JP2012015485A - Led package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an LED package in which problems such as variation in light emission efficiency, and peeling of a cured resin layer caused by insufficient affinity or adhesion between a sealing resin material and the surface of a substrate are solved.SOLUTION: In an LED package where an LED chip 110 is mounted on a substrate 140 and which is sealed by a resin material 160 containing phosphor 150, a layer containing at least one kind or more functional groups selected from a group of alkoxyl group, epoxy group, phenyl group, alkyl group, and (meth)acrylic group is provided previously on the surface of the substrate coming into contact with the resin material.

Description

  The present invention relates to an LED package in which an LED chip is mounted on a substrate and sealed with a resin containing a phosphor.

  In an LED package in which an LED chip is mounted on a substrate and sealed with a resin containing a phosphor, light having a desired wavelength is obtained by color mixture of light emitted from the LED chip and excitation light from the phosphor. Yes. In the case of an LED package used as a white LED, a blue light emitting LED chip is used as the LED chip, and is sealed with a resin containing a phosphor such as YAG (yttrium aluminum garnet). Pseudo white light is obtained by mixing the blue light emitted from the LED and the yellow region excitation light from the phosphor.

White LEDs are rapidly replacing conventional white light sources such as fluorescent lamps in recent years because of their low energy consumption (high efficiency) and long life. However, in order to meet the demand for high output, it is necessary to take a method of obtaining high brightness by increasing the input current, the amount of heat generated by the LED itself increases, and the problem of heat dissipation is highlighted.
Here, in the case of the LED package having the structure described above, the degradation target due to heat dissipation is not the LED chip but a sealing resin material, and a heat-resistant silicone resin, a hybrid resin, and the like have been studied and developed. Significant progress (see Patent Documents 1 and 2).

JP 2006-77234 A JP 2008-288572 A

In the LED package having the above structure, after the LED chip is mounted on the substrate, the sealing resin material is supplied by a dropping method using a coating method or a dispenser, and the resin material is cured to be sealed. Is stopped. Here, the affinity between the resin material described above and the surface of the substrate and / or the structure (for example, a silver thin film formed on a copper electrode as a reflective film) provided on the substrate is insufficient. In addition, since the familiarity of the supplied resin material with respect to these surfaces deteriorates, bubbles are mixed in the resin layer formed on the substrate, and the resin layer and the substrate (and / or the structure provided on the substrate). In some cases, a gap exists between the object and the object. When the resin material is cured in such a state, in the manufactured LED package, a state in which bubbles are mixed in the resin layer or between the resin layer and the substrate (and / or a structure provided on the substrate). A gap exists.
In the LED package after manufacture, if bubbles are mixed in the resin layer, or if there is a gap between the resin layer and the substrate (and / or a structure provided on the substrate), Scattering and absorption caused by the presence of the gap caused variations in the light emission efficiency of the LED package, resulting in a decrease in yield.

Further, since the LED chip becomes high temperature during light emission, the surface of the resin material and the structure provided on the substrate surface and / or the substrate (for example, a silver thin film formed on the copper electrode as a reflection film) is provided. If the adhesion between the resin layer and the resin material is insufficient, the resin layer peels off from the substrate (and / or the structure provided on the substrate) due to the difference in thermal expansion between the substrate and the resin material. There was a case that caused. Even when there is a gap between the resin layer and the substrate (and / or a structure provided on the substrate), the difference between the thermal expansion property between the substrate and the resin material causes the substrate (and In some cases, the resin layer peeled off from the structure provided on the substrate).
In these cases, although it is not known in the initial product, it appears as a deterioration with time under the high temperature use condition accompanying the lighting of the LED, and it appears as a phenomenon such as a sudden decrease in luminance after a certain period of time, which is very inconvenient.

Further, in recent years, measures such as mounting a large number of LED chips dispersed on the inner surface of the light bulb are being adopted mainly for the purpose of realizing a more uniform light emission and heat dissipation LED package mainly for light bulb applications. The light from the LED chip is treated as a point light source due to its characteristics. This property is appropriate for applications that require visibility, but may not be appropriate when used as a light source for light bulbs used in residential lighting or as a backlight for LCDs. In many cases, a diffusing element (a diffusing plate or a diffusing lens) is required. In particular, when used as a light source for a light bulb, the same texture and impression as a conventional incandescent lamp are required. In order to achieve this, in addition to using the above-described lens and other diffusing elements mounted on the LED package, a large number of small LED packages mounted with one LED chip are arranged inside the bulb base, Conventionally, a large number of LED chips are arranged together in the center, but are distributed on a larger package substrate, and each LED chip is sealed, and the bulb is viewed from the outside. Ingenuity has been devised to improve uniformity.
In the former case, a process of mounting a large number of small LED packages on a light bulb substrate is required. In the latter case, the bulb-sized substrate can be handled as one package, but “recesses” and “banking agents” as in the case of the conventional batch arrangement must be individually formed and arranged, and the sealing resin For uniform formation, costly processes such as forming groove-shaped recesses in the LED chip mounting portion and arranging a banking agent are required.

  From the above, the problem to be solved by the present invention is that light emission caused by lack of affinity and adhesion between the sealing resin material and the substrate surface and / or the surface of the structure provided on the substrate. It is an object of the present invention to provide an LED package in which problems such as variation in efficiency and peeling of a resin layer are solved. It is another object of the present invention to provide a technique that can reduce the costly process associated with the distributed arrangement of LED chips.

  In order to solve the above problems, the present invention provides the following (1) to (6).

(1) In an LED package in which an LED chip is mounted on a substrate and further sealed with a resin material containing a phosphor, the surface of the substrate in contact with the resin material and a structure provided on the substrate A layer containing at least one functional group selected from the group consisting of an alkoxyl group, an epoxy group, a phenyl group, an alkyl group, and a (meth) acryl group is provided in advance on at least one of the surfaces in contact with the resin material. An LED package which is provided.
(2) The LED package according to (1) above, wherein the substrate is an aluminum substrate having an anodized film on the surface.
(3) The LED package according to (2), wherein the anodized film has a straight tubular pore upright in the thickness direction of the anodized film.
(4) The LED package according to any one of (1) to (3), wherein the resin material includes a modified polydimethylsiloxane (PDMS) compound as a main component.
(5) The LED package according to any one of (1) to (4), wherein the functional group-containing layer is formed only on a part of the substrate.
(6) A layer including at least one kind of functional group selected from the group consisting of an alkoxyl group, an epoxy group, a phenyl group, an alkyl group, and a (meth) acryl group is provided in a pattern on a substrate in advance, A method for manufacturing an LED package, comprising: mounting an LED chip at a place where a layer containing a functional group is provided; and then sealing the portion on which the LED chip is mounted with a sealing material containing a phosphor.

In the present invention, a surface modification layer having a specific functional group is provided in advance on the surface of the substrate and / or the surface of a structure (for example, a silver thin film formed on a copper electrode as a reflective film) provided on the substrate. The affinity between the sealing resin material and the surface of the substrate and / or the structure (for example, a silver thin film formed on the copper electrode as a reflective film) provided on the substrate is improved. . As a result, the familiarity of the supplied resin material with respect to these surfaces is good, and air bubbles are mixed in the resin layer formed on the substrate, and the resin layer and the substrate (and / or the substrate are provided on the substrate). In the LED package after manufacture, there is no air bubble mixed in the resin layer, or the resin layer and the substrate (and / or on the substrate). There is no state in which there is a gap with the structure).
Further, a chemical bond is formed between the functional group present in the surface modification layer and the resin material, so that the sealing resin material and the structure provided on the substrate surface and / or the substrate ( For example, the adhesion with the surface of a silver thin film formed on a copper electrode as a reflective film is improved.
Due to these actions, the LED package of the present invention solves problems such as variations in luminous efficiency and peeling of the resin layer due to a difference in thermal expansion between the substrate and the resin material. Thereby, the stability improvement of the light emission of LED package and the lifetime improvement are achieved.
In the present invention, when an aluminum substrate provided with an anodized film on the surface is used as a substrate for an LED package, the surface of the anodized film having pores called pores emits light from the LED chip and excites from the phosphor. By functioning as a light reflecting layer that reflects light, the luminous efficiency of the LED package is improved.
Further, due to the presence of the pores, the sealing resin material and the surface of the substrate and / or the structure provided on the substrate (for example, a silver thin film formed on a copper electrode as a reflective film) are in close contact with each other. More improved.
Moreover, according to the present invention, when manufacturing an LED package in which a plurality of LED chips are dispersedly arranged, the cost of forming a recess for each individually mounted LED chip and / or arranging a banking agent is reduced. Without performing this process, the individually mounted LED chips can be reliably sealed.

FIG. 1 is a schematic view showing a configuration example of an LED package of the present invention. FIG. 2 is a schematic view showing an electrode pattern formed on the resin insulating layer substrate [A]. FIG. 3 is a schematic diagram showing electrode patterns formed on the anodized substrates [A] and [B]. FIG. 4 is a schematic view showing a pattern of the surface modification layer formed on the substrate in Example 15. 5 (X) to (Z) are schematic views showing the state of the substrate surface after heat drying of the sealing resin material in Example 15. FIG.

  The LED package of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic view showing a configuration example of an LED package of the present invention.
In the LED package 100 shown in FIG. 1, an LED chip 110 is mounted on a substrate 140 having electrodes 120 and 130 for external connection. The LED chip 110 is sealed with a resin material 160 including a phosphor (fluorescent particle) 150. In the LED package 100, light having a desired wavelength can be obtained by mixing the light emitted from the LED chip 110 and the excitation light from the phosphor 150. In the case of an LED package used as a white LED, a blue light emitting LED chip is used as the LED chip 110 and sealed with a resin containing a phosphor (fluorescent particle) 150 such as YAG (yttrium aluminum garnet). The pseudo white light is emitted in the direction of the arrow on the light emitting surface side by the color mixture of the blue light emission from the light source and the yellow region excitation light from the phosphor (fluorescent particle) 150.

  The LED package 100 of the present invention is in contact with the resin material 160 of the surface that contacts the resin material 160 of the substrate 140 and the structure (electrodes 120 and 130 in the case of the LED package 100 shown) provided on the substrate 140. A layer (surface modification layer) containing at least one functional group selected from the group consisting of an alkoxyl group, an epoxy group, a phenyl group, an alkyl group, and a (meth) acryl group is provided in advance on at least one surface It is characterized by being.

By forming a surface modification layer containing these specific functional groups, the surface of the substrate and / or the structure provided on the substrate (for example, a silver thin film formed on a copper electrode as a reflective film) is sealed. The affinity of the resin material for stopping is improved.
Due to the formation of the surface modification layer, the affinity of the sealing resin material to the surface of the substrate and / or the surface of a structure provided on the substrate (for example, a silver thin film formed on a copper electrode as a reflective film) is improved. The details of the reason for the improvement are unknown, but hydrogen bonds are formed between the functional groups present in the surface modification layer and the resin material supplied on the surface modification layer, and / or It is considered that the affinity of the resin material to the surface to which the sealing resin material is supplied is improved by the generation of van der Waals force and the like.

As a result, the familiarity of the sealing resin material with respect to the supplied surface is improved, and bubbles are mixed in the resin layer formed on the substrate, and the resin layer and the substrate (and / or the substrate are provided on the substrate). In other words, there is no state in which there is a gap with the structure.
And in the LED package after manufacture, it may be in a state where air bubbles are mixed in the resin layer or in a state where a gap exists between the resin layer and the substrate (and / or a structure provided on the substrate). Absent.

In addition, when the sealing resin material is a thermosetting or ultraviolet curable resin material, when the resin material is cured, the functional group present in the surface modification layer is interposed between the resin material and the resin material. A chemical bond is formed. On the other hand, when the sealing resin material is a thermoplastic resin material, a chemical bond is formed between the functional group present in the surface modification layer and the resin material when the resin material is supplied. Is done.
In this way, a chemical bond is formed between the functional group present in the surface modification layer and the resin material, so that the sealing resin material and the substrate surface and / or the substrate are provided. Adhesion with the surface of a structure (for example, a silver thin film formed on a copper electrode as a reflective film) is improved.

Due to these actions, the LED package of the present invention solves problems such as variations in luminous efficiency and peeling of the resin layer due to a difference in thermal expansion between the substrate and the resin material.
That is, in the manufactured LED package, bubbles are mixed in the cured resin layer, or there is a gap between the resin layer and the substrate (and / or a structure provided on the substrate). Therefore, there is no variation in luminous efficiency.
In addition, the adhesion between the sealing resin material and the surface of the substrate and / or the structure provided on the substrate (for example, a silver thin film formed on the copper electrode as a reflective film) is improved. And that there is no gap between the resin cured product layer and the substrate (and / or the structure provided on the substrate), the high temperature use conditions associated with the light emission of the LED chip The peeling of the resin layer below is suppressed.

"Surface modification layer"
As a method of forming the surface modification layer on the surface of the substrate and / or the structure (for example, a silver thin film formed on the copper electrode as a reflective film) provided on the substrate, the surface of the substrate and / or the substrate may be used. Because it has excellent adhesion to the surface of a structure provided above (for example, a silver thin film formed on a copper electrode as a reflective film) and has good affinity with a sealing resin material. A modifying agent having at least one functional group selected from the group consisting of an alkoxyl group, an epoxy group, a phenyl group, an alkyl group, and a (meth) acryl group, such as an alkoxyl group, an epoxy group, a phenyl group, A silane coupling agent having at least one functional group selected from the group consisting of an alkyl group and a (meth) acryl group, and is provided on the substrate surface and / or the substrate. It was structure (e.g., formed silver thin film or the like onto a copper electrode as a reflective film) by treating the surface, it is preferable to form a surface modification layer on the surfaces.
Here, as a silane coupling agent, it can select suitably from a viewpoint of the affinity with respect to the resin material for sealing, It is preferable to use what has a functional group used as an optimal combination. A silane coupling agent having a functional group that is an optimum combination with respect to the sealing resin material will be described later.

A silane coupling agent is an organosilicon compound having both an organic functional group and a hydrolyzable group. In the above treatment, an alkoxyl group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group) is used as the organic functional group. Group, hexatoxyl group), epoxy group, phenyl group, alkyl group (for example, methyl group, ethyl group, propyl group, butyl group) and at least one functional group selected from the group consisting of (meth) acrylic group Use what has. A silane coupling agent may have only 1 type among these functional groups, and may have 2 or more types.
Since the silane coupling agent adheres to the surface of the substrate and / or the structure provided on the substrate (for example, a silver thin film formed on a copper electrode as a reflective film) through the hydrolyzable group, the treatment is performed. Even when the target is an inorganic material substrate such as alumina or aluminum nitride, it can be used without any problem. When the treatment target is the above-described inorganic material substrate, it is preferable to use a silane coupling agent having a hydroxyl group as a hydrolyzable group.

Specific examples of the silane coupling agent used in the treatment include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (aminoethylamino) propyltrimethoxysilane, 3- (aminoethylamino) propyltri Ethoxysilane, 3- (aminoethylaminoethylamino) propyltrimethoxysilane, 3- (aminoethylaminoethylamino) propyltriethoxysilane, 3-aminopropylsilsesquioxane, bis- (3-trimethoxysilylpropyl) Amine, N-benzyl-N-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N-phenyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (Triet Cysilylpropyl) -diethylenetriamine, poly (ethyleneimine) trimethoxysilane; γ-isocyanatopropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltris (β- Methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and other vinylsilanes; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane and other acrylic silanes; β- (3,4-epoxycyclohexyl) And epoxy silanes such as ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane; .
Among these, when the sealing resin material contains an epoxy resin as a main component, that is, a sealing material matrix, it is preferable to use a silane coupling agent having an epoxy group as an organic functional group. When the sealing resin material contains a silicone resin such as a modified PDMS compound as a main component, it is preferable to use a silane coupling agent having a phenyl group and a methoxy group as the organic functional group.

Further, when selecting a silane coupling agent to be used for the treatment, the object to be treated, that is, a structure provided on the substrate surface and / or the substrate (for example, a silver thin film formed on the copper electrode as a reflective film, etc. ) It is preferable to consider the adhesion to the surface.
For example, when processing a silver thin film formed on a copper electrode as a reflective film, the sealing resin material is cured by using a silane coupling agent having a mercapto group in addition to the above organic functional group. At this time, a chemical bond is formed between the silver and the mercapto group of the silver thin film, which is preferable because adhesion to the silver thin film is improved.

Further, when an aluminum substrate having an anodized film on the surface is used as the substrate, in addition to the silane coupling agent described above, an addition-polymerizable ethylenic compound described in JP-A-10-282679 is used. Examples thereof include a silane coupling agent having a heavy bond reactive group and a silane coupling agent containing a phosphorus compound having an ethylenic double bond reactive group described in JP-A-2-304441. Further, as described in JP-A-2005-125549 and JP-A-2006-188038, more preferable are high groups having an adsorptive group, a hydrophilic group, and a crosslinkable group that can be adsorbed on the anodized substrate surface. A silane coupling agent containing a molecular resin can be mentioned. The polymer resin is preferably a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group. More specifically, a phenolic hydroxyl group, a carboxyl _{group, -PO 3 H 2, -OPO 3} H 2, -CONHSO 2 -, - SO 2 NHSO 2 -, - having an adsorptive group such as COCH ₂ COCH ₃ Examples thereof include a polymer resin that is a copolymer of a monomer, a monomer having a hydrophilic sulfo group, and a monomer having a polymerizable crosslinkable group such as a methacryl group or an allyl group. This polymer resin may have a crosslinkable group introduced by salt formation between a polar substituent of the polymer resin, a substituent having a counter charge and a compound having an ethylenically unsaturated bond, Other monomers, preferably hydrophilic monomers may be further copolymerized.
These silane coupling agents all have at least one functional group selected from the group consisting of an alkoxyl group, an epoxy group, a phenyl group, an alkyl group, and a (meth) acryl group as the organic functional group. have.

  When using the silane coupling agent containing the above-described polymer resin, the content of unsaturated double bonds in the polymer resin is preferably 0.1 to 10.0 mmol, most preferably, per 1 g of the polymer resin. 2.0-5.5 mmol. The mass average molar mass of the polymer resin is preferably 5000 or more, more preferably 10,000 to 300,000.

  If necessary, the silane coupling agent may contain a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, and the like. In addition, in the case of using a substrate having an anodized film formed on the surface of an aluminum substrate, a compound having an amino group or a functional group having a polymerization inhibiting ability and a group interacting with the anodized film surface, etc. (For example, 1,4-diazabicyclo [2,2,2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil, sulfophthalic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminedioxide Acetic acid, hydroxyethyliminodiacetic acid, and the like).

It does not specifically limit as a method to process with a silane coupling agent, Various processing methods, such as an immersion method and the apply | coating method, can be used. As an example of the treatment by the coating method, a solution obtained by diluting the above silane coupling agent in an organic solvent (for example, isopropyl alcohol, methyl ethyl ketone, etc.) is provided on the surface to be treated, that is, the substrate surface and / or the substrate. The method of spray-coating on the surface of a structure (for example, a silver thin film formed on a copper electrode as a reflective film) is mentioned.
When the coating method is used, the silane coupling agent is applied to the surface to be processed, that is, the surface of the substrate and / or the surface of a structure provided on the substrate (for example, a silver thin film formed on a copper electrode as a reflective film). the coating amount (solid content) is preferably from 0.1-100 mg / m ² Doo, and more preferably 1 to 30 mg / m ^2.

As described above, the LED package 100 of the present invention includes the surface of the substrate 140 in contact with the resin material 160 and the structure provided on the substrate 140 (in the case of the LED package 100 illustrated, the electrodes 120 and 130). A layer containing at least one functional group selected from the group consisting of an alkoxyl group, an epoxy group, a phenyl group, an alkyl group, and a (meth) acryl group is provided in advance on at least one of the surfaces in contact with the resin material 160. The other features of the LED package 100 are not particularly limited.
Accordingly, the substrate 140, the LED chip, the phosphor 150, and the resin material 160 used in the LED package 100 can be widely selected from those using conventionally known LED packages. Further, the shape of the LED package 100 is not limited to the illustrated shape, and can be widely selected from conventionally known LED package shapes.

The LED package of the present invention may be an LED package in which a plurality of LED chips are distributed on a substrate.
As described above, the LED package of the present invention is provided with a surface modification layer on a substrate, whereby adhesion between the sealing resin material and the surface of the substrate and / or the structure surface provided on the substrate is achieved. Is improved. Here, by providing a surface modification layer in a pattern on the substrate and supplying a sealing resin material only to the pattern portion, only the pattern portion can be sealed. Since the surface modification layer is not formed in the peripheral portion of the pattern, the affinity of the sealing resin material is low, and the spread of the resin material to the peripheral portion can be suppressed. For this reason, by forming the surface modification layer in a pattern according to the positions where the LED chips are dispersedly arranged, it is possible to individually form a recess for each individually mounted LED chip, or without placing a banking agent. It becomes possible to reliably seal the LED chip mounted on.

  The configuration of each part of the LED package is shown below.

"LED chip"
As the light emitting layer, a semiconductor layer using a semiconductor such as GaAlN, ZnS, ZnSe, SiC, GaP, GaAlAs, AlN, InN, AlInGaP, InGaN, GaN, or AlInGaN can be used. Examples of the semiconductor structure include a homostructure, a heterostructure, or a double heterostructure having a MIS junction, a PIN junction, or a PN junction. The emission wavelength can be variously selected from ultraviolet light to infrared light depending on the semiconductor material and the degree of mixed crystal.

"Substrate material"
The substrate material is not particularly limited as long as it has insulating properties, and can be selected from various materials. For example, as the resin substrate material, epoxy resin, polyamide resin, liquid crystal polymer resin, silicone resin, or the like can be used. As the polyamide resin, polyphthalamide (PPA) resin, PA6T (heat resistant polyamide resin using nonanediamine as a starting polymer) can be used.
As the composite substrate material, a glass epoxy composite substrate called FR-4, CEM-3 or the like can be used.

  As the ceramic substrate material, sintered alumina or sintered aluminum nitride can be used, and LTCC (low temperature sintered ceramic substrate) can also be used.

  Moreover, the board | substrate which provided the insulating layer in the metal substrate surface can also be used. As a specific example of the metal substrate provided with such an insulating layer, a layer of the above-described resin substrate material (for example, epoxy resin) is provided as an insulating layer on the surface of a metal substrate having high thermal conductivity such as aluminum or copper. What was provided can also be used.

Furthermore, what provided not the organic layer (resin layer) but the inorganic layer as the insulating layer in the metal substrate can also be used. As an inorganic layer, the oxide layer formed in the metal substrate surface is mentioned, For example, what formed the anodic oxide film in the aluminum substrate surface is mentioned.
Moreover, what formed the glass layer on the metal substrate surface is mentioned. In this case, the glass layer can be formed by various techniques such as scissors and sol-gel methods.

Among these, an anodized film formed on the surface of an aluminum substrate is a light reflecting layer in which the anodized film surface having pores called pores reflects light emitted from the LED chip and excitation light from the phosphor. As the light emitting efficiency of the LED package is improved, and the presence of the pores improves the adhesion of the resin material for sealing to the substrate surface.
When using an aluminum substrate surface having an anodized film formed thereon, it is desirable that the aluminum material used for the substrate has a high purity of 99.9% or more. Further, it is desirable that the anodized film functioning as an insulating layer has few defects due to intermetallic compounds. The structure of the anodic oxide film is generally said to be porous. In particular, it is desirable that the hole called a pore is a straight tube and is upright in the thickness direction. Further, when a through hole is provided for application to an SMD (surface mount device), it is desirable that an insulating layer by an anodic oxide coating is also provided on the inner wall portion.

"Resin material for sealing"
Conventionally, epoxy resin has been used as a resin material for sealing LED chips, but in order to meet the recent demand for longer life, the use of silicone resin materials that do not easily change color (yellowing) Has increased. The problem with silicone-based resin materials is that they are inferior in adhesion to the substrate surface and the structure surface provided on the substrate. In the present invention, the surface of the substrate and the substrate are formed by forming a surface modification layer. Adhesion with the surface of the structure provided above can be improved.

  The problem of the epoxy resin is the above-mentioned discoloration, and a system using a mixture of alicyclic epoxy resins having high yellowing resistance is being adopted as an improvement measure. However, alicyclic epoxy resins are expensive.

  In terms of heat resistance, which is a requirement for high-power LEDs, higher performance is required for any resin material. As a solution, a modified polydimethylsiloxane (PDMS) compound that can reduce organic components is used. The use of various silicone-based resin materials has also been proposed.

  Various components can be used as the main component of the resin material for sealing, i.e., the matrix of the sealing material.For example, a low molecular organic matrix, an organic resin matrix, a low molecular inorganic matrix, an inorganic resin matrix (for example, Polysiloxane, fluorinated silicon oxide, phosphazene, etc.) or a composite matrix thereof (for example, an organic silica film made of silicone, trifluoromethylsilane, trimethoxyphenylsilane, triethoxymethylsilane, etc., an inorganic compound in the organic matrix) , Organic-inorganic hybrid films, etc.).

  The material constituting the low-molecular organic matrix may be any material that can be formed into a glass state by mixing a crystalline low-molecular compound or a material that can form a matrix with low molecules. For example, phthalocyanine or the like may be used as an electronic material. Benzocyclobutene and the like are known. Moreover, the substance which is seen by Unexamined-Japanese-Patent No. 8-32217, 11-116663 etc. can be illustrated.

  Examples of the material constituting the organic resin matrix include various organic resins used in this field. Typical examples include an epoxy resin, and a bisphenol A type epoxy resin and an alicyclic epoxy resin that has high weather resistance and little yellowing even when used for a long time.

  Examples of the material constituting the inorganic resin matrix include siloxane-based materials such as hydrogenated silsesquioxane, methylsilsesquioxane, and hydrogenated methylsilsesquioxane.

  You may use the matrix which used those materials which comprise the said various matrix, and used those composites.

In the present invention, it is desirable to use an organic resin matrix and an inorganic resin matrix which are superior in terms of suppressing gas permeation as compared with a low molecular weight matrix, and it is desirable to use an inorganic resin matrix which is superior in terms of heat resistance.
Among those that form the inorganic resin matrix, it is desirable to use a modified polydimethylsiloxane compound (modified PDMS) into which a unit for suppressing the remaining organic components during film formation is introduced.

  Various organic resins can be used as the matrix used as the matrix. For example, (i) a thermoplastic resin, (ii) a thermosetting resin, (iii) a radiation curable resin, and (iv) ) A composite resin composed of two or more of thermoplastic resins, thermosetting resins and radiation curable resins, or (v) a mixture of two or more of (i) to (iv) above can be used. Examples of these matrices are “New materials and process technology for next-generation ULSI multilayer wiring” (Technical Information Society of 2000), “Transforming packaging materials and layering technology – high frequency, high density, low temperature sintering, environmental response — (2003 TIC). Among these, at least one resin selected from the group consisting of a thermoplastic resin, a thermosetting resin, and a composite resin of a thermoplastic resin and a thermosetting resin can be preferably used.

<Thermoplastic resin>
Examples of the thermoplastic resin include polyolefin resins such as polyethylene resin, polypropylene resin, poly 1-butene resin, poly 4-methyl-1-pentene resin; polyester resins such as polyethylene terephthalate resin and polyethylene naphthalate resin; nylon 6, nylon Polyamide resin such as 66; Fluorine resin such as polytetrafluoroethylene resin and polytrifluoride ethylene resin; Other polystyrene resin, polyvinyl chloride resin, polymethyl (meth) acrylate resin, polycarbonate resin, polyether sulfone resin, polyphenylene ether Examples thereof include resins and polyamideimide resins.

<Radiation curable resin>
As the radiation curable resin, those used in the field of electronic parts and the like can be widely used. Basically, it is possible to use a compound having two or more double bonds. In order to form a fine pattern, a side chain having a double bond and a carboxyl group for enabling aqueous development can be used. It is often used as an ultraviolet curable type. As these radiation curable resins, for example, those described in JP-A-61-2243869, JP-A-2002-294131, JP-A-2005-154780 and the like can be used.

  Typically, examples of the radiation curable resin include those obtained by reacting “an ethylenically unsaturated monomer having a carboxyl group” with “a compound containing two or more epoxy groups”.

  Here, “compounds containing two or more epoxy groups” include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A-novolac type epoxy resin, alicyclic epoxy. Resin (for example, “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.) and a polyfunctional epoxy resin (for example, EPPN-502H manufactured by Nippon Kayaku Co., Ltd.) and Taku manufactured by Dow Chemical Co., Ltd. There are epoxy resins such as Tex-742 and XD-9053).

  In addition, as the “compound containing two or more epoxy groups”, the following copolymer of an epoxy compound and an ethylenically unsaturated monomer can also be used. That is, as epoxy compounds, glycidyl (meth) acrylates such as glycidyl (meth) acrylate and 2-methylglycidyl (meth) acrylate, and (meth) acrylic such as (3,4-epoxycyclohexyl) methyl (meth) acrylate And epoxycyclohexyl derivatives of acids. Examples of the ethylenically unsaturated monomer include aliphatic or alicyclic alkyl (meth) acrylates; aromatic (meth) acrylates such as benzyl (meth) acrylate; hydroxyethyl (meth) acrylate and methoxy Ethylene glycol ester (meth) acrylate such as ethyl (meth) acrylate, polyethylene glycol ester (meth) acrylate and propylene glycol (meth) acrylate; (meth) acrylamide compound; N-substituted maleimide compound; vinyl pyrrolidone; (Meth) acrylonitrile; vinyl acetate; styrene; α-methylstyrene; and vinyl ether.

  In this specification, (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid, and (meth) acrylate is a generic term for acrylate and methacrylate.

  Examples of the “ethylenically unsaturated monomer having a carboxyl group” include (meth) acrylic acid, crotonic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, 2-propenoic acid, 3- (2-carboxyethoxy) -3-oxypropyl ester, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid and 2- (meth) ) Those having one ethylenically unsaturated group such as acryloyloxyethyl hexahydrophthalic acid, and hydroxy such as pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. It includes those having a plurality of ethylenically unsaturated groups such as those obtained by reacting a dibasic acid anhydride to a polyfunctional acrylate having Le group. Among these, those having one carboxyl group are preferable, and it is particularly preferable to use (meth) acrylic acid or (meth) acrylic acid as a main component. This is because the ethylenically unsaturated group introduced by (meth) acrylic acid is excellent in photoreactivity. These “ethylenically unsaturated monomers having a carboxyl group” can be used alone or in appropriate combination.

  Moreover, as what added the carboxyl group for performing a double bond and aqueous development to a side chain, said "compound containing two or more epoxy groups" to "the ethylenically unsaturated monomer which has a carboxyl group" In addition, a product obtained by reacting the following “polycarboxylic carboxylic acid anhydride” can be raised. Examples of the “polycarboxylic anhydride” include succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Dibasic acid anhydrides such as methyl nadic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, and trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride and methylcyclohexene tetracarboxylic acid anhydride An acid anhydride having 3 or more basic acids may be mentioned. Each of these “polycarboxylic anhydrides” can be used alone or in appropriate combination.

<Thermosetting resin>
Examples of the thermosetting resin include polyimide resin, bismaleimide triazine resin (BT resin), crosslinkable polyphenylene oxide, curable polyphenylene ether, phenol resin, melamine resin, urea resin, epoxy resin, unsaturated polyester resin, alkyd resin, Diallyl phthalate resin, xylene resin, (meth) acrylic resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, bisphenol A, resorcin, various novolac type epoxy resins, bisphenol A type epoxy resin Examples include brominated bisphenol A type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, halogenated epoxy resins, and spirocyclic epoxy resins. .

<Composite resin>
Examples of the composite resin of the thermoplastic resin and the thermosetting resin include polyphenylene ether / epoxy resin, polyamideimide / epoxy resin, polyamide / epoxy resin, and polyamideimide / polyimide resin.

  Specifically, epoxy resin, polyester resin, polycarbonate, polyimide, polyetherimide, polyphenylene sulfide, COPNA, polybenzimidazole, fluorine resin, fluorinated polymer, amorphous polyolefin resin, syndiotactic polystyrene, polynaphthalene, polyindane , Polyphenylene ether, liquid crystal polymer, polyquinoline, polyphenylquinoxaline, cyanate resin, polysulfone, polyethersulfone, polyetheretherketone, polyetherethernitrile, aromatic polyether and the like.

  Among the sealing resin materials described above, (a) an epoxy resin, (b) an addition condensate of bisphenol A and formaldehyde, (c) a curing accelerator and (d) a compound having a triazine ring or an isocyanuric ring, or urea An organic resin matrix containing, as an essential component, a compound having a nitrogen content of 60% by mass or less and containing no derivative is preferred.

  In the above organic resin matrix, (b) the addition condensate of bisphenol A and formaldehyde has a phenolic hydroxyl group in the range of 0.5 to 1.5 equivalents relative to the epoxy group of the epoxy resin, and (c) the curing accelerator is an epoxy. A compound containing 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin and (d) a compound having a triazine ring or an isocyanuric ring, or a compound having a nitrogen content of 60% by mass or less and containing no urea derivative is nitrogen-containing with respect to the resin solid content. It is preferable to contain so that a rate may become the range of 0.1-10 mass%.

  If necessary, in addition to the above (a) to (d), (e) a flame retardant may be contained in the organic resin matrix.

  Examples of the epoxy resin (a) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and bisphenol A novolak. Type epoxy resin, bisphenol F novolak type epoxy resin, phenol salicylaldehyde novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, other glycidyl etherified products of bifunctional phenols, two A glycidyl etherified product of a functional alcohol, a glycidyl etherified product of a polyphenol, a hydrogenated product thereof, a halide, etc. may be mentioned without particular limitation. Several kinds of these compounds can be used in combination.

  The addition condensate of bisphenol A and formaldehyde (b) functions as a curing agent for the epoxy resin (a), and there is no restriction on the molecular weight, and a bisphenol A monomer is contained. Also good.

  Further, as the component (b), a curing agent other than an addition condensate of bisphenol A and formaldehyde may be used in combination. For example, bisphenol F, polyvinylphenol or phenol, cresol, alkylphenol, catechol, bisphenol F and the like are used as raw materials. And novolak resin. There is no restriction | limiting also about the molecular weight of these compounds, Several types can be used together.

  (B) It is preferable that the compounding quantity of a component is the range whose phenolic hydroxyl group is 0.5-1.5 equivalent with respect to the epoxy group of an epoxy resin. Outside this range, the dielectric properties and heat resistance become poor.

  The curing accelerator (c) may be any compound as long as it has a catalytic function that promotes the etherification reaction of an epoxy group and a phenolic hydroxyl group. For example, an alkali metal compound, alkaline earth Examples thereof include metal compounds, imidazole compounds, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. Among them, it is preferable to use an imidazole whose imino group is masked with acrylonitrile, isocyanate, melamine acrylate, or the like, because a prepreg having storage stability twice or more that of the prior art can be obtained.

  Examples of the imidazole compound used here include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, and 2-heptadecylimidazole. 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole , 2-ethyl imidazoline, 2-isopropyl imidazoline, 2,4-dimethyl imidazoline, 2-phenyl-4-methyl imidazoline, etc., and the masking agents include acrylonitrile, phenylene diisocyanate. Sulfonates, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, isophorone diisocyanate, and the like melamine acrylate.

  Some of these curing accelerators may be used in combination, and the blending amount is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin. If it is less than 0.01 part by mass, the promoting effect is small, and if it exceeds 5 parts by mass, the storage stability is deteriorated.

  Examples of the compound having a triazine ring or isocyanuric ring (d) or a compound having a nitrogen content of 60% by mass or less not containing a urea derivative include aromatic amine type epoxy resins, aliphatic amine type epoxy resins, and hydantoin types. There are epoxy resins, glycidylamine type epoxy resins, isocyanurate type epoxy resins, cyanurates, isocyanurates, melamines, addition condensates of phenols and compounds having a triazine ring and aldehydes, and glycidyl ethers thereof. There is no particular limitation. Any of these compounds may be used, and several types may be used in combination. These compounds are preferably blended in an amount such that the nitrogen content is 0.1 to 10% by mass with respect to the total resin solid content used in the nanotube composite molded article or nanowire composite molded article for printed wiring boards. When the nitrogen content is less than 0.1% by mass, it is difficult to improve the adhesiveness with the copper foil, and when it exceeds 10% by mass, the water absorption is increased. Here, total resin solid content is resin solid content computed from the mass ratio before and behind the process for 30 minutes in a 210 degreeC hot-air drying furnace.

  The flame retardant of the above (f) may be any as long as it is generally called a flame retardant, for example, bisphenol A, bisphenol F, bisphenol S, polyvinylphenol, phenol, cresol, alkylphenol, catechol. Although there are halides such as novolak resin, glycidyl ether, etc., there is no particular limitation, and antimony trioxide, tetraphenylphosphine, etc. may be used in combination. Among them, examples of the difficult agent include tetrabromobisphenol A or glycidyl ether of tetrabromobisphenol A.

  It is also preferable to use an inorganic resin matrix as the sealing resin material. As the desirable inorganic resin used as the matrix, various resins can be used, and for example, polysiloxane, fluorinated silicon oxide, phosphazene, and the like can be used. In particular, it is desirable to use a modified polysiloxane in which the terminal of the polysiloxane is substituted with a silicate compound. The modified PDMS, which is a desirable polydimethylsiloxane compound, will be described below.

Modified PDMS is a PDMS end modified with a silicate compound, PDMS having a silanol group at both ends, and an alkoxy having an alkoxy group that is a hydrolyzable functional group on one or both sides of the main chain. It is obtained by reacting with a silane partial condensate.
Here, the silicate compound is a metal alkoxide oligomer made of silicon (Si), which has a siloxane (—Si—O—Si—) skeleton in the main chain and an alkoxy group (RO) introduced into the outer chain. That is. Here, (R) which is the alkyl part of the alkoxy group (RO) is exemplified by a methyl group, an ethyl group, a propyl group, and the like. This silicate compound has the property of easily reacting with water.
The silicate compound is an oligomer of a metal alkoxide, has a higher molecular weight and lower volatility than the metal alkoxide, and contributes to the suppression of volatilization of the highly volatile low molecular weight siloxane contained in the modified PDMS when the silicate compound is hydrolyzed. . As the silicate compound, methyl silicate, ethyl silicate, propyl silicate and the like can be used. Ethyl silicate is preferred from the standpoints of quality stability and safety. Methyl silicate may be used to increase the reactivity.

  PDMS modified with the above silicate compound has a significantly higher functional group concentration and higher condensation reactivity with the silicate compound than ordinary PDMS, so the condensation reaction of the alkoxysilane moiety contained in the modified PDMS Accelerated, polymerized and cured. The mass average molecular weight is preferably in the range of 5,000 to 100,000. When used, a mixture having a silicate compound and the above-described modified PDMS is subjected to the following hydrolysis reaction and condensation reaction. Both the silicate compound and the modified PDMS are hydrolyzed in the presence of water to produce highly reactive silanol groups (—OH groups), so that the condensation reaction with the modified PDMS proceeds smoothly without acceleration of silanol aggregation. proceed. Thereby, the low molecular siloxane contained in the modified PDMS is also taken into the reaction product, and the low molecular siloxane becomes a part of the constituent material.

The silicate compound is represented by [Chemical Formula 1] Si _n O _(n-1) (RO) _{2 (n + 1)} (R = alkyl group, n = 4 to 16). Modified PDMS is represented by [Chemical formula 2] Si _n O _(n-1) (RO) _{2 (n + 1)} (OSi (CH ₃ ) ₂ ) _m (RO) _{2 (n + 1)} Si _n O _{(n-1 )} (R = alkyl group, n = 4 to 16, m> 50).

  In addition to the various matrices that form the main component of the resin material, additives such as a curing accelerator, an antioxidant, and an ultraviolet absorber may be mixed in the sealing resin material as necessary.

When the resin material used as the matrix is a thermosetting resin, a curing accelerator may be mixed in the sealing resin material.
Examples of the curing accelerator include tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, and the like; tertiary amine; quaternary ammonium salt Bicyclic amidines such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof; imidazoles such as 2-methylimidazole and 2-phenyl-4-methylimidazole; However, there is no particular limitation as long as the curability is good and there is no coloring. These curing accelerators may be used alone or in combination of two or more. Bicyclic amidines such as 1,8-diazabicyclo (5,4,0) undecene-7, and imidazoles exhibit high activity against thermosetting resins even with a small addition amount, and have a relatively low curing temperature. However, it is more preferable because it can be cured in a short time, for example, about 150 ° C. in about 90 seconds. As commercially available products, Nikka Octix zinc (trade name) manufactured by Nippon Chemical Industry Co., Ltd., U-CAT5003 (trade name) manufactured by San Apro Co., Ltd., etc. can be preferably used.

  When such a curing accelerator is used, the preferred use ratio is 0.003 to 0.04, more preferably 0.004 to 0.02, in terms of mass ratio to the thermosetting resin. If it is this range, sufficient hardening promotion effect will be acquired and it will not cause the physical-property fall and coloring of hardened | cured material.

  Moreover, when the resin material used as a matrix is a thermosetting resin, you may add antioxidant to the resin material for sealing. By adding an antioxidant, it is possible to prevent oxidative deterioration during heating and to obtain a cured product with little coloring. Examples of antioxidants are phenolic, sulfur and phosphorus antioxidants. A preferable blending ratio when using the antioxidant is 0.0001 to 0.1 by mass ratio based on the thermosetting resin.

  Specific examples of the antioxidant include monophenols (2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), bisphenols (2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4- Ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxy Saspiro [5,5] undecane, etc.), polymer type phenols (1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2) , 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) Propionate] methane, bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-) t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, etc.), sulfur-based antioxidant (dilauryl-3,3′-thiodipropio) , Dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate), phosphites (riphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (Nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2 , 4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl- 4- {2- (octadecyloxy Rubonyl) ethyl} phenyl] hydrogen phosphite), and oxaphosphaphenanthrene oxides (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-) t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide etc.). These antioxidants can be used alone, but it is particularly preferable to use them in combination with phenolic / sulfuric or phenolic / phosphorous. As commercially available phenolic antioxidants, IRGANOX 1010 (trade name) and IRGAFOS 168 (trade name) manufactured by Ciba Japan Co., Ltd. can be used singly or in combination. You can also.

  Moreover, in order to improve light resistance, you may mix | blend a ultraviolet absorber with the resin material for sealing as needed. As an ultraviolet absorber, a general ultraviolet absorber for plastics can be used, and a preferable blending ratio thereof is 0.0001 to 0.1 in terms of a mass ratio based on a resin material serving as a matrix.

  Specific examples of the ultraviolet absorber include salicylic acids such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy- Benzophenones such as 5-sulfobenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-3 ' 5′-ditert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′) , 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-amylphenyl) benzotriazole, 2-{(2′-hydroxy-3) Benzotriazoles such as', 3 '', 4 '', 5 '', 6 ''-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole, and bis (2,2,6,6-tetramethyl -4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Ntamechiru 4-piperidyl) is [{3,5-bis (1,1-dimethylethyl) -4-hydrido hydroxyphenyl} methyl] hindered amines such as butyl malonate.

Furthermore, you may mix | blend the following component with the resin material for sealing as needed.
(1) Powdery reinforcing agents and fillers, for example, metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, transparent fillers such as glass beads, aluminum hydroxide, etc. Metal hydroxide, kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc.
These are blended within a range that does not impair the transparency of the resin material serving as a matrix. A desirable ratio when these are blended is in a range of 0.10 to 1.0 in terms of mass ratio with respect to the resin material serving as a matrix.

(2) Colorants or pigments such as titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red and organic dyes.
(3) Flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds.
(4) Ion adsorbent.
A desirable ratio when these components are blended is 0.0001 to 0.30 in terms of a mass ratio with respect to a resin material to be a matrix.
(5) A nanoparticle dispersion of a metal oxide such as zirconia, titania, alumina, or silica.
A preferable ratio when blending these components (1) to (6) is 0.01 to 0.50 in terms of mass ratio with respect to the resin material to be a matrix.

In the present invention, in addition to the above components, a phosphor (fluorescent particle) 150 having an excitation band corresponding to light emission from the LED chip 110 is added to the sealing resin material 160.
For example, when combined with an LED chip that emits blue or ultraviolet light, a phosphor having an excitation band in the ultraviolet to blue wavelength region generated from the LED chip 110 is added to the sealing resin material.
Specific examples of the phosphor are Y ₂ O ₃ S: Eu, La ₂ O ₂ S: Eu, 3.5 MgO · 0.5 MgOF ₂ .GeO ₂ : Mn, (La, Mn, Sm) ₂ O ₂ S · Ga ₂ O ₃ (red phosphor), ZnS: Cu · Al, SrAl ₂ O ₄ : Eu, BAM: Eu · Mn (green phosphor), YAG: Ce (yellow phosphor), BAM: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, ZnS: Ag, (Sr, Ga, Ba, Mg) 10 (PO ₄ ) ₆ Cl: Eu (blue phosphor).

  When the LED package of the present invention is used as a white LED, the oxynitride glass phosphor described in JP-A-2001-214162, JP-A-2003-336059, and JP-A-2003-124527 are described. The phosphor described in JP-T-2003-515655 and the like containing nitrogen such as a silicon nitride-based phosphor can be used.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.
(Examples 1-14 and Comparative Examples 1-11)
〔substrate〕
The substrates listed in the table below are as follows.
Resin insulation layer substrate [A]: A copper-clad substrate (NRA-8 manufactured by Nippon Rika Kogyo Co., Ltd.) with a resin insulation layer provided on an aluminum base is processed into a 10 mm square so that the wiring pattern shown in FIG. 2 is obtained. Copper electrodes 120 and 130 were formed on the substrate 140. Thereafter, a silver thin film was formed on the surface of the copper electrode by displacement plating in order to impart reflectivity to the electrode surface. In FIG. 2, the LED chip 110 used in the high temperature and high quality bias test is indicated by a broken line.
Resin insulation layer substrate [B]: The same copper-clad substrate as [A] was used, and the entire surface of the copper layer was removed to expose the resin insulation layer.
Anodized substrates [A] and [B]: A substrate (A) and (B) processed by the method shown below and processed into a 10 mm square so that the wiring pattern shown in FIG. The electrodes 120 and 130 were formed on the substrate 140 using a printing method. However, the electrodes 120 and 130 are Au electrodes. In FIG. 3, the LED chip 110 used in the high temperature and high quality bias test is indicated by a broken line.
Specifically, 50 g of Au nanoparticles (Nanotech: manufactured by C-I Kasei Co., Ltd.) was added to 50 g of xylene, and then stirred at room temperature for 8 hours to obtain a stable Au ink dispersion. As a result of solid powder analysis, the gold content was 26.8% by mass. A silane coupling agent (Shin-Etsu Polymer Co., Ltd., product name KBM603) additionally mixed with the above ink dispersion in an amount of 2% by mass of the ink dispersion was used as the metal ink. The viscosity was 10 cps in this state. The metal ink thus prepared was supplied by screen printing using TU2030-B (manufactured by Celitec), printed, and maintained for about 5 minutes with a hot air dryer set at 160 ° C. 120, 130 were formed.

(Production method of anodized substrates (A) and (B))
(1) Mirror finish (electropolishing)
A high-purity aluminum substrate (manufactured by Sumitomo Light Metal Co., Ltd., purity 99.90 mass%, thickness 0.4 mm) is cut so that it can be anodized in an area of 10 cm square, and an electrolytic polishing liquid having the following composition is used. The electropolishing treatment was performed under conditions of a temperature of 65 ° C. and a liquid flow rate of 3.0 m / min.
The cathode was a carbon electrode, and GP0110-30R (manufactured by Takasago Seisakusho) was used as the power source. The flow rate of the electrolytic solution was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE).
(Electrolytic polishing liquid composition)
-660 mL of 85% by mass phosphoric acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.)
・ Pure water 160mL
・ Sulfuric acid 150mL
・ Ethylene glycol 30mL

(2) Anodizing substrate (A)
An anodized film was formed on the surface of the aluminum substrate by subjecting the aluminum substrate after the electrolytic polishing treatment to an anodizing treatment under the following conditions.
The aluminum substrate after the electropolishing treatment was anodized for 5 hours with an electrolytic solution of 10 M / L sulfuric acid under the conditions of a current density of 20 A / dm ² , a liquid temperature of 35 ° C., and a liquid flow rate of 3.0 m / min. .
Substrate (B)
The anodized film having straight tubular pores upright in the thickness direction by subjecting the aluminum substrate after electrolytic polishing treatment to anodization treatment by a self-ordering method according to the procedure described in JP-A-2007-204802 Was formed on the surface of an aluminum substrate.
The aluminum substrate after the electropolishing treatment was subjected to a pre-anodization treatment for 5 hours with an electrolytic solution of 0.50 mol / L oxalic acid at a voltage of 40 V, a liquid temperature of 15 ° C., and a liquid flow rate of 3.0 m / min. .
Thereafter, a film removal treatment was performed in which the aluminum substrate after the pre-anodizing treatment was immersed in a mixed aqueous solution (liquid temperature: 50 ° C.) of 0.2 mol / L chromic anhydride and 0.6 mol / L phosphoric acid for 12 hours.
Then, re-anodizing treatment was performed for 10 hours with an electrolyte solution of 0.50 mol / L oxalic acid at a voltage of 40 V, a liquid temperature of 15 ° C., and a liquid flow rate of 3.0 m / min to form an oxide film with a film thickness of 80 μm. Obtained.
In both the pre-anodizing treatment and the re-anodizing treatment, the cathode was a stainless electrode, and the power source was GP0110-30R (manufactured by Takasago Seisakusho). Moreover, NeoCool BD36 (made by Yamato Kagaku) was used for the cooling device, and Pear Stirrer PS-100 (made by EYELA) was used for the stirring / heating device. Furthermore, the flow rate of the electrolyte was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE).

(Formation of surface modification layer)
A surface modification layer was formed on the surface of the substrate prepared by the above procedure using an immersion (dip) method. About the board | substrate used for affinity, adhesiveness, and a thermo cycle test, the board | substrate created above was immersed and taken out in the modification processing agent shown below, and a surface modification layer was dried by 100 degreeC and the conditions for 1 minute. Formed.
For the substrate used for the high-temperature and high-humidity bias test, after the LED chip is mounted on the substrate in advance, the same modification treatment agent is poured on the surface of the LED so that it does not adhere to the LED surface, and the excess liquid is removed and dried in the same way. By doing so, a surface modification layer was formed.
In addition, about the comparative examples 1-11, the formation procedure of the above-mentioned surface modification layer was not implemented.

(Modifying agent)
(1) M0928 (manufactured by Tokyo Chemical Industry Co., Ltd.): (3-mercaptopropyl) trimethoxysilane (the following formula)
Organic functional group: methoxy group, mercapto group (2) Silane coupling agent Z6040 (manufactured by Toray Dow Corning): 3-glycidoxypropyltrimethoxysilane (following formula)
Organic functional group: Epoxy group, methoxy group (3) Siloxane 3074 (manufactured by Toray Dow Corning): Dimethylphenylmethoxysiloxane Organic functional group: Phenyl group, methoxy group (4) Modification treatment agent containing compound represented by the following formula
Organic functional group: methacrylic group The composition of the silane coupling agent (4) is as follows.
Compound of the above formula: 0.017 g
Methanol: 9.00 g
Water: 1.001g
(5) Silanol at both ends (manufactured by Gelest, DMS-S12): polydimethylsiloxane (the following formula)
In addition, n in a formula is 3-7.
Organic functional group: methyl group

[Sealing with resin material]
After forming the surface modification layer by the above procedure (for Comparative Examples 1 to 11 directly with respect to the substrate created by the above procedure), the sealing resin material shown below is 1 g as the solid content. A certain amount was dropped onto the substrate using a dispenser and dried by heating at 200 ° C. for 60 minutes.

(Resin material for sealing)
(1) Composition containing modified PDMS prepared by the method described later (2) Celoxide 2021P (manufactured by Daicel Chemical Industries): 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate The product was diluted with methanol to a solid content concentration of 10% by mass.
(3) KER6100 / CAT-PH (manufactured by Shin-Etsu Chemical Co., Ltd.): Dimethyl silicone-based sealing material The solvent was diluted with a solution of water / methanol 1: 5.

(Preparation of modified PDMS-containing composition)
Into a reaction vessel equipped with a stirrer, a thermometer, and a dropping line, 1.0 g of ethyl silicate (manufactured by Tama Chemical Industry Co., Ltd., silicate 40 n = 4 to 6) is put, and polydimethyl having ethyl silicate alkoxy-modified at both ends. 32.0 g of siloxane (mass average molecular weight; equivalent to 32,000) (HBSIL039 manufactured by Arakawa Chemical Co., Ltd.) was stirred and mixed in the atmosphere (room temperature) for about 30 minutes to obtain a raw material liquid A as a hybrid. Here, silicates having the same type and the same characteristics were used as silicates used in ethyl silicate and polydimethylsiloxane obtained by alkoxy-modifying ethyl silicate at both ends.
Then, in the hydrolysis step and the condensation step, the raw material liquid A was added dropwise with a required amount of 0.93 g of water over about 1 hour and stirred and mixed. Then, it naturally cooled to room temperature over about 30 minutes, stirring, and obtained modified | denatured PDMS containing composition.

  The following evaluation was implemented with respect to the board | substrate sealed using the resin material in said procedure.

[Affinity evaluation]
About the board | substrate interface which dripped the resin material, the cross section was grind | polished and SEM observation was performed and peeling with a resin material and a board | substrate interface was confirmed. Moreover, the presence or absence of bubbles in the substrate interface and the resin material was confirmed. In the SEM observation, 100 visual fields were observed with respect to a cross section at a magnification of 200 times for each specimen.
Exfoliation, evaluation of bubbles exceeding 10 in 100 fields of view, evaluation of 5 to less than 10 △, evaluation of 3 to less than 5 ○ △ evaluation of less than 3 ○ did.

[Adhesion evaluation (Thermocycle test (TCT))]
Using a liquid layer type thermal shock tester LTS-50-A manufactured by Hutech, the temperature increase / decrease in the liquid layer was alternately repeated for 3 minutes each in Galden held at -65 ° C and 150 ° C, 300 cycles were performed.
Then, it cut | disconnected in the center part of the board | substrate surface, the cross section was grind | polished, SEM observation was performed, and the presence or absence of peeling with a resin material and a board | substrate interface was confirmed. In the SEM observation, 100 visual fields were observed with respect to a cross section at a magnification of 200 times for each specimen.
If the number of peels exceeds 10 in 100 fields, Δ ×, 5 or more but less than 10 Δ, 3 or more but less than 5 ○ △, 1 or more but less than 3 ○, 0 items were evaluated as ◎.

[Evaluation of light emission behavior over time (high-temperature, high-humidity bias test (HHBT))]
In order to make it closer to the actual use system, LED chip (Nitride Semiconductor UV-LED (taken from NS375W wafer output 3.5 mW)) mounted on each substrate, surface modification layer formation, and resin material The LED package obtained by carrying out the sealing according to the above was fixed on a printed circuit board, and 4000 cycles were repeated in which lighting and extinguishing were repeated every 1 hour under conditions of a temperature of 85% and a humidity of 85%.
The test was performed while actually measuring the luminance at the time of lighting, and the luminance change after applying a 4000 cycle bias (referred to as “the end”) before the test (referred to as “the initial”) was used as an evaluation standard.
X when the luminance change is 40% or more, △ when it is 20% or more and less than 40%, △ when it is 10% or more but less than 20%, or △ when it is 5% or more but less than 10%, A value of less than 5% was evaluated as ○.

The results of each evaluation are shown in the following table. In any evaluation result, it was judged that it was unusable if it was Δ or less.

(Example 15)
In this example, a surface modification layer was formed in a pattern on a substrate using the same modification treatment agent (modification treatment agent (5)) as used in Example 12, and the surface modification layer in the pattern form The formed part was sealed.
The modification treatment agent (5) used in Example 12 was further diluted 10-fold with methanol and dropped into the substrate 140 (anodized substrate A) in a pattern using a dispenser, and at 100 ° C. for 1 minute. The surface modification layer 180 was provided in a pattern on the substrate 140 by drying under conditions. FIG. 4 shows a pattern of the surface modification layer 180 formed on the substrate 140.
Next, a resin material 160 for sealing (sealing resin agent (1)) is dropped on the surface treatment layer 180 formed in a pattern on the substrate 140 using a dispenser, and dried by heating at 200 ° C. for 60 minutes. I let you. This was made into the board | substrate (X).
For comparison, a sealing resin material 160 (sealing resin agent (1)) was dropped in a pattern on a substrate 140 (anodized substrate A) on which a surface modification layer was not formed, using a dispenser. A substrate 140 (anodizing treatment), and a substrate 140 having a surface modification layer 180 formed on the entire surface by a dipping method (using the modification treatment agent (5)) in the same procedure as in Example 12. A substrate (A) was prepared by dropping a sealing resin material 160 (sealing resin agent (1)) in a pattern using a dispenser (referred to as substrate (Z)).
For the substrates (X) to (Z), the states after heat drying of the sealing resin material 160 are shown in FIGS. 5 (X) to (Z), respectively. In addition, about FIG. 5 (Z), the pattern shape of the surface modification layer in FIG. 4 was shown with the broken line.
As is clear from comparison between FIG. 4 and FIG. 5 (X), in the substrate (X), the sealing resin (sealing resin material) 160 maintains the pattern of the surface modification layer 180 on the substrate 140. No peeling or the like was observed.
As is clear from a comparison between FIG. 4 and FIG. 5 (Y), in the substrate (Y), due to the lack of affinity of the sealing resin material for the surface of the substrate 140, the sealing resin (for sealing) The resin material) 160 was interrupted.
As is clear from a comparison between FIG. 4 and FIG. 5 (Z), since the surface modification layer 180 is formed on the entire surface of the substrate 140 in the substrate (Z), the sealing resin material immediately after dropping with the dispenser. 160 spread on the substrate 140, and a pattern with a predetermined shape (shown by a broken line) could not be formed.

  As is clear from the above results, the present invention improves the affinity of the resin material for sealing with respect to the substrate surface, prevents entrainment of bubbles and the like when supplying the resin material, and is also suitable for temperature cycles. High adhesion is maintained, and the resin layer peeling from the substrate interface can be suppressed. Furthermore, the light emission characteristics can be maintained for a long time due to the above effects.

DESCRIPTION OF SYMBOLS 100 LED package 110 LED chip 120,130 Electrode 140 Board | substrate 150 Phosphor 160 Resin material (sealing resin)
180 Surface modification layer

Claims (6)

  In an LED package in which an LED chip is mounted on a substrate and sealed with a resin material containing a phosphor, the surface of the substrate in contact with the resin material, and the resin of the structure provided on the substrate A layer containing at least one functional group selected from the group consisting of an alkoxyl group, an epoxy group, a phenyl group, an alkyl group, and a (meth) acryl group is provided in advance on at least one of the surfaces in contact with the material. An LED package characterized by comprising:   The LED package according to claim 1, wherein the substrate is an aluminum substrate having an anodized film provided on a surface thereof.   The LED package according to claim 2, wherein the anodized film has a straight tubular pore upright in a thickness direction of the anodized film.   The LED package according to claim 1, wherein the resin material contains a modified polydimethylsiloxane compound as a main component.   The LED package according to claim 1, wherein the functional group-containing layer is formed only on a part of the substrate.   A layer containing at least one functional group selected from the group consisting of an alkoxyl group, an epoxy group, a phenyl group, an alkyl group, and a (meth) acryl group is provided in a pattern on the substrate in advance, A method for manufacturing an LED package, comprising: mounting an LED chip at a location where a layer including the LED chip is provided; and sealing a portion where the LED chip is mounted with a sealing material containing a phosphor.