent by swelling with water or a mixed solvent of a solvent such as water and an alcohol. According to the silver surface treatment agent used in the present embodiment, after the liquid B is applied onto the surface of the silver, the undercoat layer is formed by drying, and the liquid A containing the layered tannic acid compound is applied thereon. By layering the acidification by removing the solvent The particles of the composition are laminated on the undercoat layer. The inventors of the present invention thought that it is possible to form a film which is excellent in the shielding property of the gas in the atmosphere (for example, sulfur gas or hydrogen sulfide gas), and the film is improved by the undercoat layer. Insulation reliability, water resistance, and crack resistance.

In the first silver surface treatment agent, examples of the layered citric acid compound contained in the liquid A include bentonite such as stellite, hectorite, saponite, montmorillonite, and beide, and swellable mica. . These may be used alone or in combination of two or more.

In the second silver surface treatment agent, the oxygen permeability contained in the liquid A is 0.0001 to 10 cc/m ² . 24h. A compound of atm can be exemplified by a layered citric acid compound. Examples of the layered citric acid compound include bentonite such as stellite, hectorite, saponite, montmorillonite, and beide, and swellable mica. These may be used alone or in combination of two or more.

Among the first and second silver surface treatment agents, examples of the swellable mica include fluorphlogopite, K tetrasilisic mica, and Na tetrasilisic mica. Na taeniolite, Li taeniolite, and the like.

The above compound has a flat plate shape having a thickness of 1 nm to 30 nm and an average long side length of 30 to 50,000 nm, and can be more effectively exhibited gas shielding properties against a gas such as hydrogen sulfide by being laminated on the surface of silver.

The layered tannic acid compound has an average long side length of preferably 30 nm or more and 50000 nm, more preferably 100 nm or more and 50,000 nm or less, and more preferably 100 nm or more and 20,000 nm or less from the viewpoint of gas shielding properties such as hydrogen sulfide. It is particularly preferably 100 nm or more and 10000 nm or less. Again, from gas shielding From the viewpoint of properties and maintaining the original gloss of silver, the average long side length is preferably 100 nm or more and 5000 nm or less.

Further, when the long side length of the layered tannic acid compound is a flat plate-shaped particle viewed from above the vertical line, as shown in Fig. 27, when the length of the long side of the circumscribed rectangle 310 of the particle 300 is the largest In the meantime, it means that the length Lmax of the long side can be measured by using, for example, a transmission electron microscope or the like. In addition, the average long-side length refers to a value obtained by averaging the long-side length values of all the particles in the image in the range of 100 μm in the longitudinal direction and 100 μm in the horizontal direction of the transmission electron microscope. Further, in the method of automatically obtaining the average long side length, it is also possible to use an image analysis software of a secondary image (manufactured by Sumitomo Metal Technology, Particle Analysis Ver3.5).

The thickness of the layered tannic acid compound is preferably from 1 nm to 30 nm, more preferably from 1 nm to 20 nm, even more preferably from 1 nm to 10 nm, from the viewpoint of obtaining a gas barrier function. The above thickness means a value measured by an atomic force microscope (AFM) or a small angle X-ray scattering method.

Among the first silver surface treatment agents, the liquid containing the layered citric acid compound of the present embodiment may contain a solvent. As the solvent, water can be suitably used, and a polar solvent such as methanol, ethanol, propanol, butanol, acetonitrile, dimethyl hydrazine, cyclobutyl hydrazine or formamide can also be used. The solvent may be used singly or in combination of two or more.

The solid content concentration in the liquid A containing the layered citric acid compound of the present embodiment is preferably 0.005 from the viewpoints of film formability and discoloration of silver, that is, gas (for example, hydrogen sulfide gas). Mass%~2% by mass, more preferably 0.01% by mass to 1.5% by mass, and even more preferably 0.05% by mass %~1% by mass.

The second silver surface treatment agent contains the oxygen permeability of the present embodiment of 0.0001 to 10 cc/m ² . 24h. The liquid A of the atm compound may contain a solvent. As the solvent, water can be suitably used, and a polar solvent such as methanol, ethanol, propanol, butanol, acetonitrile, dimethyl hydrazine, cyclobutyl hydrazine or formamide can also be used. The solvent may be used singly or in combination of two or more.

In the second silver surface treatment agent, the oxygen permeability used in the present embodiment is 0.0001 to 10 cc/m ² . 24h. The solid content concentration in the liquid A of the compound of atm is preferably 0.005 mass% to 2 mass% from the viewpoints of film forming properties and discoloration of silver, that is, shielding properties of gas (for example, hydrogen sulfide gas). More preferably, it is 0.01% by mass to 1.5% by mass, and still more preferably 0.05% by mass to 1% by mass.

The liquid B constituting the first silver surface treatment agent contains a second phthalic acid compound other than the layered citric acid compound. As described above, by forming a layer containing the second bismuth acid compound on the silver plating surface with the B liquid, a layer containing the layered citric acid compound is formed thereon, so that the stratified film formed of the surface treatment agent is water-resistant. As well as the adhesion to silver, the adhesion to the transparent sealing resin used for covering or sealing is also improved.

In the first silver-based surface treatment agent, the second bismuth acid compound of the present embodiment is preferably a cured product having properties such as water resistance, weather resistance, heat resistance, and properties such as hardness and stretch. . As the second phthalic acid compound, a polyfluorene-based resin or an inorganic glass can be used.

The liquid B constituting the second silver surface treatment agent contains a volume resistivity of 10 ¹⁰ ~ 10 ¹⁶ Ω. Cm compound. As described above, the volume resistivity of 10 ¹⁰ ~ 10 ¹⁶ Ω is formed by forming the liquid B on the silver plating surface. The layer of the compound of cm is formed thereon to have an oxygen permeability of 0.0001 to 10 cc/m ² . 24h. The layer of the atm compound makes the adhesion film formed by the surface treatment agent, the insulation, the water resistance and the adhesion to the silver are improved, and the adhesion to the transparent sealing resin for covering or sealing is also improved.

In the second silver surface treatment agent, the volume resistivity of the liquid B is 10 ¹⁰ ~ 10 ¹⁶ Ω. The compound of cm is exemplified by a second phthalic acid compound other than the layered citric acid compound. In this case, excellent light insulation characteristics can be obtained without impeding the light-emitting characteristics of the light-emitting device. The second phthalic acid compound is preferably a cured product which is excellent in properties such as insulating properties, water resistance, weather resistance, heat resistance, and properties such as hardness and stretch. Further, the second phthalic acid compound is preferably a compound having the above linear expansion coefficient. Further, the second phthalic acid compound is preferably a compound capable of satisfying the above light transmittance. As the second phthalic acid compound, a polyfluorene-based resin or an inorganic glass can be used.

In the first and second silver surface treatment agents, the polyoxonium-based resin can be composed of a composition represented by the following formula (1), formula (2), formula (3) or formula (4). Unit of resin.

Further, the polyfluorene-based resin may have a known functional group capable of imparting adhesiveness, and may also contain an additive capable of imparting adhesiveness.

As the inorganic glass, a material having SiO ₂ , LiO ₂ , and the following formula (5) can be used. These can be used individually or in mixture of 2 or more types.

From the viewpoint of forming a cured product having excellent properties such as water resistance, weather resistance, heat resistance, and rubber properties such as hardness and stretch, it is preferable to use, for example, a ruthenium-oxygen bond as a main skeleton. The polyoxyethylene rubber composed of a siloxane coupling. Further, from the viewpoint of heat resistance, polydimethyl oxyhydroxide rubber is more preferable.

The polyoxyxene rubber may further contain a thermosetting polyoxonium oxide, a phthalic acid compound such as a hemi-oxyalkylene, and the like, for example, can be heat-treated at 20 ° C to 200 ° C for 1 minute to 10 hours. And hardened to use.

The polyoxyethylene rubber may have a methyl group, a phenyl group, a methylphenyl group, a glycidyl group, an isocyanate group, a vinyl group or the like as a side chain or a functional group.

In the first silver surface treatment agent, the second ruthenic acid compound preferably has a linear expansion coefficient of from 180 ppm to 450 ppm from the viewpoint of obtaining adhesiveness by flexibility. Within this range, as the adhesion from the softness is ensured to be easy, the transparent sealing resin for covering or sealing can suppress the occurrence of deformation in the tannic acid compound. The linear expansion coefficient of the second bismuth acid compound is more preferably from 200 ppm to 450 ppm from the viewpoint of improving the adhesion derived from softness, from the viewpoint of improving the reliability with respect to the transparent sealing resin for covering or sealing. More preferably, it is 200ppm~350ppm. The linear expansion coefficient of the phthalic acid compound is a value measured by TMA (Thermal Mechanical Analysis) according to JIS K7197 "Testing Method for Measuring Linear Thermal Expansion Coefficient of Plastics by Thermomechanical Analysis".

In the first silver surface treatment agent, the second bismuth acid compound preferably has a volume resistivity of 10 ¹⁰ to 10 ¹⁶ Ω from the viewpoint of ensuring insulation. Cm. From the technical limit and practicality of the measurement of volume resistivity, the upper limit of volume resistivity is 10 ¹⁶ Ω. Cm is appropriate. The volume resistivity of the second bismuth acid compound is more preferably 10 ¹² to 10 ¹⁶ Ω from the viewpoint of improving the insulating property. Cm, and more preferably 10 ¹³ ~ 10 ¹⁶ Ω. Cm. The volume resistivity of the tannic acid compound is a value measured by a volume resistivity measurement test piece according to JIS C2139. The volume resistivity measurement test piece is a substrate in which a tannic acid compound is applied to a copper-attached electrode, and is 150. It was obtained by drying at °C for 3 hours.

The light transmittance of the second bismuth compound is mainly used for illumination The center wavelength of the blue light diode used is a light transmittance of 450 nm, and the light transmittance of the thickness of 1 mm is preferably from 80 to 100%, which is preferable from the viewpoint of light extraction efficiency. It is preferably from 85 to 100%, more preferably from 90 to 100%, from the viewpoint of applicability to a higher luminance light-emitting diode. The light transmittance of the tannic acid compound is a value obtained by measuring a tannic acid compound coated on a PET film by a spectrophotometer (UV-Vis).

In the first and second silver surface treatment agents, the curing temperature of the second bismuth acid compound is preferably from 20 ° C to 200 ° C in view of the heat stability of the luminescent acid compound, from the viewpoint of storage stability of the phthalic acid compound. In terms of productivity, it is preferably from 40 ° C to 200 ° C, and more preferably from 40 ° C to 160 ° C from the viewpoint of productivity. When the undercoat layer is formed of the B liquid, it is also possible to carry out multi-stage heating within the above temperature range from the viewpoint of film formability.

Further, the hardening time can be set in the range of 1 minute to 10 hours. From the viewpoint of productivity, it is more preferably in the range of 1 minute to 8 hours, and more preferably in the range of 3 minutes to 8 hours from the viewpoint of the leveling property of the undercoat layer. Hardening can also be carried out separately before and after the gas barrier layer is provided on the undercoat layer.

In the first silver surface treatment agent, the liquid B containing the second phthalic acid compound of the present embodiment may contain a solvent. The solvent can be selected from an aliphatic hydrocarbon solvent, an aromatic solvent, a ketone solvent, an ether, or an ester solvent from the viewpoint of solubility of the above-described phthalic acid compound. Examples of such a solvent include saturated hydrocarbons such as pentane, hexane, heptane, octane, decane, and decane; and cyclic hydrocarbons such as cyclohexane and alkylcyclohexane. Further, as the hydrocarbon, it can be used in a linear form, a branched chain, a ring shape or the like. These can be used individually or in mixture of 2 or more types.

In the first silver surface treatment agent, the solvent of the liquid B containing the second bismuth acid compound of the present embodiment is preferably removed by evaporation in a heating step for hardening, and preferably has a boiling point of 50 ° C to 200 ° C. Solvent. When the boiling point exceeds 200 ° C, the drying property is low, and there is a possibility that the solvent remains to reduce the adhesion. Further, when the boiling point of the solvent is low, the risk of ignition is improved, and from the viewpoint of safety, a solvent having a boiling point of 50 ° C or higher is preferable. The boiling point of the solvent is preferably from 50 ° C to 160 ° C from the viewpoint of productivity, and more preferably from 50 ° C to 120 ° C from the viewpoint of the temperature and time at which the heating step for curing can be freely selected.

Specifically, in the silver surface treatment agent of the present embodiment, after the B liquid containing the second phthalic acid compound is coated on silver or a silver alloy, the solvent can be removed and/or cured to be silver or A layer (undercoat layer) containing a second bismuth acid compound is formed on the silver alloy. Further, after the solution A containing the layered tannic acid compound is applied, a layer (gas barrier layer) containing a layered tannic acid compound can be formed by removing the solvent.

In the second silver surface treatment agent, the volume resistivity used in the present embodiment is 10 ¹⁰ to 10 ¹⁶ Ω. The liquid B of the compound of cm may contain a solvent. The solvent can be selected from an aliphatic hydrocarbon solvent, an aromatic solvent, a ketone solvent, an ether, or an ester solvent from the viewpoint of solubility of the above-described phthalic acid compound. Examples of such a solvent include saturated hydrocarbons such as pentane, hexane, heptane, octane, decane, and decane; and cyclic hydrocarbons such as cyclohexane and alkylcyclohexane. Further, as the hydrocarbon, it can be used in a linear form, a branched chain, a ring shape or the like. These can be used individually or in mixture of 2 or more types.

The second silver surface treatment agent contains a volume resistivity of 10 ¹⁰ ~ 10 ¹⁶ Ω. The solvent of the liquid B of the compound of cm is preferably removed by evaporation in a heating step for hardening, preferably a solvent having a boiling point of from 50 ° C to 200 ° C. When the boiling point exceeds 200 ° C, the drying property is low, and there is a possibility that the solvent remains to reduce the adhesion. Further, when the boiling point of the solvent is low, the risk of ignition is improved, and from the viewpoint of safety, a solvent having a boiling point of 50 ° C or higher is preferable. The boiling point of the solvent is preferably from 50 ° C to 160 ° C from the viewpoint of productivity, and more preferably from 50 ° C to 120 ° C from the viewpoint of the temperature and time at which the heating step for curing can be freely selected.

Specifically, the surface treatment agent for silver used in the present embodiment contains a volume resistivity of 10 ¹⁰ to 10 ¹⁶ Ω. After the solution B of the cm compound is coated on the silver or silver alloy, the volume resistivity of 10 ¹⁰ ~ 10 ¹⁶ Ω can be formed on the silver or silver alloy by removing and/or hardening the solvent. A layer of a compound of cm (undercoat layer). Moreover, the coating contains an oxygen permeability of 0.0001 to 10 cc/m ² . 24h. After the solution A of the atm compound, the oxygen permeability can be formed by removing the solvent by 0.0001 to 10 cc/m ² . 24h. A layer of a compound of atm (gas barrier layer).

In the method of applying the first and second silver surface treatment agents of the present embodiment, for example, a bar coating method, a dip coating method, a spin coating method, a spray coating method, or a potting method can be suitably used. And other methods.

In addition, the method of removing the solvent from the coating film of the first and second silver surface treatment agents of the present embodiment can be suitably dried, and the drying temperature is not particularly limited as long as it is at least room temperature. In addition, the room temperature is 20 to 25 °C.

By using the first silver surface treatment agent, it can be in silver or silver alloy An anti-tarnish film having a layer containing a phthalic acid compound and a layer containing a layered citric acid compound is formed on the surface. Such a film is excellent in shielding property of, for example, hydrogen sulfide gas, and can exhibit a function as an anti-silver vulcanization film.

By using the second silver surface treatment agent, a color-resistant film can be formed on the surface of the silver or silver alloy, which has a volume resistivity of 10 ¹⁰ ~ 10 ¹⁶ Ω. The layer of the compound of cm and the oxygen permeability of 0.0001~10cc/m ² . 24h. The layer of the compound of atm. Such a film is excellent in shielding property of, for example, hydrogen sulfide gas, and can exhibit a function as an anti-silver vulcanization film.

The present invention can provide a silver or a silver alloy having a film composed of the solid components contained in the first and second silver surface treatment agents of the above-described embodiment. Further, it is possible to provide a substrate having such a silver or silver alloy and a light-emitting device including the light-emitting diode. Such a light-emitting device can also be sealed with a transparent resin. The transparent resin may, for example, be a polyoxyn resin. Further, the substrate having silver or a silver alloy may have an uneven shape on the surface, and the silver or the silver alloy may have an uneven shape.

Next, a method of manufacturing the light-emitting device of the eleventh and twelfth embodiments will be described. The common points will be aggregated together, and the differences will be explained individually.

Fig. 28 is a flow chart showing a method of manufacturing the light-emitting device of the eleventh and twelfth embodiments. As shown in Fig. 28, in the method of manufacturing a light-emitting device, first, as a substrate preparation step (stage S101), an insulating base body 212 on which a copper-plated plate 214 is wired on the surface is prepared; as a silver plating layer forming step (Stage S102), a silver plating layer 216 is formed on the surface of the copper plate 214.

Next, as a reflector forming step (stage S103), a reflector 220 is formed on the surface of the substrate 210. As a wafer mounting step (stage S104), a blue LED 230 is mounted on the substrate 210. The mounting of the blue LED 230 on the substrate 210 is performed in the inner space 222 surrounded by the reflector 220 by bonding the blue LED 230 to the silver plating layer 216 on either the anode side or the cathode side. Thereby, the blue LED 230 is electrically connected to the silver plating layer 216 of either the anode side and the cathode side via the die bonding material 232, and the blue LED 230 is surrounded by the reflector 220 to be accommodated in the inner space 222.

Next, in the case of producing the light-emitting device of the eleventh embodiment, as the coating step of the liquid B (stage S105), the silver-containing surface treatment agent of the present embodiment is coated with the second bismuth acid compound. Liquid B, the silver plating layer 216 is covered with liquid B.

In the case of producing the light-emitting device of the twelfth embodiment, as the coating step of the liquid B (stage S105), the surface treatment agent for silver on the silver plating layer 216 is coated to have a volume resistivity of 10 ¹⁰ to 10 ¹⁶ Ω. The liquid B of the compound of cm is covered with the silver plating layer 216 with the liquid B.

The application of the liquid B in the coating step (stage S105) of the liquid B is carried out, for example, by dropping or dispersing a surface treatment agent for silver into the inner space 222 from the surface side of the substrate 210. At this time, the amount of instillation or the amount of dispersion of the liquid B is adjusted so that at least all of the silver plating layer 216 is covered with the liquid B. In this case, for example, as shown in (a) of FIG. 29, the liquid B may be dripped or dispersed into the inner space 222 by covering all of the silver plating layer 216 and the blue LED 230 with the liquid B. ; can also be used as shown in Figure 29 (b) The entire silver plating layer 216 and the blue LED 230 and a portion of the inner circumferential surface 220a of the reflector 220 are covered with the liquid B, and the liquid B is dripped or dispersed into the inner space 222; as shown in Fig. 29 (also as shown in Fig. 29) In the case of c), the B liquid M is dropped or dispersed into the inner space 222 so that the inner peripheral surface 220a of the entire silver plating layer 216, the blue LED 230, and the reflector 220 is covered with the liquid B.

Next, as a drying step (stage S106), the coating film for silver applied to the silver plating layer 216 is dried, and the coating film of the liquid B is dried to form a second tannic acid in the silver sulfide-resistant film. A layer of the compound (basecoat 250).

In the case of producing the light-emitting device of the eleventh embodiment, the application step (stage S107) of the liquid A is applied to the undercoat layer 250, and the surface treatment agent for silver of the present embodiment is coated. In the liquid A of the citric acid compound, at least a portion of the undercoat layer 250 covering the silver plating layer 216 is covered with the A liquid.

In the case of producing the light-emitting device of the twelfth embodiment, as the coating step of the liquid A (stage S107), the surface treatment agent for silver is applied to the undercoat layer 250 to have an oxygen permeability of 0.0001 to 10 cc/m. ² . 24h. In the liquid A of the atm compound, at least a portion of the undercoat layer 250 covering the silver plating layer 216 is covered with the A liquid.

The application of the liquid A in the coating step (stage S107) of the liquid A is carried out, for example, by dropping or dispersing a surface treatment agent for silver into the inner space 222 from the surface side of the substrate 210. The method of dropping or scattering can be carried out in the same manner as the coating step of the liquid B in the step S105.

Next, in the case of manufacturing the light-emitting device of the eleventh embodiment, In the drying step (stage S108), the coating film of the liquid A applied to the silver plating layer 216 is dried, and a layer (gas barrier layer 252) containing a layered tantalum compound is formed in the anti-tarnish film 260.

In the case of producing the light-emitting device of the twelfth embodiment, as a drying step (stage S108), the coating film of the liquid A applied to the silver plating layer 216 is dried, and oxygen is formed in the anti-tarnish film 260. The penetration rate is 0.0001~10cc/m2.24h. A layer of a compound of atm (gas barrier layer 252).

The drying step (stages S106 and S108) can be carried out at a temperature at which the solvent is volatilized. For example, it is preferably set to a temperature range of 30 ° C or higher and 80 ° C or lower, more preferably 30 ° C or higher and 70 ° C or lower. More preferably, the range is set in a temperature range of 30 ° C or more and 60 ° C or less. The time for holding the temperature region is, for example, 5 minutes or longer, and preferably 5 minutes or more and 1 day or less, and more preferably from the viewpoint of improving productivity. It is 5 minutes or more and 30 minutes or less.

Thus, by performing the drying step, the liquid B shown in (a) of FIG. 29, as shown in (a) of FIG. 30, becomes the undercoat layer 250 covering all of the silver plating layer 216 and the blue LED 230. The liquid B shown in (b) of Fig. 29, as shown in Fig. 30(b), is a part of the inner peripheral surface 220a covering the entire silver plating layer 216 and the blue LED 230 and covering the reflector 220. The undercoat layer 250; the liquid B shown in (c) of FIG. 29, as shown in FIG. 30(c), is an inner peripheral surface 220a covering all of the silver plating layer 216, the blue LED 230, and the reflector 220. The undercoat layer 250. The gas barrier layer 252 formed by the drying of the A liquid is also the same. The area covered by the gas barrier layer 252 is preferably smaller than the area covered by the undercoat layer 250.

In the present embodiment, it is preferred to sufficiently dry the anti-tarnish film 260 composed of two layers at 150 ° C for 30 minutes after the drying step. Thereby, it is possible to obtain an effect of further reducing the discoloration resistance between the layers of the undercoat layer 250 and the gas barrier layer 252.

Next, as the wire bonding step (stage S109), the blue LED 230 is wire-bonded to any other silver plating layer 216 on the anode side and the cathode side. At this time, since the silver plating layer 216 is covered with the anti-tarnish film 260, the two ends of the lead are bonded to the blue LED 230 and the silver plating by breaking the anti-tarnish film 260 covering the blue LED 230 and the silver plating layer 216. Layer 216 conducts blue LED 230 and silver plated layer 216. Further, the breakthrough of the discoloration resistant film 260 can be performed, for example, by adjusting the layer thickness of the anti-tarnish film 260, adjusting the load of the bonding head for wire bonding, or vibrating the bonding head.

Next, as a transparent sealing resin filling step (stage S110), the transparent sealing resin 240 containing the phosphor 242 is filled in the inner space 222 formed by the inner peripheral surface 220a of the reflector 220. Thereby, the blue LED 230 and the silver plating layer 216 are sealed by the transparent sealing resin 240 (transparent sealing portion).

By performing the transparent sealing resin filling step, as shown in (a) of FIG. 31, all of the silver plating layer 216 and the blue LED 230 are formed of a two-layer anti-tarnish film 260 (primer coating). In the state covered by the layer 250 and the gas barrier layer 252), the silver plating layer 216 and the blue LED 230 are sealed by the transparent sealing resin 240; as shown in FIG. 31(b), all the silver plating layers are provided. a portion of the inner peripheral surface 220a of the 216 and the blue LED 230 and the reflector 220 is covered with the anti-tarnish film 260, and the silver plating layer 216 is The blue LED 230 is sealed by the transparent sealing resin 240; further, as shown in FIG. 31(c), all of the silver plating layer 216, the blue LED 230, and the inner circumferential surface 220a of the reflector 220 are resistant to discoloration. In the state covered by the film 260, the silver plating layer 216 and the blue LED 230 are sealed by the transparent sealing resin 240.

In the case where the light-emitting device of the eleventh embodiment is manufactured as the light-emitting device 201, the silver-plated layer 216 is covered with the first silver surface treatment agent (liquid A and liquid B) of the present embodiment. The coating film of the surface treatment agent for silver is dried to form a gas-resistant film 260 having a gas barrier layer which is formed by laminating a layered tantalum compound contained in a surface treatment agent for silver. The silver plating layer 216 is covered with a color resist film 260. Thereby, it is possible to form the anti-tarnish film 260 composed of two layers which can appropriately cover the silver plating layer 216.

When the light-emitting device of the twelfth embodiment is manufactured as the light-emitting device 201, the silver-plated layer 216 is covered with the second silver surface treatment agent (liquid A and liquid B) of the present embodiment, and then silver is used. The coating film of the surface treatment agent is dried to form a gas-resistant film 260 having a gas barrier layer which is an oxygen permeability of 0.0001 to 10 cc/m ² contained in the surface treatment agent for silver. 24h. The compound of atm is laminated, and the silver plating layer 216 is covered with the anti-tarnish film 260. Thereby, it is possible to form the anti-tarnish film 260 composed of two layers which can appropriately cover the silver plating layer 216.

When the silver surface treatment agent of the present embodiment is dropped or dispersed in the inner space 222 of the reflector 220 provided in the light-emitting device 201, the anti-tarnish film 260 covering the silver plating layer can be easily formed.

[13th and 14th embodiments]

Next, the thirteenth and fourteenth embodiments of the method of manufacturing a light-emitting device will be described. The method of manufacturing the light-emitting device according to the thirteenth and fourteenth embodiments is basically the same as the method of manufacturing the light-emitting device according to the eleventh and twelfth embodiments, but only in the order of the steps and the light-emitting device of the eleventh and twelfth embodiments. The manufacturing method is different. Therefore, in the following description, only the portions different from the method of manufacturing the light-emitting device of the eleventh and twelfth embodiments will be described, and the description of the same portions as the method of manufacturing the light-emitting device of the eleventh and twelfth embodiments will be omitted. Further, the above surface treatment agent for silver can be used.

Figure 33 is a flow chart showing a method of manufacturing the light-emitting device in the thirteenth and fourteenth embodiments. Figure 34 is a cross-sectional view showing a light-emitting device manufactured by the manufacturing method of Figure 33.

In the method of manufacturing the light-emitting device 201 of the thirteenth and fourteenth embodiments, the substrate preparation step (stage S201) and the silver plating layer forming step are sequentially performed in the same manner as in the eleventh and twelfth embodiments. (stage S202) and reflector forming step (stage S203). Further, a substrate preparation step (stage S201), a silver plating layer forming step (stage S202), and a reflector forming step (stage S203), and a substrate preparation step (stage S101) and a silver plating layer forming step (stage) of the eleventh embodiment S102) is the same as the reflector forming step (stage S103).

Next, as a coating step of the liquid B (stage S204), the liquid B is applied onto the silver plating layer 216, and the silver plating layer 216 is covered with the liquid B. Further, the coating step (stage S204) can be applied to the coating steps of the eleventh and twelfth embodiments. The step (stage S105) is performed in the same manner.

Next, as a drying step (stage S205), the coating film of the liquid B applied on the silver plating layer 216 is dried to form the undercoat layer 250. Further, the drying step (stage S205) can be carried out in the same manner as the drying step (stage S106) of the eleventh and twelfth embodiments.

Next, as the coating step of the A liquid (stage S206), the liquid A is applied onto the undercoat layer 250, and at least the portion of the undercoat layer 250 covering the silver plating layer 216 is covered with the liquid A. Further, the coating step (stage S206) can be carried out in the same manner as the coating step (stage S105) of the eleventh and twelfth embodiments.

Next, as a drying step (stage S207), the coating film of the liquid A applied on the silver plating layer 216 is dried to form a gas barrier layer 252. Further, the drying step (stage S207) can be carried out in the same manner as the drying step (stage S106) of the eleventh and twelfth embodiments.

Next, as a wafer mounting step (stage S208), the blue LED 230 is bonded to the silver plating layer 216 of either the anode side and the cathode side. At this time, similarly to the wire bonding step (stage S109) of the eleventh and twelfth embodiments, the blue LED 230 is bonded to the silver plating layer 216 by breaking the anti-tarnish film covering the silver plating layer 216 to make the blue light The LED 230 is electrically connected to the silver plated layer 216.

Next, as a wire bonding step (stage S209), the blue LED 230 is wire-bonded to any other silver plating layer 216 on the anode side and the cathode side. At this time, since the silver plating layer 216 is covered with the anti-tarnish film 260, it is the same as the wire bonding step (stage S109) of the eleventh and twelfth embodiments, and the two layers of the silver plating layer 216 are covered by the breakthrough. Anti-discoloration In the manner of the film 260, one end of the lead is bonded to the silver plated layer 216. On the other hand, since the blue LED 230 is not covered with the anti-tarnish film 260, the other end of the bonding wire 234 can be bonded to the blue LED 230 as usual. Thereby, the blue LED 230 and the silver plating layer 216 are turned on.

Next, a transparent sealing resin filling step is performed as the stage S210.

According to the method for manufacturing a light-emitting device according to the thirteenth and fourteenth embodiments, the wafer mounting step after the application step and the drying step of the silver surface treatment agent can be performed as shown in FIG. The blue LED 230 does not have the light-emitting device 201 covered with the anti-tarnish film 260 composed of two layers. Therefore, when one end of the bonding wire 234 is bonded to the blue LED 230 in the wire bonding step, it is not necessary to break the two-layer anti-tarnish film 260 by the manufacturing method of the light-emitting device according to the eleventh and twelfth embodiments. .

[15th and 16th Embodiments]

Next, the fifteenth and sixteenth embodiments of the method of manufacturing a light-emitting device will be described. The method of manufacturing the light-emitting device according to the fifteenth and sixteenth embodiments is basically the same as the method of manufacturing the light-emitting device according to the eleventh and twelfth embodiments, but only in the order of the steps and the light-emitting device of the eleventh and twelfth embodiments. The manufacturing method is different. Therefore, in the following description, only the portions different from the method of manufacturing the light-emitting device of the eleventh and twelfth embodiments will be described, and the description of the same portions as the method of manufacturing the light-emitting device of the eleventh and twelfth embodiments will be omitted. Further, the above surface treatment agent for silver can be used.

Figure 35 is a flow chart showing a method of manufacturing the light-emitting device in the fifteenth and sixteenth embodiments. Figure 36 is made by the manufacturing method of Figure 35 A cross-sectional view of the resulting illuminating device.

As shown in Fig. 35, in the method of manufacturing the light-emitting device 201 of the fifteenth and sixteenth embodiments, first, in the same manner as in the eleventh and twelfth embodiments, the substrate preparation step (stage S301) and the silver plating layer forming step are sequentially performed. (stage S302). The substrate preparation step (stage S301) and the silver plating layer formation step (stage S302) are the same as the substrate preparation step (stage S101) and the silver plating layer formation step (stage S102) of the eleventh and twelfth embodiments.

Next, as a coating step of the liquid B (stage S303), the liquid B is applied onto the silver plating layer 216, and the silver plating layer 216 is covered with the liquid B. At this time, from the viewpoint of workability, it is preferable to apply the liquid B to the entire surface of the substrate 210 formed by the silver plating layer 216, but it is also possible to apply the liquid B so as to cover only the silver plating layer 216.

Next, as a drying step (stage S304), the coating film of the liquid B applied on the silver plating layer 216 is dried to form the undercoat layer 250. Further, the drying step (stage S304) can be carried out in the same manner as the drying step (stage S106) of the eleventh and twelfth embodiments.

Next, as a coating step of the A liquid (stage S305), the liquid A is applied onto the undercoat layer 250, and at least the portion of the undercoat layer 250 covering the silver plating layer 216 is covered with the liquid A. At this time, from the viewpoint of workability, it is preferable to apply the liquid A to the entire undercoat layer 250, but it is also possible to apply the liquid A so as to cover only the portion of the undercoat layer 250 covering the silver plating layer 216.

Next, as a drying step (stage S306), the coating film of the liquid A applied to the undercoat layer 250 is dried to form a gas barrier layer 252. In addition, the drying step (stage S306) can be combined with the eleventh and twelfth embodiments The drying step (stage S106) is carried out in the same manner.

Next, as a reflector forming step (stage S307), a reflector 220 is formed on the surface of the substrate 210. At this time, in the case where the surface treatment agent for silver is applied onto the entire surface of the substrate 210 by the coating step (stages S303 and S305) of the surface treatment agent for silver (stages S303 and S305), the surface of the substrate 210 is covered. A reflector 220 is formed on the surface of the anti-tarnish film 260 composed of two layers.

Next, as a wafer mounting step (stage S308), the blue LED 230 is die-bonded to any one of the anode side and the cathode side of the silver plating layer 216. At this time, similarly to the wire bonding step (stage S109) of the eleventh and twelfth embodiments, the blue LED 230 is bonded to the resist color-changing film 260 which is covered by the two layers of the silver plating layer 216. The silver plating layer 216 is such that the blue LED 230 and the silver plating layer 216 are turned on.

Next, as the wire bonding step (stage S309), the blue LED 230 is wire-bonded to any other silver plating layer 216 on the anode side and the cathode side. At this time, since the silver plating layer 216 is covered with the anti-tarnish film 260, it is the same as the wire bonding step (stage S109) of the eleventh and twelfth embodiments, and the two layers of the silver plating layer 216 are covered by the breakthrough. In the manner of forming the anti-tarnish film 260, one end of the lead is bonded to the silver plating layer 216. On the other hand, since the blue LED 230 is not covered with the anti-tarnish film 260, the other end of the bonding wire 234 can be bonded to the blue LED 230 as usual. Thereby, the blue LED 230 and the silver plating layer 216 are turned on.

Next, a transparent sealing resin filling step is performed as the stage S310.

In this way, according to the illuminating device according to the fifteenth and sixteenth embodiments In the manufacturing method, the reflector forming step and the wafer mounting step are performed after the coating step and the drying step of the surface treatment agent for silver, and as shown in FIG. 36, the blue LED 230 can be manufactured without being composed of two layers. The light-emitting device 201 covered by the anti-tarnish film 260. Therefore, when one end of the bonding wire 234 is bonded to the blue LED 230 in the wire bonding step, it is not necessary to break the two-layer anti-tarnish film 260 by the manufacturing method of the light-emitting device according to the eleventh and twelfth embodiments. .

Although the above is a description of a preferred embodiment of the present invention, the present invention is not limited to the above embodiment.

In the above embodiment, the light-emitting diode to be bonded to the light-emitting device 201 is described as a blue LED 230 that emits blue light, but a light-emitting diode that emits light other than blue may be used.

Further, although the light-emitting device 201 of the above-described embodiment is described with the reflector 220 surrounding the blue LED 230, the reflector 220 may not be provided.

According to the surface treatment agent for silver of the present embodiment, a discoloration resistant film excellent in discoloration resistance of silver can be formed, and in particular, an anti-silver vulcanization film having excellent sulfur resistance which is formed of silver can be used, even if it is used from the past. Y ₂ O ₂ S: Eu (red), ZnS: Cu (green), ZnS: Ag (blue), a sulfur-containing compound such as a compound represented by JP-A-H08-085787, and a light-emitting device of a phosphor. Sufficient sulfidation resistance can also be obtained.

The silver surface treatment agent of the present embodiment can be applied to, for example, a plasma display including a silver-containing antireflection film, a liquid crystal display, or the like in addition to the above-described light-emitting device.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples.

(Example A1)

As the layered citric acid compound, a mica aqueous dispersion (manufactured by Co-op Chemical Co., Ltd., trade name: MEB-3) having an average long side length of 10000 nm was prepared. Distilled water was added to 12.5 g of this mica aqueous dispersion to have a total mass of 100 g, and then mixed using a autorotation stirrer (manufactured by THINKY Co., Ltd., trade name: ARE-310) at 2000 rpm for 10 minutes, and defoamed at 2200 rpm. In the minute, a surface treatment agent A containing 1% by mass of mica having an average long side length of 10000 nm was obtained.

The average length of the long side of the layered silicate compound, using a transmission electron microscope: all of the particles within the image (JEOL Inc., trade name JEM-2100F), the longitudinal cross-range 100 μ m × 100 μ m of the The long side length values are averaged and obtained. Further, the length of the long side of each particle is the length of the long side when the length of the long side of the circumscribed rectangle of the particle is the largest.

As a second phthalic acid compound, 99 g of n-heptane was added to 1 g of a polyoxyl resin (trade name: OE-6370M) manufactured by Dow Corning Co., Ltd. to make a total weight of 100 g, and it was prepared to contain 1% by mass of the second citric acid. Surface treatment agent B of the compound.

<Production of silver substrate for evaluation>

On a silver substrate having a thickness of 100 nm deposited on a glass slide made of soda glass, a surface treatment containing 1% by mass of the second bismuth compound obtained above was performed using a bar coater having a wet thickness of 12 μm . After the application of the agent B, the solvent was allowed to stand at 22 ° C for 30 minutes, and the solvent was removed at 150 ° C for 1 hour. Then, the surface treatment agent A containing the 1% by mass of the layered tannic acid compound obtained above was applied and allowed to stand at 22 ° C for 12 hours to remove the solvent to obtain an undercoat layer and a gas barrier layer (mica film) on the surface. Silver substrate (silver substrate for evaluation). Further, the wet thickness is the thickness of the surface treatment agent immediately after the solvent is removed.

<Production of Light-Emitting Device for Evaluation>

In the lead frame LED (trade name: OP4) ENOMOTO Manufacturing Co., size of the light-emitting device 3528, connected to the light emitting wavelength 467.5nm 470nm, capacity 3.7 μ L of the light emitting diode chip - with gold wire, made into. Thereafter, 0.03 mL of the surface treatment agent B (second bismuth citrate compound layer forming material) containing 1% by mass of the second phthalic acid compound obtained above was dropped on the light-emitting diode using a dropper at 22 ° C. The solvent was removed by standing for 30 minutes, and heat treatment was performed at 150 ° C for 1 hour. Thereafter, 0.03 mL of the surface treatment agent A was dropped by a dropper, and the mixture was allowed to stand at 22 ° C for 12 hours to remove the solvent, thereby obtaining a light-emitting device having an undercoat layer and a gas barrier layer on the silver-plated substrate. Thereafter, after heat treatment at 150 ° C for 1 hour, it was sealed with a transparent polyxylene sealing material (trade name: OE-6631) manufactured by Dow Corning Co., Ltd., and cured by heat treatment at 150 ° C for 5 hours. A light-emitting device for evaluation was obtained. Fig. 37 is a cross-sectional transmission electron microscope (TEM) photograph of a material obtained by using an example of an anti-silver sulfochromic film formed by using a surface treatment agent for silver in the examples.

<Evaluation of hydrogen sulfide gas tolerance of silver substrate coated with surface treatment agent>

First, the visible light reflectance at a wavelength of 550 nm of the silver substrate for evaluation obtained above was measured using a spectrophotometer (manufactured by JASCO Corporation, trade name: V-570) to obtain [reflectance before exposure to hydrogen sulfide]. Next, the evaluation silver substrate was allowed to stand in a 10 ppm hydrogen sulfide gas flow, 40 ° C, and 90% RH (relative humidity) for 96 hours, and then the visible light reflectance at a wavelength of 550 nm was measured as [reflectance after hydrogen sulfide exposure]. .

The reflection reduction rate was determined by [reflectance before hydrogen sulfide exposure] - [reflectance after exposure to hydrogen sulfide] = [reflection reduction rate]. The results are shown in Table 1.

<Evaluation of hydrogen sulfide gas tolerance of a light-emitting device coated with a surface treatment agent>

The evaluation light-emitting device was used to emit light with a forward current of 20 mA and a forward voltage of 3.3 V, and the luminescence intensity was measured by using a multi-channel spectrometer (manufactured by Otsuka Electronics Co., Ltd., trade name: MCPD-3700) for an exposure time of 30 msec. [Luminescence intensity before hydrogen sulfide exposure]. Next, the evaluation light-emitting device was allowed to stand in a 10 ppm hydrogen sulfide gas flow, 40 ° C, and 90% RH (relative humidity) for 96 hours, and then emitted with a forward current of 20 mA and a forward voltage of 3.3 V, using a multi-channel spectrometer. The luminescence intensity was measured at an exposure time of 30 msec as [luminescence intensity after hydrogen sulfide exposure].

The luminous intensity maintenance ratio was determined by ([luminescence intensity after hydrogen sulfide exposure] / [luminescence intensity before hydrogen sulfide exposure]) × 100 = [luminescence intensity maintenance ratio]. The results are shown in Table 1.

<Insulation reliability evaluation of light-emitting device coated with surface treatment agent>

The evaluation light-emitting device was used to emit light with a forward current of 20 mA and a forward voltage of 3.3 V, and the luminescence intensity was measured by using a multi-channel spectrometer (manufactured by Otsuka Electronics Co., Ltd., trade name: MCPD-3700) for an exposure time of 30 msec. [Pre-test luminous intensity]. The evaluation light-emitting device was irradiated with a forward current of 20 mA and a forward voltage of 3.3 V, and was allowed to stand at 85 ° C and 85% RH (relative humidity) for 50 hours, and then visually observed. Further, the light was emitted by a forward current of 20 mA and a forward voltage of 3.3 V, and the luminescence intensity was measured by using a multi-channel spectrometer (manufactured by Otsuka Electronics Co., Ltd., trade name: MCPD-3700) for an exposure time of 30 msec. Post-luminescence intensity]. By visual observation, the discoloration between the electrodes due to the occurrence of electrochemical migration was determined by ([post-test luminous intensity] / [pre-test luminous intensity] × 100 = [luminescence intensity maintenance ratio]. When discoloration between the electrodes was confirmed, when the luminescence intensity retention rate was 97% or less, it was evaluated as × as a defect, and there was no discoloration between the electrodes at all. When the luminescence intensity retention rate was 100%, it was evaluated as ○. By visual observation, although the discoloration was slightly discernible between the electrodes, the case where the luminous intensity maintenance rate exceeded 97% was evaluated as Δ as an allowable. The results are shown in Table 1.

<Adhesion evaluation of light-emitting device coated with surface treatment agent: red ink test>

The light-emitting device for evaluation was immersed in a pen-filled red ink (manufactured by PILOT Co., Ltd., trade name: INK30R) at 25 ° C for 24 hours, and then taken out and washed with water. Use a solid microscope to observe the coloration caused by the ink, it will not In the case where the red color of the ink was infiltrated, it was judged as ○ as good adhesion, and it was judged as × as a poor adhesion. The results are shown in Table 1.

<Production of light-emitting device for peeling test>

A light-emitting diode of a light-emitting diode having a light-emitting wavelength of 467.5 nm to 470 nm and a capacity of 3.7 μL was connected to a lead frame for LEDs (trade name: OP4) of a size 3528 manufactured by ENOMOTO Co., Ltd., and a light-emitting device was produced. Thereafter, 0.03 mL of the surface treatment agent B (second bismuth citrate compound layer forming material) containing 1% by mass of the second phthalic acid compound obtained above was dropped on the light-emitting diode using a dropper at 22 ° C. The solvent was removed by standing for 30 minutes, and heat treatment was performed at 150 ° C for 1 hour. Thereafter, 0.03 mL of the surface treatment agent A was dropped by a dropper, and the mixture was allowed to stand at 22 ° C for 12 hours to remove the solvent, thereby obtaining a light-emitting device having an undercoat layer and a gas barrier layer on the silver-plated substrate. Thereafter, after heat treatment at 150 ° C for 1 hour, it was sealed with a transparent polyxylene sealing material (trade name: OE-6631) manufactured by Dow Corning Co., Ltd., and a φ 1.8 mm copper stud pin manufactured by Quad Group ( The column side of the stud pin) (trade name: 901070U) was vertically stood in the sealing material, and the light-emitting device for peeling test was obtained by hardening by heat treatment at 150 ° C for 5 hours.

<Peel test of light-emitting device coated with surface treatment agent>

The peeling test light-emitting device was attached to a stud pull tester (trade name: stud pin pull tester) manufactured by Romulus, and peeled off at a rate of 1.5 N/sec to measure the peeling force. The results are shown in Table 1.

(Example A2)

A surface treatment agent was produced in the same manner as in Example A1 except that mica (manufactured by Topy Industries Co., Ltd., trade name: NTS-5) having an average long side length of 1000 nm was used, except that distilled water was added to this mica 1 g to make the total weight 100 g. The evaluation was carried out in the same manner as in Example A1.

(Example A3)

A mica having an average length of 500 nm (manufactured by Topy Industries Co., Ltd., trade name: NHT-B2) was used, and a surface treatment agent was prepared in the same manner as in Example A1 except that distilled water was added to this mica 1 g to make a total weight of 100 g. The evaluation was carried out in the same manner as in Example A1.

(Example A4)

A montmorillonite (manufactured by Kunimine Industries Co., Ltd., trade name: Kunipia F) having an average long-side length of 5000 nm was used in the same manner as in Example A1 except that distilled water was added to 1 g of montmorillonite to have a total weight of 100 g. The surface treatment agent was evaluated in the same manner as in Example A1.

(Example A5)

A montmorillonite (manufactured by Kunimine Industries Co., Ltd., trade name: Kunipia F) having an average long side length of 2000 nm was used in the same manner as in Example A1 except that distilled water was added to 1 g of montmorillonite to have a total weight of 100 g. The surface treatment agent was evaluated in the same manner as in Example A1.

(Example A6)

A montmorillonite (manufactured by Kunimine Industries Co., Ltd., trade name: Kunipia F) having an average long side length of 1000 nm was used in the same manner as in Example A1 except that distilled water was added to 1 g of montmorillonite to have a total weight of 100 g. The surface treatment agent was evaluated in the same manner as in Example A1.

(Example A7)

A surface treatment agent was prepared in the same manner as in Example A1 except that 0.01 g of lithium niobate (manufactured by Nissan Chemical Co., Ltd., trade name: LSS35) was used as the second phthalic acid compound, and evaluated in the same manner as in Example A1.

(Example A8)

As the second phthalic acid compound, 1 g of a polypyridoxane 20% solution (manufactured by AZ Electronic Materials, trade name: NL120A-20) was dissolved in 39 g of dehydrated dibutyl ether, and this solution was used as a second bismuth acid compound. A surface treatment agent was prepared in the same manner as in Example A1 except for the above, and the evaluation was carried out in the same manner as in Example A1.

(Example A9)

As the second phthalic acid compound, 3 g of a polypyridoxane 20% solution (manufactured by AZ Electronic Materials, trade name: NAX120-20) was dissolved in 17 g of dehydrated dibutyl ether, and this solution was used as a second bismuth acid compound. A surface treatment agent was prepared and treated in the same manner as in Example A1 except for use. Example A1 was evaluated in the same manner.

(Comparative Example A1)

The silver substrate and the light-emitting device were produced without using a surface treatment agent, and evaluated in the same manner as in Example A1.

(Comparative Example A2)

The silver substrate and the light-emitting device were produced without using a surface treatment agent containing a layered tannic acid compound, and evaluated in the same manner as in Example A1.

(Comparative Example A3)

The silver substrate and the light-emitting device were produced without using a surface treatment agent containing a second phthalic acid compound, and evaluated in the same manner as in Example A1.

The layered tannic acid compound is pulverized by an ultrasonic disperser, and the average long side length is adjusted to a predetermined size.

As shown in Table 1, it is understood that in Examples A1 to A9, the hydrogen sulfide gas resistance of the silver substrate and the hydrogen sulfide gas resistance of the light-emitting diode can be obtained. Further, it is understood that an appropriate adhesion can be obtained in a light-emitting device using a light-emitting diode.

(Example B1)

As the layered citric acid compound, a mica aqueous dispersion (manufactured by Co-op Chemical Co., Ltd., trade name: MEB-3) having an average long side length of 10000 nm was prepared. Add distilled water to 12.5g of this mica aqueous dispersion to make the total mass After 100 g, the mixture was mixed at 2000 rpm for 10 minutes using a rotary revolution mixer (manufactured by THINKY Co., Ltd., trade name: ARE-310), and defoamed at 2200 rpm for 10 minutes to obtain mica containing 1% by mass of an average long side length of 10000 nm. Surface treatment agent A.

The average long-side length of the layered tannic acid compound is a long-side length value of all the particles in the image in the range of 100 μm in length × 100 μm in width, using a transmission electron microscope (manufactured by JEOL Ltd., trade name: JEM-2100F). It is obtained by averaging. Further, the length of the long side of each particle is the length of the long side when the length of the long side of the circumscribed rectangle of the particle is the largest.

As a second phthalic acid compound, 97 g of n-heptane was added to 3 g of a polyoxyxylene resin (OE-6370M) manufactured by Dow Corning Co., Ltd. to make a total weight of 100 g, and a surface treatment containing a 3% by mass of a second phthalic acid compound was prepared. Agent B.

<Production of silver substrate for evaluation>

On a silver substrate having a thickness of 100 nm deposited on a glass slide made of sodium glass, a surface treatment agent containing 3% by mass of a second bismuth acid compound obtained as described above was used using a bar coater having a thickness of 12 μm. After coating with B, the solvent was removed by standing at 22 ° C for 30 minutes, and heat treatment was performed at 150 ° C for 1 hour. Then, the surface treatment agent A containing the 1% by mass of the layered tannic acid compound obtained above was applied and allowed to stand at 22 ° C for 12 hours to remove the solvent, thereby obtaining a silver substrate having an undercoat layer and a gas barrier layer on the surface. (Silver substrate for evaluation). Further, the wet thickness is the thickness of the surface treatment agent immediately after the solvent is removed.

<Production of Light-Emitting Device for Evaluation>

In the lead frame LED (trade name: OP4) ENOMOTO Manufacturing Co., size of the light-emitting device 3528, connected to the light emitting wavelength 467.5nm 470nm, capacity 3.7 μ L of the light emitting diode chip - with gold wire, made into. Thereafter, 0.03 mL of the surface treatment agent B (second bismuth citrate compound layer forming material) containing the 3% by mass of the second bismuth compound obtained above was dropped on the light-emitting diode using a dropper at 22 ° C. The solvent was removed by standing for 30 minutes, and heat treatment was performed at 150 ° C for 1 hour. Thereafter, 0.03 mL of the surface treatment agent A was dropped by a dropper, and the mixture was allowed to stand at 22 ° C for 12 hours to remove the solvent, thereby obtaining a light-emitting device having an undercoat layer and a gas barrier layer on the silver-plated substrate. Thereafter, after heat treatment at 150 ° C for 1 hour, it was sealed with a transparent polyxylene sealing material (trade name: OE-6631) manufactured by Dow Corning Co., Ltd., and heat-treated at 150 ° C for 5 hours, and was evaluated by hardening. Use a light-emitting device. Fig. 37 is a cross-sectional TEM photograph of a material obtained by taking an example of an anti-silver sulfochromic film formed using a surface treatment agent for silver in the examples.

<Evaluation of hydrogen sulfide gas tolerance of silver substrate coated with surface treatment agent>

First, the visible light reflectance at a wavelength of 550 nm of the silver substrate for evaluation obtained above was measured using a spectrophotometer (manufactured by JASCO Corporation, trade name: V-570) to obtain [reflectance before exposure to hydrogen sulfide]. Next, the evaluation silver substrate was allowed to stand in a 10 ppm hydrogen sulfide gas flow, 40 ° C, and 90% RH (relative humidity) for 96 hours, and then the visible light reflectance at a wavelength of 550 nm was measured as [reflectance after hydrogen sulfide exposure]. .

The reflection reduction rate was determined by [reflectance before hydrogen sulfide exposure] - [reflectance after exposure to hydrogen sulfide] = [reflection reduction rate]. The results are shown in Table 2.

<Evaluation of hydrogen sulfide gas tolerance of a light-emitting device coated with a surface treatment agent>

The evaluation light-emitting device was used to emit light with a forward current of 20 mA and a forward voltage of 3.3 V, and the luminescence intensity was measured by using a multi-channel spectrometer (manufactured by Otsuka Electronics Co., Ltd., trade name: MCPD-3700) for an exposure time of 30 msec. [Luminescence intensity before hydrogen sulfide exposure]. Next, the evaluation light-emitting device was allowed to stand in a 10 ppm hydrogen sulfide gas flow, 40 ° C, and 90% RH (relative humidity) for 96 hours, and then emitted with a forward current of 20 mA and a forward voltage of 3.3 V, using a multi-channel spectrometer. The luminescence intensity was measured at an exposure time of 30 msec as [luminescence intensity after hydrogen sulfide exposure].

The luminous intensity maintenance ratio was determined by ([luminescence intensity after hydrogen sulfide exposure] / [luminescence intensity before hydrogen sulfide exposure]) × 100 = [luminescence intensity maintenance ratio]. The results are shown in Table 2.

<Insulation reliability evaluation of light-emitting device coated with surface treatment agent>

The evaluation light-emitting device was used to emit light with a forward current of 20 mA and a forward voltage of 3.3 V, and the luminescence intensity was measured by using a multi-channel spectrometer (manufactured by Otsuka Electronics Co., Ltd., trade name: MCPD-3700) for an exposure time of 30 msec. [Pre-test luminous intensity]. The evaluation light-emitting device was irradiated with a forward current of 20 mA and a forward voltage of 3.3 V, and was allowed to stand at 85 ° C and 85% RH (relative humidity) for 50 hours, and then visually observed. Further, the light was emitted by a forward current of 20 mA and a forward voltage of 3.3 V, and the luminescence intensity was measured by using a multi-channel spectrometer (manufactured by Otsuka Electronics Co., Ltd., trade name: MCPD-3700) for an exposure time of 30 msec. Post-luminescence intensity]. By visual observation, The discoloration between the electrodes due to the occurrence of electrochemical migration was determined by ([luminescence intensity after test] / [luminescence intensity before test]) × 100 = [luminance intensity retention rate]. When discoloration between the electrodes was confirmed, when the luminescence intensity retention rate was 97% or less, it was evaluated as × as a defect, and there was no discoloration between the electrodes at all. When the luminescence intensity retention rate was 100%, it was evaluated as ○. By visual observation, although the discoloration was slightly discernible between the electrodes, the case where the luminous intensity maintenance rate exceeded 97% was evaluated as Δ as an allowable. The results are shown in Table 2.

<Adhesion evaluation of light-emitting device coated with surface treatment agent: red ink test>

The light-emitting device for evaluation was immersed in a pen-filled red ink (manufactured by PILOT Co., Ltd., trade name: INK30R) at 25 ° C for 24 hours, and then taken out and washed with water, and a solid microscope was used to observe the presence or absence of coloring by the ink. The case where there was no red coloration due to ink penetration was judged as ○ as good adhesion, and it was judged as × as coloring failure. The results are shown in Table 2.

<Production of light-emitting device for peeling test>

In the lead frame LED (trade name: OP4) ENOMOTO Manufacturing Co., size of the light-emitting device 3528, connected to the light emitting wavelength 467.5nm 470nm, capacity 3.7 μ L of the light emitting diode chip - with gold wire, made into. Thereafter, 0.03 mL of the surface treatment agent B (second bismuth citrate compound layer forming material) containing the 3% by mass of the second bismuth compound obtained above was dropped on the light-emitting diode using a dropper at 22 ° C. The solvent was removed by standing for 30 minutes, and heat treatment was performed at 150 ° C for 1 hour. Thereafter, 0.03 mL of the surface treatment agent A was dropped by a dropper, and the mixture was allowed to stand at 22 ° C for 12 hours to remove the solvent, thereby obtaining a light-emitting device including a second ruthenic acid compound layer and a mica film on the silver-plated substrate. Thereafter, after heat treatment at 150 ° C for 1 hour, it was sealed with a transparent polyxylene sealing material (trade name: OE-6631) manufactured by Dow Corning Co., Ltd., and a φ 1.8 mm copper stud pin manufactured by Quad Group ( The column side of the product name: 901070U) stands vertically in the sealing material, and the light-emitting device for peeling test is obtained by hardening by heat treatment at 150 ° C for 5 hours. The results are shown in Table 2.

<Peel test of light-emitting device coated with surface treatment agent>

The peeling test light-emitting device was attached to a stud tensile tester manufactured by Romulus, and peeled off at a rate of 1.5 N/sec to measure the peeling force. The results are shown in Table 2.

(Example B2)

A mica having an average length of 1000 nm (manufactured by Topy Industries, Inc., trade name: NTS-5) was used, and a surface treatment agent was prepared in the same manner as in Example B1 except that distilled water was added to this mica 1 g to make a total weight of 100 g. The evaluation was carried out in the same manner as in Example B1. The results are shown in Table 2.

(Example B3)

A mica having an average long-side length of 500 nm (manufactured by Topy Industries Co., Ltd., trade name: NHT-B2) was used, and a surface treatment agent was prepared in the same manner as in Example B1 except that distilled water was added to this mica 1 g to make a total weight of 100 g. The evaluation was carried out in the same manner as in Example B1. The results are shown in Table 2.

(Example B4)

A montmorillonite (manufactured by Kunimine Industries Co., Ltd., trade name: Kunipia F) having an average long side length of 5000 nm was produced in the same manner as in Example B1 except that distilled water was added to 1 g of montmorillonite to have a total weight of 100 g. The surface treatment agent was evaluated in the same manner as in Example B1. The results are shown in Table 2.

(Example B5)

In the same manner as in Example B1 except that montmorillonite (manufactured by Kunimine Industries Co., Ltd., trade name: Kunipia F) having an average long-side length of 2000 nm was used, the distilled water was added to 1 g of the montmorillonite to have a total weight of 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 2.

(Example B6)

A montmorillonite (manufactured by Kunimine Industries, Ltd., trade name: Kunipia F) having an average long-side length of 1000 nm was used in the same manner as in Example B1 except that distilled water was added to 1 g of montmorillonite to have a total weight of 100 g. The surface treatment agent was evaluated in the same manner as in Example B1. The results are shown in Table 2.

(Example B7)

The second phthalic acid compound was prepared by adding 99.5 g of n-heptane to 0.05 g of a polyoxyxylene resin (trade name: OE-6370M) manufactured by Dow Corning Co., Ltd. to make a total weight of 100 g. B1 was produced in the same manner to prepare a surface treatment agent, and was evaluated in the same manner as in Example B1. The results are shown in Table 2.

(Example B8)

In the same manner as in the example B1, the second phthalic acid compound was prepared by adding 94 g of n-heptane to 6 g of a polyoxyl resin (trade name: OE-6370M) manufactured by Dow Corning Co., Ltd. to make a total weight of 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 2.

(Example B9)

In the same manner as in the example B1, the second phthalic acid compound was prepared by adding 97 g of n-heptane to 3 g of a polyoxyl resin (trade name: OE-6370HF) manufactured by Dow Corning Co., Ltd. to make a total weight of 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 2.

(Example B10)

In the same manner as in Example B1, the second phthalic acid compound was prepared by adding 97 g of n-heptane to 3 g of a polyoxyl resin (trade name: OE-6351) manufactured by Dow Corning Co., Ltd. to make a total weight of 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 2.

(Example B11)

In the same manner as in Example B1, the second phthalic acid compound was prepared by adding 97 g of n-heptane to 3 g of a polyoxyl resin (trade name: OE-6336) manufactured by Dow Corning Co., Ltd. to make a total weight of 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 2.

(Example B12)

As the second phthalic acid compound, 97 g of n-heptane was added to 3 g of a polyoxyl resin (trade name: EG-6301) manufactured by Dow Corning Co., Ltd. to make the total weight. The surface treatment agent was prepared in the same manner as in Example B1 except that the amount was 100 g, and the evaluation was carried out in the same manner as in Example B1. The results are shown in Table 3.

(Example B13)

In the same manner as in the example B1, the second phthalic acid compound was prepared by adding 97 g of n-heptane to 3 g of a polyoxyl resin (trade name: KER-2600) manufactured by Shin-Etsu Chemical Co., Ltd. to make a total weight of 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 3.

(Example B14)

In the same manner as in the example B1, the second phthalic acid compound was prepared by adding 97 g of n-heptane to 3 g of a polyoxyl resin (trade name: OE-6630) manufactured by Dow Corning Co., Ltd. to make a total weight of 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 3.

(Example B15)

The second phthalic acid compound was prepared in the same manner as in Example B1 except that 97 g of n-heptane was added to 3 g of a polyoxyl resin (trade name: LUMISIL 868) manufactured by WACKER Co., Ltd. to make a total weight of 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 3.

(Example B16)

The second phthalic acid compound was prepared in the same manner as in Example B1 except that 97 g of n-heptane was added to 3 g of a polyoxyl resin (trade name: LUMISIL 815) manufactured by WACKER Co., Ltd., and the total weight was 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 3.

(Example B17)

In the same manner as in the example B1, the second phthalic acid compound was prepared by adding 97 g of n-heptane to 3 g of a polyoxyl resin (trade name: KER-6000) manufactured by Shin-Etsu Chemical Co., Ltd. to make a total weight of 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 3.

(Comparative Example B1)

The silver substrate and the light-emitting device were produced without using a surface treatment agent, and evaluated in the same manner as in Example B1. The results are shown in Table 3.

(Comparative Example B2)

The silver substrate and the light-emitting device were produced without using a surface treatment agent containing a layered tannic acid compound, and evaluated in the same manner as in Example B1. The results are shown in Table 3.

(Comparative Example B3)

Except that the film thickness of the second bismuth compound was set to 8 nm, and examples B5 was produced in the same manner to prepare a surface treatment agent, and evaluated in the same manner as in Example B1. The results are shown in Table 3.

(Comparative Example B4)

A silver substrate and a light-emitting device were produced without using a surface treatment agent containing a second phthalic acid compound, and montmorillonite (manufactured by Kunimine Industries, Ltd., trade name: Kunipia F) having an average long side length of 1000 nm was used, and the montmorillonite was used here. The evaluation was carried out in the same manner as in Example B1 except that distilled water was added to 1 g to make the total weight 100 g. The results are shown in Table 3.

(Comparative Example B5)

In the same manner as in Example B1, the second phthalic acid compound was prepared by adding 97 g of ethyl acetate to 3 g of a primer (trade name: R-3) manufactured by Shin-Etsu Chemical Co., Ltd. to make a total weight of 100 g. The surface treatment agent was prepared and evaluated in the same manner as in Example B1. The results are shown in Table 3.

The layered tannic acid compound is pulverized by an ultrasonic disperser, and the average long side length is adjusted to a predetermined size.

<Measurement of oxygen permeability>

Weighed and mixed so that the layered phthalic acid compound of the following Table 5 was 5% by mass, and the water was 95% by mass, and the mixture was mixed at 2000 rpm using a rotary revolution mixer (manufactured by THINKY Co., Ltd., trade name: ARE-310). After 10 minutes, defoaming was carried out at 2,200 rpm for 10 minutes.

In a PET film (manufactured by Toyobo Co., Ltd., trade name: A4300-125) with an easy-adhesion layer, a layered tantalum compound obtained in the above manner was used in an amount of 5 mass% using a bar coater having a wet thickness of 100 μm . After the surface treatment agent was applied, the solvent was allowed to stand at 22 ° C for 12 hours to remove the solvent, thereby obtaining a PET film having a layered tantalum compound film on its surface. The oxygen permeability of the PET film having the layered tantalum compound film on the surface was measured in accordance with JIS K7126-1 (GC method). The results are shown in Table 4.

<Measurement of volume resistivity>

3 g of the second bismuth acid compound described in Table 5 was applied onto a substrate with a copper electrode, and dried at 150 ° C for 3 hours to measure a test piece as a volume resistivity. The volume resistivity was measured in accordance with JIS C2139. The results are shown in Table 5.

As shown in Table 2 and Table 3, it was found that in Examples B1 to B17, the hydrogen sulfide gas resistance of the silver substrate and the hydrogen sulfide gas resistance of the light-emitting diode were obtained. Further, it is understood that an appropriate adhesion can be obtained in a light-emitting device using a light-emitting diode. Moreover, it is known that good insulation reliability can be obtained.

1‧‧‧Optical semiconductor device

10‧‧‧Substrate

10a‧‧‧ surface

12‧‧‧ base

14‧‧‧copper plate

16‧‧‧Silver plating

20‧‧‧Reflector (light reflection part)

20a‧‧‧Light reflecting surface

20b‧‧‧ top surface

20c‧‧‧ outer perimeter

22‧‧‧ inside space

30‧‧‧Blu-ray diode

32‧‧‧Grain joints

34‧‧‧bonding leads

40‧‧‧Transparent seal

42‧‧‧Fluorite

50‧‧‧ gas barrier

60‧‧‧Undercoat

60a‧‧‧Undercoat reflective face

70‧‧‧Anti-silver vulcanized film

U‧‧‧Exposed Department

Claims (10)

An optical semiconductor device comprising: a substrate having a silver plating layer formed on a surface thereof; a light emitting diode bonded to the silver plating layer; and a light reflecting portion surrounding the light reflecting surface of the light emitting diode Forming an inner space for accommodating the light-emitting diode; an anti-silver vulcanization film covering the silver plating layer; and a transparent sealing portion filling the inner space to seal the light-emitting diode; wherein the anti-silver The vulcanized film has: a gas barrier layer having gas barrier properties derived from clay; and an undercoat layer disposed on a lower layer of the gas barrier layer and having adhesiveness; and the transparent seal portion and the aforementioned undercoat layer Contacted. The optical semiconductor device according to claim 1, wherein the undercoat layer is formed on the light reflecting surface, and the gas barrier layer is laminated on a part of the undercoat layer on the light reflecting surface, and the transparent sealing portion is The gas barrier layer on the light reflecting surface is not laminated on the undercoat layer and is in contact with the undercoat layer. The optical semiconductor device according to claim 2, wherein the light emitting diode is a blue light emitting diode that emits blue light. An optical semiconductor device comprising: a substrate having a silver plating layer formed on a surface thereof; a light emitting diode bonded to the silver plating layer; a light reflecting portion that surrounds a light reflecting surface of the light emitting diode to form an inner space for accommodating the light emitting diode; and a transparent sealing portion filled in the foregoing Sealing the light-emitting diode in an inner space; and forming a gas barrier layer at a position away from the substrate and having a gas barrier property derived from clay; wherein the gas barrier layer is embedded in the transparent sealing portion in. A light-emitting device comprising: a substrate having a silver plating layer; a light-emitting diode mounted on the substrate; and a multi-layer film covering at least a surface of the silver plating layer; wherein the multilayer film has a first layer And comprising a layered tannic acid compound; and a second layer comprising the second tannic acid compound other than the layered tannic acid compound. The light-emitting device according to claim 5, wherein the second layer and the first layer are sequentially provided on a surface of the silver plating layer. A light-emitting device according to claim 5 or 6, which is covered or sealed by a transparent sealing resin. A light-emitting device comprising: a substrate having a silver plating layer; a light-emitting diode mounted on the substrate; and a multilayer film covering at least a surface of the silver plating layer; the multilayer film having a first layer containing oxygen The penetration rate is 0.0001~10cc/m ² . 24h. a compound of atm; and, layer 2, which has a volume resistivity of 10 ¹⁰ ~ 10 ¹⁶ Ω. Cm compound. The light-emitting device according to claim 8, wherein the second layer and the first layer are sequentially provided on a surface of the silver plating layer. A light-emitting device according to claim 8 or 9, which is covered or sealed by a transparent sealing resin.