JP4325645B2 - Transfer mold tablet, manufacturing method thereof, light emitting device and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone resin-based tablet capable of coating a light-emitting device therewith using a conventional molding machine. <P>SOLUTION: The tablet for transfer molding is based on a curable silicone resin composition comprising (A) an organopolysiloxane of resin structure composed of R<SP>1</SP>SiO<SB>1.5</SB>units, R<SP>2</SP><SB>2</SB>SiO units and R<SP>3</SP><SB>a</SB>R<SP>4</SP><SB>b</SB>SiO<SB>(4-a-b)/2</SB>units ( wherein, R<SP>1</SP>to R<SP>3</SP>are each methyl, phenyl or the like; R<SP>4</SP>is vinyl or the like; (a) is 0-2; and b is 1 or 2, wherein (a+b) is 2 or 3 ), wherein the recurring number of the R<SP>2</SP><SB>2</SB>SiO units is 5-300, (B) an organohydrogenpolysiloxane of resin structure composed of R<SP>1</SP>SiO<SB>1.5</SB>units, R<SP>2</SP><SB>2</SB>SiO units and R<SP>3</SP><SB>c</SB>H<SB>d</SB>SiO<SB>(4-c-d)/2</SB>units( wherein, c is 0-2; and d is 1 or 2, wherein (c+d) is 2 or 3 ), wherein the recurring number of the R<SP>2</SP><SB>2</SB>SiO units is 5-300 and (C) a platinum group-based catalyst. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a light emitting device used for a lighting fixture, a display, a backlight of a mobile phone, a moving image illumination auxiliary light source, other general consumer light sources, a manufacturing method thereof, and the like.

  A light-emitting device using a light-emitting element emits light with a small color, high power efficiency, and vivid colors. In addition, since this light emitting element is a semiconductor element, there is no fear of a broken ball. Further, it has excellent initial driving characteristics and is strong against vibration and repeated on / off lighting. Because of such excellent characteristics, light-emitting devices using light-emitting elements such as light-emitting diodes (LEDs) and laser diodes (LDs) are used as various light sources.

Conventionally, a white light emitting device is known that is covered with a resin lens in which a YAG phosphor is dispersed (see, for example, Patent Document 1). In this light emitting device, a blue LED chip is covered with a lens in which a YAG phosphor made of a (Y, Gd) ₃ Al ₅ O ₁₂ : Ce composition that emits yellow light is dispersed in an epoxy resin. This lens is formed by transfer molding.

  In addition, a method for manufacturing a light emitting device using a transfer mold is disclosed (for example, see Patent Documents 2 and 3). All of these use an epoxy resin as a mold member for covering the light emitting element chip.

  In the conventional light-emitting device, after forming a mold member by transfer molding, the mold member is cut into individual light-emitting devices. Epoxy resins have the advantage that they can be easily cut.

Japanese Patent Laid-Open No. 2002-50798 JP 2002-76444 A JP 2005-145049 A

  However, due to recent technological development, the output of the light emitting element chip has been increased, and there is a problem that conventional epoxy resins have poor light resistance and heat resistance.

  In addition, as a resin used for transfer molding, there is a document in which an epoxy resin and a silicone resin are described in the same row, but a silicone resin is softer than an epoxy resin, and a mold member cannot be cut after transfer molding. The problem is obvious and not commercialized.

  In view of the above, an object of the present invention is to provide a light emitting device having excellent light resistance and heat resistance. It is another object of the present invention to provide a method for manufacturing a light emitting device that is excellent in mass productivity.

In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, the present invention has been completed.
<Tablet>

The present invention relates to a tablet for transfer molding used in a light emitting device, comprising (A) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit. (However, R ¹ , R ² and R ³ independently represent a methyl group, an ethyl group, a propyl group, a cyclohexyl group or a phenyl group, R ⁴ represents a vinyl group or an allyl group, and a is 0, 1 or 2. , B is 1 or 2, and a + b is 2 or 3), an organopolysiloxane having a resin structure in which the number of repeating R ² ₂ SiO units is 5 to 300,
(B) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _c H _d SiO _{(4-cd) / 2} unit (provided that R ¹ , R ² and R ³ are as described above, (c is 0, 1 or 2, d is 1 or 2, and c + d is 2 or 3), and the resin structure organohydrogenpolysiloxane has a repeating number of 5 to 300 R ² ₂ SiO units: (A) The amount of hydrogen atoms bonded to silicon atoms in component (B) relative to the vinyl group or allyl group in component in an molar ratio of 0.1-4.0, and (C) platinum group metal catalyst: Effective amount of curing,
Provided is a tablet for transfer molding used for coating a light-emitting element, comprising a curable silicone resin composition comprising This tablet is suitable for mass production of light emitting devices suitable for transfer molding and having excellent light resistance.

In the tablet, it is preferable that the curable silicone resin composition further contains at least one of a fluorescent substance and a filler. When the composition contains a fluorescent substance, the emission wavelength can be adjusted. Moreover, when this composition contains a filler, cutting of a molded object becomes easy and the dimensional stability after cutting becomes favorable.
<Light emitting device>

  The present invention also provides a light emitting device comprising a cured silicone product having a Shore D hardness of 30 or more obtained by curing the curable silicone resin composition. When the silicone cured product has such hardness, it can be separated into pieces by cutting.

  The cured product preferably has at least one dicing surface. As a result, the light emitting device can be miniaturized. That is, it is because the protrusion of the board | substrate from the said hardened | cured material can be eliminated.

  The curable silicone resin composition preferably contains a fluorescent material. Thereby, a desired color tone can be realized.

  It is preferable that the component (A) and / or the component (B) of the curable silicone resin composition contain a silanol group. Thereby, adhesiveness with the other structural member of the hardened | cured material obtained improves.

<Tablet manufacturing method (dry method)>
The present invention is also a method for producing a tablet for transfer molding used for coating a light emitting device,
Preparing a silicone composition containing at least one of a fluorescent material and a filler;
A step of forming a tablet by molding the silicone composition thus prepared under pressure,
A method for producing a tablet characterized by comprising: Such a tablet has an advantage of enabling a manufacturing method of a light emitting device excellent in mass productivity.

<Light emitting device (dry method)>
Therefore, the present invention is also a method for manufacturing a light emitting device in which a light emitting element mounted on a substrate is covered with a cured silicone product,
Preparing a silicone composition containing at least one of a fluorescent material and a filler;
A step of forming a tablet by molding the silicone composition thus prepared under pressure,
Transferring the tablet around the light emitting element mounted on the substrate;
Curing the transfer-molded composition to convert to a silicone cured product having a Shore D hardness of 30 or more;
A method for manufacturing a light-emitting device is provided. As a result, a method for manufacturing a light emitting device excellent in mass productivity can be provided. In addition, a light-emitting device having excellent light resistance and heat resistance can be provided.

  In the manufacturing method of the said light-emitting device, it is preferable that the said silicone composition is a curable silicone resin composition formed by containing the (A) component, (B), and (C) component mentioned above. Thereby, it is possible to provide a light emitting device that is particularly excellent in light resistance and heat resistance. In addition, since the composition is solid or semi-solid at room temperature, transfer molding can be easily performed by using an existing transfer molding apparatus that has been conventionally used for solid epoxy resins without change.

  When the silicone composition contains a fluorescent material, the amount of the fluorescent material is preferably 1 to 50% by weight, more preferably, for producing a white LED, for example, in adjusting the color tone in the silicone composition. Is in the range of 3 to 20% by weight.

  When the silicone composition contains a filler, the amount of the filler is preferably 80% by weight or less in the silicone composition from the viewpoint of easy cutting of the mold member to be obtained and dimensional stability after cutting. More preferably, it is 10 to 60% by weight.

  In the step of producing the tablet, the silicone composition is preferably 4.9 MPa to 29.4 MPa, more preferably 6 MPa to 20 MPa, from the dimensional stability of the resulting tablet and the stability of the resin moldability. It is preferable to produce a tablet by molding under the pressure of

  The manufacturing method preferably further includes a step of cutting the obtained cured silicone product by dicing. Thus, a plurality of light emitting devices can be manufactured in a short time.

  It is preferable that at least a part of the light emitting element is covered with at least one of a fluorescent substance-containing resin, a fluorescent substance-containing glass, a fluorescent substance-free resin, and a fluorescent substance-free glass. By having the fluorescent material, the color tone can be further changed. Moreover, it can coat | cover with a harder thing than an inner side.

<Tablet manufacturing method (wet method)>
The present invention also comprises a silicone composition containing at least one component of an alkenyl group-containing organopolysiloxane as a main agent, an organohydrogenpolysiloxane as a cross-linking agent, a platinum group metal catalyst, and a fluorescent material and a filler. A method for producing a tablet for transfer molding used in a light emitting device,
(A1) melting at least a part of at least one of the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane to obtain a melt;
(A2) solidifying the melt;
(A3) forming the obtained solidified product into a tablet;
Have
further,
(Α1) If the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane are present in the remainder, the remainder is added to the melt obtained in step (a1) before solidifying the melt. Process,
(Α2) The alkenyl group-containing organopolysiloxane and / or organo, which is subjected to melting before melting in the step (a1), with the platinum group metal catalyst and at least one component of the fluorescent material and filler. Adding to the hydrogen polysiloxane and / or adding to the melt obtained by melting after melting in step (a1) and / or in step (a3), Adding the solidified product before forming into a tablet; and
A method for producing the tablet having the above is provided.

In the above production method, at least a part of at least one of the alkenyl group-containing organopolysiloxane and the organohydrogenpolysiloxane is melted in the step (a1). Either one or both of both compounds may be used, and some or all of the molten compounds may be used. When a part is melted, the remainder is post-added to the melt obtained in step (α1).
The platinum group metal catalyst and at least one component of the fluorescent substance and filler are all added in one of the following three stages 1) to 3) as defined in (α2). Alternatively, it may be introduced in two or three stages.

1) Before melting in the step (a1), the alkenyl group-containing organopolysiloxane and / or organohydrogenpolysiloxane to be melted is added and melted together.
2) It is added to the melt obtained by melting after melting in the step (a1).
3) In the step (a3), before the solidified product is formed into a tablet, it is added to the solidified product and subjected to molding together.

In a preferred embodiment in which one or both of the fluorescent material and the filler are added, the alkenyl group-containing organopolysiloxane and the organohydrogenpolysiloxane are melted in their entirety, and the platinum group metal catalyst, the fluorescent material is added to the obtained melt. And all of the fillers are added, mixed with good stirring and solidified, and then tableted. If it carries out like this, a fluorescent substance and a filler will be disperse | distributed more uniformly in a silicone composition, As a result, after mold shaping | molding and separating into pieces, white LED with few dispersion | variation in chromaticity of light emission is obtained.

In another preferred embodiment in which one or both of the fluorescent material and the filler are added, these are added in two or more stages. That is, all the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane are melted, and the platinum group metal catalyst, a fluorescent substance and / or a part of the filler are added to the resulting melt, and the mixture is thoroughly stirred. Then, it is solidified, and the remainder of the platinum group metal catalyst, fluorescent substance and / or filler is added before tablet formation, and then the tablet is formed. This embodiment has an advantage that the content of the fluorescent material in the obtained tablet can be easily adjusted immediately before tableting, and the chromaticity of the LED can be easily adjusted.

  In addition, the above-mentioned rule of addition is applied independently to both the fluorescent substance and filler components, and they may be added in separate steps or may be added together.

The present invention further comprises a silicone composition containing at least one component of an alkenyl group-containing organopolysiloxane as a main agent, an organohydrogenpolysiloxane as a cross-linking agent, a platinum group metal catalyst, and a fluorescent material and a filler. A method for producing a tablet for transfer molding used in a light emitting device,
(B1) melting at least a part of at least one of the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane to obtain a melt;
(B2) a step of solidifying the obtained melt and then pulverizing to obtain a pulverized product;
(B3) forming the obtained pulverized product into a tablet;
Have
further,
(Β1) When there is a remainder of the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane, the remainder is added to the pulverized product before forming the pulverized product into a tablet in step (b2). Process,
(Β2) The alkenyl group-containing organopolysiloxane and / or organo, which is subjected to melting before melting in the step (b1) of the platinum group metal catalyst and at least one component of the fluorescent material and filler. Add to the hydrogenpolysiloxane and / or add to the melt obtained by melting after melting in step (b1) and / or shape the crushed product into tablets in step (b3) Adding to the pulverized product before;
A method for producing the tablet having the above is provided.

  In the above production method, at least a part of at least one of the alkenyl group-containing organopolysiloxane and the organohydrogenpolysiloxane is melted in the step (b1). Either one or both of both compounds may be used, and some or all of the molten compounds may be used. When a part is melted, the remainder is added to the pulverized product in the step (β1).

The platinum group metal catalyst and at least one component of the fluorescent material and filler may be all added in one of the following three stages as defined in (β2): It may be introduced in two or three stages. That is,
1) Before melting in the step (b1), the alkenyl group-containing organopolysiloxane and / or organohydrogenpolysiloxane to be melted is added and melted together.
2) After the melting in the step (b1), it is added to the melt obtained by melting.
3) In the step (b3), the pulverized product is added to the pulverized product before it is formed into a tablet.

In a preferred embodiment in which one or both of the fluorescent material and the filler are added, the alkenyl group-containing organopolysiloxane and the organohydrogenpolysiloxane are melted in their entirety, and the platinum group metal catalyst, the fluorescent material is added to the obtained melt. And all of the fillers are added, mixed well with stirring and then solidified and then tableted. If it carries out like this, the fluorescent substance in a silicone composition and a filler will be disperse | distributed more uniformly, As a result, after mold shaping | molding and individualization, white LED with few dispersion | variation in chromaticity is made.

In another preferred embodiment in which one or both of the fluorescent material and the filler are added, these are added in two or more stages. That is, all the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane are melted, and the platinum group metal catalyst, a fluorescent substance and / or a part of the filler are added to the resulting melt, and the mixture is thoroughly stirred. After solidification, the mixture is pulverized to obtain a pulverized product. The remainder of the platinum group metal catalyst, fluorescent substance and / or filler is added thereto, and then a tablet is formed. This embodiment has an advantage that the content of the fluorescent material in the obtained tablet can be easily adjusted immediately before tableting, and the chromaticity of the LED can be easily adjusted.

  This rule of addition is applied independently to both the fluorescent substance and filler components, and they may be added in separate stages or together.

According to these tablet manufacturing methods, the main component constituting the silicone composition, the crosslinking agent, the platinum group metal catalyst, and at least one of the fluorescent substance and the filler can be divided into a plurality of stages, In particular, since it can be blended even after it is once solidified, the blending amount can be adjusted. This can be easily adjusted further by taking a fluorescent substance as an example.
The step of melting and the step of adjusting the silicone composition can be performed almost simultaneously. Thereby, it can manufacture simply.
Tablets obtained by these production methods have an advantage of enabling a production method of a light emitting device excellent in mass productivity.

<Method for Manufacturing Light Emitting Device (Wet Method)>
Therefore, the present invention also provides the following method for manufacturing a light-emitting device using the above-described tablet manufacturing method.

That is, the present invention is a method for manufacturing a light emitting device in which a light emitting element mounted on a substrate is covered with a cured silicone,
Curing of a silicone composition in which the silicone cured product contains at least one component of an alkenyl group-containing organopolysiloxane as a main agent, an organohydrogenpolysiloxane as a cross-linking agent, a platinum group metal catalyst, and a fluorescent material and a filler. Is a thing,
(A1) melting at least part of at least one of the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane to obtain a melt;
(A2) solidifying the melt;
(A3) a step of molding the obtained solidified product into a tablet;
(A4) transferring the tablet to the substrate and converting it to a silicone cured product;
(A5) mounting the light emitting element on the substrate before the transfer molding or after the transfer molding;
Have
further,
(Α1) If the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane are present in the remainder, the remainder is added to the melt obtained in step (a1) before solidifying the melt. Process,
(Α2) The alkenyl group-containing organopolysiloxane and / or organohydro, which is subjected to melting before melting in the step (a1), and the platinum group metal catalyst and at least one component of the fluorescent material and filler. And / or added to the melt obtained by melting after melting in step (a1) and / or in step (a3), the solidified product is added to the solidified product. Before molding into a tablet, and
A method for manufacturing a light-emitting device is provided. According to this method, a light-emitting device in which a light-emitting element is covered with a silicone cured product in which a fluorescent material and a filler are uniformly dispersed can be manufactured with high mass productivity.

Furthermore, the present invention is a method for manufacturing a light emitting device in which a light emitting element mounted on a substrate is covered with a cured silicone,
Curing of a silicone composition in which the silicone cured product contains at least one component of an alkenyl group-containing organopolysiloxane as a main agent, an organohydrogenpolysiloxane as a cross-linking agent, a platinum group metal catalyst, and a fluorescent material and a filler. Is a thing,
(B1) melting at least a part of at least one of the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane to obtain a melt;
(B2) a step of solidifying the obtained melt and then pulverizing to obtain a pulverized product;
(B3) forming the obtained pulverized product into a tablet;
(B4) a step of transfer-molding the tablet onto the substrate to convert it into a silicone cured product;
(B5) mounting the light emitting element on the substrate before the transfer molding or after the transfer molding;
Have
further,
(Β1) When there is a remainder of the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane, the remainder is added to the pulverized product before forming the pulverized product into a tablet in step (b2). Process,
(Β2) The alkenyl group-containing organopolysiloxane and / or organo, which is subjected to melting before melting in the step (b1) of the platinum group metal catalyst and at least one component of the fluorescent material and filler. Add to the hydrogenpolysiloxane and / or add to the melt obtained by melting after melting in step (b1) and / or shape the crushed product into tablets in step (b3) Adding to the pulverized product before;
There is also provided a method for manufacturing a light emitting device characterized by comprising: According to this method, a light-emitting device in which a light-emitting element is covered with a silicone cured product in which a fluorescent material and a filler are uniformly dispersed can be manufactured with high mass productivity.

  The alkenyl group-containing organopolysiloxane constituting the silicone composition used in the method for producing a tablet and the method for producing a light emitting device is an organopolysiloxane having a resin structure as the component (A), and the organo The hydrogen polysiloxane is preferably an organohydrogenpolysiloxane having a resin structure as the component (B). At this time, the silicone composition is suitable for transfer molding as described above, and is useful for producing a light-emitting device excellent in light resistance and heat resistance with high mass productivity.

  Even in this production method, when the silicone composition contains a fluorescent material, the amount of the fluorescent material is in the range of 1 to 50% by weight, more preferably 3 to 20% by weight in the silicone composition. Is preferred. Further, when a filler is contained, the amount of the filler is preferably 80% by weight or less, more preferably 10 to 60% by weight with respect to the silicone composition. The reason is as described above.

The manufacturing method preferably further includes a step of cutting the obtained cured silicone product by dicing. Thereby, a large number of light emitting devices can be obtained at a time.
In the above manufacturing method, at least a part of the light emitting element is covered with at least one of a fluorescent substance-containing resin, a fluorescent substance-containing glass, a fluorescent substance-free resin, and a fluorescent substance-free glass. It is preferable. By having the fluorescent material, the color tone can be further changed. Moreover, it can coat | cover with a harder thing than an inner side.

  With the transfer molding tablet of the present invention, the transfer molding molding apparatus conventionally used for epoxy resins can be used as it is in the method for manufacturing a light emitting device. Therefore, a light emitting device excellent in light resistance and heat resistance can be mass-produced and high productivity can be realized. In addition, a light-emitting device with excellent mass productivity can be provided. The effects of the various embodiments of the present invention are apparent from the foregoing and the following description.

  Hereinafter, a light-emitting device and a manufacturing method thereof according to the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to this embodiment and example.

-Silicone composition-
As a typical silicone composition used for this invention, the curable silicone resin composition which has the said (A), (B) and (C) component essential is mentioned. Each of these components will be described.

(A) Resin-structured organopolysiloxane The resin-structured (ie, three-dimensional network) organopolysiloxane, which is an important component of the composition of the present invention, comprises (A) R ¹ SiO _1.5 units, R ² ₂ SiO Unit, and R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit (provided that R ¹ , R ² and R ³ independently represent a methyl group, an ethyl group, a propyl group, a cyclohexyl group or a phenyl group) R ⁴ represents a vinyl group or an allyl group, a is 0, 1 or 2, b is 1 or 2, and a + b is 2 or 3, and the number of repeating R ² ₂ SiO units is 5 to 300. It is an organopolysiloxane. The number of repeating R ² ₂ SiO units is 5 to 300, preferably 10 to 300, more preferably 15 to 200, and still more preferably 20 to 100.
In the above, the number of repetitions of R ² ₂ SiO units is 5 to 300 amino means that the structure R ² ₂ SiO units are repeated 5 to 300 pieces in succession is present. That is, in the molecule of the component (A), the formula (1):

（１）
（但し、ｍは５〜３００の整数）
で表される直鎖状ジオルガノポリシロキサン連鎖構造が存在していることを意味する。

(1)
(Where m is an integer from 5 to 300)
It means that a linear diorganopolysiloxane chain structure represented by

The R ² ₂ SiO unit may be present in the component (A) without constituting the structure represented by the formula (1) (for example, alone or in a chain structure of 4 or less). However, 50 mol% or more (50 to 100 mol%), preferably 80 mol% or more (80 to 100 mol%) of the entire R ² ₂ SiO unit present in the component (A) is represented by the formula (1). It is desirable to exist in the structure.

Here, the R ² ₂ SiO unit forms a chain polymer, and by introducing the R ¹ SiO _1.5 unit into this, the chain polymer can be branched or three-dimensional networked. R ⁴ (vinyl group or allyl group) in R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit is R ³ _c H _d SiO _{(4-cd) / 2} unit of component (B) described later A cured product is formed by a hydrosilylation addition reaction with a hydrogen atom (ie, SiH group) bonded to a silicon atom.

The proportion of each unit constituting the component (A) is preferably from the viewpoint of the properties (particularly physical strength) of the obtained cured product,
R ¹ SiO _1.5 units, from 90 to 24 mol%, more preferably, from 70 to 28 mol%,
R ² ₂ SiO unit is 75-9 mol%, more preferably 70-20 mol%
R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit is 50 to 1 mol%, more preferably 10 to 2 mol%.
(However, the total of these three units is 100 mol%)
It is.

In this specification, the organopolysiloxane has “resin structure” or “resin-like” means that the ratio of trifunctional siloxane units R ¹ SiO _1.5 units to all siloxane units constituting the organopolysiloxane is It means 20 mol% or more and a three-dimensional network siloxane structure is formed.

  Moreover, the polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC) of this (A) component is usually in the range of 3,000 to 1,000,000, particularly 10,000 to 100,000. Since the component (A) is solid or semi-solid at normal temperature, it is preferable from the viewpoint of workability and curability.

  The organopolysiloxane having a resin structure as the component (A) is prepared by converting a compound as a raw material of each unit into the above-mentioned ratio in the product from which each unit is obtained by a method well known to those skilled in the art. It can synthesize | combine by combining, for example, performing cohydrolysis condensation in presence of an acid.

Here, as raw materials for the R ¹ SiO _1.5 unit, MeSiCl ₃ , EtSiCl ₃ , PhSiCl ₃ (Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, the same shall apply hereinafter), propyltrichlorosilane, cyclohexyltri Examples include chlorosilane and alkoxysilane such as methoxysilane corresponding to each chlorosilane.

As a raw material of the R ² ₂ SiO unit,
ClMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ Cl,
HOMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ OH,
HOMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ OH,
HOMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ OH,
MeOMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ OMe,
MeOMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ OMe,
MeOMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ OMe
(However, m = integer of 5-150, n = integer of 5-300)
Etc. can be illustrated.

R ³ _a R ⁴ _b SiO _{(4-ab) / 2} units are composed of R ³ R ⁴ SiO units, R ³ ₂ R ⁴ SiO _0.5 units, R ⁴ ₂ SiO units, and R ³ R ⁴ ₂ SiO _0.5 units. It shows that it is an arbitrary combination of one or two or more kinds of siloxane units selected, and the raw materials thereof are Me ₂ ViSiCl, MeViSiCl ₂ , Ph ₂ ViSiCl (Vi represents a vinyl group, the same applies hereinafter), PhViSiCl. ₂ and alkoxysilanes such as methoxysilane corresponding to the respective chlorosilanes.

In the component (A), R ¹ SiO _1.5 units, R ² ₂ SiO units and / or R ³ _a R ⁴ _b SiO _{(4-ab) / 2} units are by-produced during the cohydrolysis and condensation reaction. The silanol group-containing siloxane unit is usually contained in an amount of about 10 mol% or less (0 to 10 mol%), preferably about 5 mol% or less (0 to 5 mol%) based on all siloxane units in component (A). It may be a thing. Silanol group-containing siloxane units corresponding to the above siloxane units include R ¹ (HO) SiO units, R ¹ (HO) ₂ SiO _0.5 units, R ² ₂ (HO) SiO _0.5 units, R ³ _a R ⁴ _b ( HO) SiO _{(3-ab) / 2} units, R ³ _a R ⁴ _b (HO) ₂ SiO _{(2-ab) / 2} units (where a is 0 or 1, b is 1 or 2, a + b is 1 or 2).

(B) Resin-structured organohydrogenpolysiloxane A resin-structured (ie, three-dimensional network) organohydrogenpolysiloxane, which is an important component of the composition of the present invention, has R ¹ SiO _1.5 units, R ² ₂ SiO unit and R ³ _c H _d SiO _{(4-cd) / 2} unit (provided that R ¹ , R ² and R ³ are as described above, c is 0, 1 or 2 and d is 1) Or 2 and c + d is 2 or 3, and the number of repeating R ² ₂ SiO units is 5 to 300. The number of repeating R ² ₂ SiO units is preferably 10 to 300, more preferably Is 15 to 200, more preferably 20 to 100.
In the above, the number of repetitions of R ² ₂ SiO units is 5 to 300 amino means that the structure R ² ₂ SiO units are repeated 5 to 300 pieces in succession is present. That is, as in the case of the component (A), the formula (1):

(1)
It means that a linear diorganopolysiloxane chain structure represented by

The R ² ₂ SiO unit may exist in the component (B) without constituting the structure represented by the formula (1) (for example, each alone or in a chain structure of 4 or less). However, 50 mol% or more (50 to 100 mol%), preferably 80 mol% or more (80 to 100 mol%) of the entire R ² ₂ SiO unit present in the component (B) is represented by the formula (1). It is desirable to exist in the structure.

In this case, the functions of the R ¹ SiO _1.5 unit, the R ² ₂ SiO unit, and the R ³ _c H _d SiO _{(4-cd) / 2} unit are as described for the component (A).

The proportion of each unit constituting the component (B) is preferably from the viewpoint of the properties (particularly physical strength) of the obtained cured product,
R ¹ SiO _1.5 units, from 90 to 24 mol%, more preferably, from 70 to 28 mol%,
R ² ₂ SiO unit is 75-9 mol%, more preferably 70-20 mol%
R ³ _c H _d SiO _{(4-cd) / 2} unit is 50 to 1 mol%, more preferably 10 to 2 mol%.
(However, the total of these three units is 100 mol%)
It is.

  Moreover, the polystyrene conversion weight average molecular weight by GPC of this (B) component is usually in the range of 3,000 to 1,000,000, particularly 10,000 to 100,000. From the point of view, it is preferable.

  Such a resin-structured organohydrogenpolysiloxane is prepared by a method well known to those skilled in the art so that the compound as a raw material of each unit is in the above-mentioned ratio in the product from which each unit is obtained. They can be synthesized by combination and cohydrolysis.

Here, examples of the raw material of the R ¹ SiO _1.5 unit include MeSiCl ₃ , EtSiCl ₃ , PhSiCl ₃ , propyltrichlorosilane, cyclohexyltrichlorosilane, and alkoxysilanes such as methoxysilane corresponding to each chlorosilane.

As a raw material of the R ² ₂ SiO unit,
ClMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ Cl,
HOMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ OH,
HOMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ OH,
HOMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ OH,
MeOMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ OMe,
MeOMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ OMe,
MeOMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ OMe
(However, m = integer of 5-150, n = integer of 5-300)
Etc. can be illustrated.

The R ³ _c H _d SiO _{(4-cd) / 2} unit is selected from R ³ R ⁵ SiO unit, R ³ ₂ R ⁵ SiO _0.5 unit, R ⁵ ₂ SiO unit, and R ³ R ⁵ ₂ SiO _0.5 unit. The raw material is Me ₂ HSiCl, MeHSiCl ₂ , Ph ₂ HSiCl, PhHSiCl ₂ , methoxysilane corresponding to each chlorosilane, etc. An alkoxysilane etc. can be illustrated. Silanol group-containing siloxane units corresponding to the above siloxane units include R ¹ (HO) SiO units, R ¹ (HO) ₂ SiO _0.5 units, R ² ₂ (HO) SiO _0.5 units, R ³ _c H _d (HO ) SiO _{(3-cd) / 2} units, R ³ _c H _d (HO) ₂ SiO _{(2-cd) / 2} units (where c is 0 or 1, d is 1 or 2, c + d is 1 or 2) .).

  The blending amount of the organohydrogenpolysiloxane of component (B) is such that the hydrogen atoms (SiH groups) bonded to silicon atoms in component (B) with respect to the total amount of vinyl groups and allyl groups in component (A) are moles. The amount is preferably 0.1 to 4.0, more preferably 0.5 to 3.0, and still more preferably 0.8 to 2.0. If it is less than 0.1, the curing reaction does not proceed and it is difficult to obtain a silicone cured product. If it exceeds 4.0, a large amount of unreacted SiH groups remain in the cured product. Causes changes over time.

In the component (B), by-products in the R ¹ SiO _1.5 unit, R ² ₂ SiO unit and / or R ³ _c H _d SiO _{(4-cd) / 2} unit are produced during the co-hydrolysis and condensation reaction. The silanol group-containing siloxane unit is usually present in an amount of 10 mol% or less (0 to 10 mol%), preferably 5 mol% or less (0 to 5 mol%) based on the total siloxane units in component (B). May be.

-(C) Platinum group metal-based catalyst This catalyst component is blended to cause the addition curing reaction of the composition of the present invention, and includes platinum-based, palladium-based, and rhodium-based catalysts. From the viewpoint of cost, platinum-based materials such as platinum, platinum black, chloroplatinic acid, for example, H ₂ PtCl ₆ · mH ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ · mH ₂ O, K ₂ PtCl ₄ , K ₂ Platinum compounds such as PtCl ₄ · mH ₂ O, PtO ₂ · mH ₂ O (m is a positive integer); and complexes of these with hydrocarbons such as olefins, alcohols or vinyl group-containing organopolysiloxanes Can do. These can be used singly or in combination of two or more. The compounding amount of these catalyst components may be an effective amount, that is, a so-called catalyst amount, and specifically, usually in terms of the mass of platinum group metal with respect to the total amount of the component (A) and the component (B). It is used in the range of 0.1 to 500 ppm, particularly preferably 0.5 to 100 ppm.

  In addition, especially when using said composition for sealing, coating | covering, etc. of light-emitting devices, such as an LED element, it does not contain the state (namely, fluorescent substance, filler, etc.) which consists of (A)-(C) component. The cured product obtained by curing the composition in the state) is preferably 90% or more (that is, 90 to 100%) in the visible light region from 400 nm, and light transmission of 92% or more (92 to 100%). It is more preferable to have a rate.

-Other compounding agents In addition to the above-described components (A) to (C), various additives known per se can be blended with the above-described composition as necessary. Hereinafter, such optional components will be described.

..Fluorescent substance The fluorescent substance may be any substance that absorbs light from a semiconductor light emitting diode having a nitride-based semiconductor as a light emitting layer and converts it to light of a different wavelength. For example, nitride phosphors / oxynitride phosphors mainly activated by lanthanoid elements such as Eu and Ce, lanthanoid phosphors such as Eu, and alkalis mainly activated by transition metal elements such as Mn Earth halogen apatite phosphor, alkaline earth metal borate halogen phosphor, alkaline earth metal aluminate phosphor, alkaline earth silicate phosphor, alkaline earth sulfide phosphor, alkaline earth thiogallate phosphor , Alkaline earth silicon nitride phosphors, germanate phosphors, or lanthanoid elements such as rare earth aluminate phosphors, rare earth silicate phosphors or Eu that are mainly activated by lanthanoid elements such as Ce This is at least one selected from organic and organic complex phosphors activated mainly, Ca—Al—Si—O—N-based oxynitride glass phosphors, etc. It is preferred. As specific examples, the following phosphors can be used, but are not limited thereto.

A nitride-based phosphor mainly activated by a lanthanoid element such as Eu or Ce is M ₂ Si ₅ N ₈ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn) .)and so on. In addition to M ₂ Si ₅ N ₈ : Eu, MSi ₇ N ₁₀ : Eu, M _1.8 Si ₅ O _0.2 N ₈ : Eu, M _0.9 Si ₇ O _0.1 N ₁₀ : Eu (M Is at least one selected from Sr, Ca, Ba, Mg, and Zn.

An oxynitride phosphor mainly activated by a lanthanoid element such as Eu or Ce is MSi ₂ O ₂ N ₂ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, and Zn). There is.)

Alkaline earth halogen apatite phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include M ₅ (PO ₄ ) ₃ X: R (M is Sr, Ca, Ba, X is at least one selected from F, Cl, Br, and I. R is at least one of Eu, Mn, Eu and Mn. .)and so on.

In the alkaline earth metal borate phosphor, M ₂ B ₅ O ₉ X: R (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is F, Cl, And at least one selected from Br and I. R is Eu, Mn, or any one of Eu and Mn.).

Alkaline earth metal aluminate phosphors include SrAl ₂ O ₄ : R, Sr ₄ Al ₁₄ O ₂₅ : R, CaAl ₂ O ₄ : R, BaMg ₂ Al ₁₆ O ₂₇ : R, BaMg ₂ Al ₁₆ O ₁₂ : R, BaMgAl ₁₀ O ₁₇ : R (R is one or more of Eu, Mn, Eu and Mn).

Examples of the alkaline earth sulfide phosphor include La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, and Gd ₂ O ₂ S: Eu.

Examples of rare earth aluminate phosphors mainly activated with lanthanoid elements such as Ce include Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y _{3 (Al 0.8 Ga 0.2) 5 O} 12: Ce, and the like (Y, Gd) 3 (Al , Ga) YAG -based phosphor represented by the composition formula of _{5 O 12.} Further, there are Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which a part or all of Y is substituted with Tb, Lu or the like.

Other phosphors include ZnS: Eu, Zn ₂ GeO ₄ : Mn, MGa ₂ S ₄ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is F) , Cl, Br, or I.).

  The phosphor described above contains at least one selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti instead of Eu or in addition to Eu as desired. You can also

The Ca—Al—Si—O—N-based oxynitride glass phosphor is expressed in terms of mol%, CaCO ₃ is converted to CaO, 20 to 50 mol%, Al ₂ O ₃ is 0 to 30 mol%, SiO 25 to 60 mol%, AlN 5 to 50 mol%, rare earth oxide or transition metal oxide 0.1 to 20 mol%, and oxynitride glass having a total of 5 components of 100 mol% as a base material This is a phosphor. In addition, in the phosphor using oxynitride glass as a base material, the nitrogen content is preferably 15 wt% or less, and other rare earth element ions serving as a sensitizer in addition to rare earth oxide ions are used as rare earth oxides. It is preferable to contain as a co-activator in content in the range of 0.1-10 mol% in fluorescent glass.

  Moreover, it is fluorescent substance other than the said fluorescent substance, Comprising: The fluorescent substance which has the same performance and effect can also be used.

..Fillers As fillers, for example, reinforcing inorganic fillers such as fumed silica and fumed titanium dioxide, non-reinforcing inorganic fillers such as calcium carbonate, calcium silicate, titanium dioxide, and zinc oxide, (A) and (B) It can mix | blend suitably in the range of 600 mass parts or less (0-600 mass parts) per 100 mass parts of total amounts of a component.

.. Adhesion aid In addition, in order to impart adhesion to the composition, hydrogen atoms bonded to silicon atoms (SiH groups) and alkenyl groups bonded to silicon atoms (for example, Si-CH = CH) in one molecule ₂ groups), an alkoxysilyl group (for example, trimethoxysilyl group), and an epoxy group (for example, glycidoxypropyl group, 3,4-epoxycyclohexylethyl group) at least two, preferably two 3 types of linear or cyclic organosiloxane oligomers containing 4 to 50, preferably about 4 to 20 silicon atoms, organooxysilyl-modified isocyanurate compounds represented by the following general formula (2) and / or Adhesion aids such as hydrolyzed condensates (organosiloxane-modified isocyanurate compounds) are optionally blended as required. It is possible.

(In the formula, R ⁶ represents the following formula (3):

Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, but at least one is an organic group of the formula (3), and R ⁷ is a hydrogen atom or a carbon atom number 1-6. Monovalent hydrocarbon group, s is an integer of 1-6, especially 1-4. )

In this case, the monovalent hydrocarbon group containing an aliphatic unsaturated bond represented by R ⁶ includes a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, and the like. And a cycloalkenyl group having 6 to 8 carbon atoms, such as an alkenyl group having 2 to 6 carbon atoms, particularly a cyclohexenyl group, and the like. Examples of the monovalent hydrocarbon group represented by R ⁷ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group and other alkyl groups, cyclohexyl, and the like. Cycloalkyl groups such as groups, monovalent hydrocarbon groups having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms such as aryl groups such as alkenyl groups, cycloalkenyl groups and phenyl groups exemplified as R ⁶ above. Is an alkyl group.

  Examples of the adhesion assistant include compounds represented by the following formula.

(In the formula, g and h are each an integer of 1 to 49, provided that g + h is 2 to 50, preferably 4 to 20.)

  Among such organosilicon compounds, compounds having particularly excellent adhesion of the resulting cured product include organic compounds having silicon-bonded alkoxy groups and alkenyl groups or silicon-bonded hydrogen atoms (SiH groups) in one molecule. It is a silicon compound.

  In the above composition, the amount of the adhesion assistant (optional component) is usually 10 parts by mass or less (that is, 0 to 10 parts by mass), preferably 100 parts by mass in total of the component (A) and the component (B). Can be blended in an amount of 0.1 to 8 parts by mass, more preferably about 0.2 to 5 parts by mass. If the blending amount is too small, improvement in adhesion may not be obtained, and if it is too large, the hardness and surface tackiness of the cured product may be adversely affected.

  The above-mentioned silicone composition is prepared by uniformly mixing the above-described components. Usually, the silicone composition is stored in two liquids so that curing does not proceed. Do. Of course, a small amount of a curing inhibitor such as acetylene alcohol can be added and used as one liquid. This composition is cured immediately by heating, if necessary, to form a flexible cured product having high hardness and no surface tack.

  The curing conditions at the time of molding are usually 50 to 200 ° C., particularly 70 to 180 ° C. and 1 to 30 minutes, particularly 2 to 10 minutes. Further, post-curing can be performed at 50 to 200 ° C., particularly 70 to 180 ° C. for 0.1 to 10 hours, particularly 1 to 4 hours.

-Representative embodiment-
Next, typical embodiments of the present invention will be described with reference to the attached FIG. However, the scope of the present invention is not limited to the example of FIG. FIG. 1 is a cross-sectional view of a light-emitting device having a typical well-known package structure. 1 is an insulating substrate, 2 and 3 are electrodes and circuit wiring, 4 is a light-emitting diode, 5 is a bonding wire, and 6 is a phosphor dispersed. A sealed body made of a cured silicone resin. In the following description of the embodiments, the components (A), (B) and (C) mean the components of the curable silicone resin composition described above.

Embodiment 1
(Tablet → Molding → Individualization)
1. (A), (B) and (C) each component is preliminarily blended into a powdery curable silicone resin composition, which is convenient for mass production, and has problems such as bubbles in the final product. In order to remove the above, it is placed in a mold having a predetermined shape, and is pressed with an appropriate pressure, for example, a pressure of 4.9 to 29.4 MPa, and processed into a tablet.
2. Next, a silicone resin composition processed into a tablet shape using a transfer mold process in a package structure similar to the structure shown in FIG. 1, usually at 50 to 200 ° C., particularly at 70 to 180 ° C. for 1 to 30 minutes, especially The sealing body 6 can be molded by curing in 2 to 10 minutes. After the sealing body 6 is taken out from the mold, it can be cured at 50 to 200 ° C., particularly 70 to 180 ° C. for 0.1 to 10 hours, particularly 1 to 4 hours, if necessary.
3. After the curing is completed, a dicing process is performed to cut individual chip LED products according to the product pattern, and a desired chip LED can be obtained. In order to remove moisture generated in the dicing process and stabilize the product, baking may be performed at 60 to 180 ° C. for about 1 to 24 hours.

○ Embodiment 2
(Phosphor DRY blend->tablet->molding-> individualization)
1. Components (A), (B) and (C) are blended in advance, and are constant depending on the chromaticity level in which a powder-like phosphor is desired to be added to the powdery curable silicone resin composition to which no phosphor is added. The mixture is sufficiently stirred and mixed with a mixer or the like in a proportion, preferably 1 to 50% by weight after blending, more preferably 3 to 20% by weight.
2. After stirring and mixing, the mixture is put into a mold having a predetermined shape and pressed into an appropriate pressure, for example, 4.9 MPa to 29.4 MPa, and processed into a tablet.
3. Next, a curable silicone resin composition containing a phosphor processed into a tablet shape using a transfer mold process in a package structure similar to the structure shown in FIG. 1, usually 50 to 200 ° C., particularly 70 to The sealing body 6 can be formed by curing at 180 ° C. for 1 to 30 minutes, particularly 2 to 10 minutes. After taking out the sealing body from the mold, it can be cured at 50 to 200 ° C., particularly 70 to 180 ° C. for 0.1 to 10 hours, particularly 1 to 4 hours, if necessary.
4). An LED having a desired chromaticity level can be obtained by cutting into a predetermined size after completion of curing and dividing it into individual pieces.

○ Embodiment 3
(Agitation mixing of molten resin and phosphor → solidification → grinding → tableting → molding → individualization)
1. The solid silicone resin (A) component (main agent) and the solid silicone resin (B) (crosslinking agent) component are heated to the melting point of the resin component or higher and melted.
2. A predetermined amount of phosphor is stirred and dispersed in the melted silicone resin component using a mixer so as to be substantially uniform, an appropriate amount of platinum group metal catalyst (C) is added, and the mixture is uniformly dispersed with a mixer.
3. The silicone resin component in which the phosphor is dispersed is cooled to room temperature or lower and solidified.
4). After the solidified silicone resin composition containing the phosphor is pulverized, it is put into a mold having a predetermined shape and pressed into an appropriate pressure, for example, 4.9 MPa to 29.4 MPa to form a tablet. To do.
5. Next, a curable silicone resin composition containing a phosphor processed into a tablet shape using a transfer mold process in a package structure similar to the structure shown in FIG. 1, usually 50 to 200 ° C., particularly 70 to The sealing body 6 can be formed by curing at 180 ° C. for 1 to 30 minutes, particularly 2 to 10 minutes. After removing the sealing body 6 from the mold, it can be cured at 50 to 200 ° C., particularly 70 to 180 ° C. for 0.1 to 10 hours, particularly 1 to 4 hours, if necessary.
6). An LED having a desired chromaticity level can be obtained by cutting into a predetermined size after completion of curing and dividing it into individual pieces.

Embodiment 4
(Any component (A) or component (B) is melted and the phosphor is stirred and dispersed.)
When the curing reaction by the silicone resin component (A) and the component (B) and the platinum group metal catalyst (C) is extremely fast, that is, when curing is completed during melt mixing, the component (A) It is also possible to melt blend only one of the components (B) and stir and disperse the phosphor, then solidify and pulverize, and then dry blend the components (A) and (B) in a solid state. At this time, the platinum group metal catalyst (C) is mixed with the molten resin of the components (A) and (B). After the dry blended phosphor-containing silicone resin composition is tableted in the same manner as described in the first to third embodiments, the wavelength conversion encapsulant 6 can be formed using a transfer molding process. I can do it.

○ Embodiment 5
(LED composed of two or more resin layers)
The present invention is not limited to sealing the curable silicone resin composition comprising the above (A) to (C) alone, but as necessary, epoxy resin, other silicone resin, modified silicone resin, urethane resin In combination with a resin such as an oxetane resin, an acrylic resin, a polycarbonate resin, or a polyimide resin, an LED can be manufactured. Furthermore, glass can be used in addition to the resin. In the case of a combination with a plurality of resins, the phosphor may be mixed with a resin such as an epoxy resin, a silicone resin, a modified silicone resin, a urethane resin, an oxetane resin, an acrylic resin, a polycarbonate resin, or a polyimide resin as necessary. .

Each element which comprises the light-emitting device illustrated in FIG. 1 is demonstrated.
(Insulating substrate 1 / electrodes 2, 3)
The insulating substrate is not particularly limited as long as it is a material having appropriate mechanical strength and insulating properties. For example, a glass epoxy, a ceramic substrate, a metal substrate, or the like can be used. Moreover, what laminated | stacked the epoxy-type resin sheet on the multilayer may be used. The negative and positive electrodes formed on the insulating substrate are preferably metal layers containing Cu as a main component. For example, the negative and positive electrodes can be composed of Cu / Ni / Ag.

(Light-emitting diode 4 / phosphor)
The light emitting diode and the phosphor are not particularly limited as long as the phosphor can convert the wavelength of part or all of the light emitting diode. As an example, a description will be given of a combination of a light emitting diode and a phosphor suitable for forming a white light emitting device, which is currently in the highest demand.

・ Light emitting diode 4
As a light-emitting diode suitable for configuring a white light emitting device, the use of which using a nitride semiconductor _{(In X Al Y Ga 1-} X-Y N, 0 ≦ X, 0 ≦ Y, X + Y ≦ 1) Can do. This light emitting diode has In _x Ga _1-x N (0 <x <1) as a light emitting layer, and the light emission wavelength can be arbitrarily changed from about 365 nm to 650 nm depending on the degree of mixed crystal.

  In the case of emitting white light, considering the complementary color relationship with the light emitted from the phosphor, the light emission wavelength of the light emitting diode 8 is preferably set to 400 nm or more and 530 nm or less, and set to 420 nm or more and 490 nm or less. It is more preferable. An LED chip that emits light having a wavelength in the ultraviolet region shorter than 400 nm can also be applied by selecting the type of phosphor.

  In the light emitting devices of the first to fifth embodiments described above, an example in which the light emitting diode 4 that emits light from the electrode side is used, and the electrode of the light emitting diode 4 and the electrodes 2 and 3 on the insulating substrate 1 are wire bonded. Show. However, the present invention is not limited to this, and the light emitting diode 4 may be flip-chip bonded on the insulating substrate 1. Specifically, the light-emitting diode is placed so that the p-side electrode and the n-side electrode of the light-emitting diode 4 are opposed to the positive and negative electrodes formed on the insulating substrate 1, respectively. Each is mounted by bonding with a conductive adhesive member such as solder.

  The light emitting diode for flip chip bonding is basically configured in the same manner as the light emitting diode for wire bonding. For example, in the case of a nitride semiconductor light emitting device, a plurality of nitride semiconductor layers including n-type and p-type nitride semiconductor layers are stacked on one main surface of a light-transmitting substrate, and the uppermost p is formed. Forming a p-side electrode on the n-type nitride semiconductor layer (p-type contact layer) and removing the p-type nitride semiconductor layer to remove a portion of the p-type nitride semiconductor layer; An electrode is formed, and the other main surface of the light-transmitting substrate may be a main light extraction surface.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following examples, the viscosity is a value of 25 ° C. Moreover, a weight average molecular weight is a polystyrene conversion value by gel permeation chromatography (GPC). Ph represents a phenyl group, Me represents a methyl group, and Vi represents a vinyl group.

[Synthesis Example 1]
-Vinyl group-containing organopolysiloxane resin (A1)-
Organosilane represented by PhSiCl ₃ : 27 mol, ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 1 mol, MeViSiCl ₂ : 3 mol was dissolved in toluene solvent, dropped into water, co-hydrolyzed, further washed with water, alkali After neutralization and dehydration by washing, the solvent was stripped to synthesize a vinyl group-containing resin (A1). This resin had a weight average molecular weight of 62,000 and a melting point of 60 ° C.

[Synthesis Example 2]
-Hydrosilyl group-containing organopolysiloxane resin (B1)-
Organosilane represented by PhSiCl ₃ : 27 mol, ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 1 mol, MeHSiCl ₂ : 3 mol were dissolved in toluene solvent, dropped into water, co-hydrolyzed, further washed with water, alkali After neutralization and dehydration by washing, the solvent was stripped to synthesize a hydrosilyl group-containing resin (B1). This resin had a weight average molecular weight of 58,000 and a melting point of 58 ° C.

[Synthesis Example 3]
-Vinyl group-containing organopolysiloxane resin (A2)-
Organosilane represented by PhSiCl ₃ : 27 mol, ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 1 mol, Me ₂ ViSiCl: 3 mol dissolved in toluene solvent, dropped into water, cohydrolyzed, further washed with water, After neutralization and dehydration by alkali washing, the solvent was stripped to synthesize a vinyl group-containing resin (A2). The resin had a weight average molecular weight of 63,000 and a melting point of 63 ° C.

[Synthesis Example 4]
-Hydrosilyl group-containing organopolysiloxane resin (B2)-
Organosilane represented by PhSiCl ₃ : 27 mol, ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 1 mol, Me ₂ HSiCl: 3 mol dissolved in toluene solvent, dropped into water, cohydrolyzed, further washed with water, After neutralization and dehydration by alkali washing, the solvent was stripped to synthesize a hydrosilyl group-containing resin (B2). This resin had a weight average molecular weight of 57,000 and a melting point of 56 ° C.

[Example 1]
Vinyl group-containing resin (A1) of Synthesis Example 1: 189 g, Hydrosilyl group-containing resin (B1) of Synthesis Example 2: 189 g, acetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor: 0.2 g, octyl alcohol of chloroplatinic acid Denatured solution: The composition to which 0.1 g was added was thoroughly stirred with a planetary mixer heated to 60 ° C. to prepare a silicone resin composition. This composition was a plastic solid at 25 ° C.
[Example 2]
Vinyl group-containing resin (A1) of Synthesis Example 1: 189 g, Hydrosilyl group-containing resin (B1) of Synthesis Example 2: 189 g, acetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor: 0.2 g, octyl alcohol of chloroplatinic acid Denaturing solution: 90 parts by mass of the composition to which 0.1 g was added, and 10 parts by mass of a phosphor (YAG) having a particle size of 5 μm (average particle size) was added and stirred well with a planetary mixer heated to 60 ° C. Then, a silicone resin composition was prepared. This composition was a plastic solid at 25 ° C.

This composition was subjected to the following evaluation test.
1) Mechanical properties Compression molding was performed with a compression molding machine, and heat molding was performed at 150 ° C. for 5 minutes to obtain a cured product. Further, a material obtained by secondarily curing at 150 ° C. for 4 hours, in accordance with JIS K 6251 and JIS K 6253, tensile strength (0.2 mm thickness), hardness (measured using a type D spring tester) And the elongation (0.2 mm thickness) was measured.
2) Surface tackiness The tackiness of the surface of the cured product secondary-cured as described above was confirmed by finger touch. Further, the cured product was placed in a commercially available silver powder (average particle size: 5 μm), and after taking out, it was tested whether or not silver powder adhering to the surface like dust could be removed by blowing air.
3) Dispersion stability of phosphor The resin composition immediately after the above preparation is placed in a recess formed on an alumina substrate having a diameter of 6 mm, a center depth of 2 mm, and a bottom having a concave curved surface, and heated under the same conditions as above. The lens molding 21 having the shape shown in FIG. 2 was molded by curing. A part is cut out from each of the upper part 22 and the lower part 23 of this lens molding 21, and each is heated and ashed at 800 degreeC, The content (mass%) of the fluorescent substance in the obtained ash is measured, and upper part is measured. 22 and the content in the lower part 23 were compared. Further, after the composition was stored in a freezer at −20 ° C. for 3 months, the composition was molded into a lens molded product in the same manner as described above, and the phosphor contents in the upper part and the lower part were compared in the same manner. Thus, the dispersion stability of the phosphor was measured.
These measurement results are shown in Table 1.

[Example 3]
Vinyl group-containing resin (A-2) of Synthesis Example 3: 189 g, Hydrosilyl group-containing resin (B-2) of Synthesis Example 4: 189 g, acetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor: 0.2 g, platinum chloride An acid octyl alcohol-modified solution: To 70 parts by mass of a composition to which 0.1 g is added, after further adding 30 parts by mass of a phosphor (YAG) having a particle size of 5 μm (average particle size), these are heated to 60 ° C. The mixture was thoroughly stirred with a warmed planetary mixer to prepare a silicone resin composition. This composition was a plastic solid at 25 ° C. The composition was evaluated as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
Instead of the silicone resin composition prepared in Example 1, the main component is a vinyl group-containing organopolysiloxane resin that does not contain a linear diorganopolysiloxane chain structure having 5 to 300 repeating units and is liquid at room temperature. A phosphor (YAG) having the same particle diameter of 5 μm (average particle diameter) as in Example 1 with respect to 90 parts by mass of KJR-632 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a commercially available addition reaction curable silicone varnish. ) After adding 10 parts by mass, each property was evaluated in the same manner as in Example 1 for the composition well stirred with a planetary mixer heated to 60 ° C. The results are shown in Table 1.

[Comparative Example 2]
Instead of the silicone resin composition prepared in Example 1, the main component is a vinyl group-containing organopolysiloxane resin that does not contain a linear diorganopolysiloxane chain structure having 5 to 300 repeating units and is liquid at room temperature. A phosphor having the same particle diameter of 5 μm (average particle diameter) as in Example 1 with respect to 70 parts by mass of KJR-632L-1 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a commercially available addition reaction curable silicone varnish. After adding 30 parts by weight of (YAG), each property was evaluated in the same manner as in Example 1 for the composition well stirred with a planetary mixer heated to 60 ° C. The results are shown in Table 1.

(note)
* 1: Molar ratio of silicon atom-bonded hydrogen atom in hydrosilyl group-containing resin to silicon atom-bonded vinyl group in vinyl group-containing resin

[Example 4]
A blue light-emitting diode chip is mounted on a printed circuit board on which a circuit is formed, and is electrically connected with a conductive wire. It was cured in a mold at 150 ° C. for 15 minutes using a molding process. After taking out from the mold, it was cured at 150 ° C. for 4 hours as additional curing in an oven. After the additional curing, it was cut into a predetermined size using a dicing process to obtain LED pieces.

[Example 5]
The silicone resin composition prepared in Example 1 and 15 parts by mass of YAG phosphor were dry blended and then tableted. The resin tablet containing a phosphor was cured in a mold at 150 ° C. for 15 minutes using a transfer molding process. After taking out from the mold, it was cured at 150 ° C. for 4 hours as additional curing in an oven. After the additional curing, it was cut into a predetermined size using a dicing process to obtain individual pieces of white LEDs.

[Example 6]
A blue light emitting diode chip is mounted and fixed on a printed circuit board on which a circuit is formed, electrically connected with a conductive wire, and then a liquid silicone resin to which 25 parts by mass of YAG phosphor is added is used to surround the chip. Only coated. Thereafter, the solid silicone resin composition prepared in Example 1 was tableted into tablets and cured in a mold at 150 ° C. for 15 minutes using a transfer molding process. After taking out from the mold, it was cured at 150 ° C. for 4 hours as additional curing in an oven. After the additional curing, it was cut into a predetermined size using a dicing process to obtain individual pieces of white LEDs.
[Example 7]
After mounting a plurality of blue light-emitting diode chips on a substrate in a row (in this embodiment, in a row, but two or more in parallel) may be bonded and fixed and electrically connected with a conductive wire Using a liquid silicone resin composition to which a YAG phosphor was added, coating was performed so as to cover individual blue light emitting diode chips arranged in a row. Thereafter, the chip thus coated is placed in a dome-shaped mold having a substantially semicircular longitudinal cross section, and the solid silicone resin composition prepared in Example 1 is compressed into a tablet and coated by transfer molding. And cured. After the chip coated with the cured silicone resin was taken out from the mold, the coating resin was additionally cured in an oven. After the post-curing, it was cut into a predetermined size using a dicing process, and white LED pieces could be obtained. As for the shape of the separated white LED, a substantially hemispherical phosphor-containing silicone resin layer was formed around the chip, and a translucent substantially hemispherical silicone resin layer was formed on the outer periphery thereof.

Sectional drawing of the light-emitting device which has a typical package structure. The front view which shows the lens type molded object produced for the dispersion stability evaluation test of the fluorescent substance in a composition.

Explanation of symbols

1. 1. Insulating substrate 2. Electrode and wiring 3. Electrode and wiring 5. Light emitting diode Encapsulant 21. Lens molding 22. Upper 23. beneath

Claims (13)

(A) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit (provided that R ¹ , R ² and R ³ are each independently a methyl group, An ethyl group, a propyl group, a cyclohexyl group or a phenyl group, R ⁴ represents a vinyl group or an allyl group, a is 0, 1 or 2, b is 1 or 2, and a + b is 2 or 3. An organopolysiloxane having a resin structure in which the number of repeating R ² ₂ SiO units is 10 to 300;
(B) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _c H _d SiO _{(4-cd) / 2} unit (provided that R ¹ , R ² and R ³ are as described above, (c is 0, 1 or 2, d is 1 or 2, and c + d is 2 or 3), and the resin structure organohydrogenpolysiloxane has a repeating number of 5 to 300 R ² ₂ SiO units: (A) The quantity by which the hydrogen atom bonded to the silicon atom in the component (B) relative to the vinyl group or allyl group in the component is 0.1 to 4.0 in molar ratio ,
(C) platinum group metal catalyst: effective amount of curing, and
(E) A tablet for transfer molding used for coating a light-emitting element, comprising a curable silicone resin composition containing a fluorescent substance . The doublet according to claim 1, wherein the curable silicone resin composition further contains a filler .   A light-emitting device comprising a cured silicone product having a Shore D hardness of 30 or more obtained by curing the curable silicone resin composition according to claim 1.   The light emitting device according to claim 3, wherein the cured product has at least one dicing surface. The light emitting device according to claim 3 or 4, wherein the silicone resin composition contains a filler . The light emitting device according to any one of claims 3 to 5, wherein the component (A) and / or the component (B) in the silicone resin composition contains a silanol group . A method for producing a tablet for transfer molding used for coating a light emitting element,
Preparing a curable silicone resin composition according to claim 1;
A step of forming a tablet by molding the silicone resin composition thus prepared under pressure,
A method for producing a tablet, comprising: A method of manufacturing a light-emitting device in which a light-emitting element mounted on a substrate is covered with a silicone cured product,
Preparing a curable silicone resin composition according to claim 1 ;
A step of forming a tablet by molding the silicone resin composition thus prepared under pressure,
Transferring the tablet around the light emitting element mounted on the substrate;
Curing the transfer-molded composition to convert to a silicone cured product having a Shore D hardness of 30 or more;
A method for manufacturing a light-emitting device , comprising: The method of manufacturing a light emitting device according to claim 8, wherein the amount of the fluorescent substance in the silicone resin composition is in the range of 1 to 50% by weight of the silicone resin composition . The method for manufacturing a light emitting device according to claim 8 or 9 , wherein the silicone resin composition contains a filler, and the amount of the filler is less than 80% by weight of the silicone resin composition . In the process of making the tablet,
The method for manufacturing a light emitting device according to any one of claims 8 to 10, wherein the tablet is manufactured by molding the silicone resin composition under a pressure of 4.9 MPa to 29.4 MPa . Furthermore, the manufacturing method of the light-emitting device as described in any one of Claims 8 thru | or 11 which has the process of cut | disconnecting the obtained said silicone hardened | cured material by dicing . The at least part of the light emitting element is covered with at least one of a fluorescent substance-containing resin, a fluorescent substance-containing glass, a fluorescent substance-free resin, and a fluorescent substance-free glass. The manufacturing method of the light-emitting device as described in any one of thru | or 12.

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