JP4872296B2 - Silicone rubber-sealed light emitting device and method for manufacturing the light emitting device - Google Patents

Description

  The present invention relates to a silicone rubber sealed light emitting device, and more particularly to a silicone rubber sealed light emitting device in which tackiness of a sealing body made of silicone rubber is reduced, and a method for manufacturing the device.

It is known that a silicone rubber composition forms a cured product having excellent properties such as weather resistance and heat resistance, and rubber properties such as hardness and elongation.
Light-emitting diodes are sealed (molded) with cured silicone, but hard resin of silicone cured products is generally susceptible to cracking and bonding wire deformation, and soft rubber is dusty due to surface tack. And adhesion of the sealing resin (mold resin) in the parts feeder are likely to occur frequently. As a countermeasure, a general method is to use a soft rubber or gel type on the inside and coat the outside with a hard rubber or a hard resin (Patent Document 1). However, in this method, since a small amount of vinyl groups remain in the polymer after being cured, the soft rubber or soft gel is affected by the hard rubber or resin outside, and the soft rubber or gel inside the soft rubber over time. Therefore, the bonding wire is easily broken or deformed.

Japanese Patent Laid-Open No. 3-178433

  Accordingly, an object of the present invention is to provide a silicone rubber encapsulant that has a reduced surface tack property while stabilizing the characteristics as an elastic body of a cured soft rubber type silicone rubber used as an LED encapsulant. To provide a stationary light emitting device and a method for manufacturing the same.

  As a result of intensive studies, the present inventors have determined that the balance of silicon atom-bonded hydrogen atoms (Si-H) / silicon atom-bonded alkenyl groups involved in crosslinking as a soft rubber in the addition reaction curable liquid silicone rubber composition is SiH excess, And it discovered that the said subject can be solved by using the silicone rubber composition which gives the hardened | cured material which has a predetermined type A hardness after hardening, and coat | covering this soft rubber surface with the hard silicone resin which has a predetermined type D hardness. The present invention has been reached.

According to the present invention, first,
A package having a recess having a bottom surface and a side surface;
A light emitting diode placed on the bottom surface of the recess of the package;
A sealing body disposed in the recess of the package and sealing the light emitting diode;
A light emitting device comprising
The sealing body includes a first sealing member that covers the light emitting diode, and a second sealing member that covers the surface of the first sealing member,
In the first sealing member, the molar ratio of hydrogen atoms bonded to silicon atoms to alkenyl groups bonded to silicon atoms in the composition is 1.0 or more, and the type A hardness defined in JISK6253 after curing is 20 It consists of a cured product of the following curable silicone rubber composition,
A silicone rubber-sealed light emitting device characterized in that the second sealing member comprises a cured silicone resin layer having a type D hardness specified in JIS K6253 of 30 or more and a thickness of 0.5 mm or less. Provided.

The present invention secondly,
Curability of the light emitting diode in which the molar ratio of hydrogen atoms bonded to silicon atoms to alkenyl groups bonded to silicon atoms in the composition is 1.0 or more, and the type A hardness specified in JIS K6253 is 20 or less after curing. Sealed with a cured product of silicone rubber composition,
A curable silicone resin having a specified type D hardness of 30 or more is applied to the cured JISK6253 on the surface of the cured product formed for the sealing,
Curing the coating film coated with the curable silicone resin to form a cured silicone resin layer having a thickness of 0.5 mm or less;
Provided is a method for producing a silicone rubber-sealed light emitting device having a process.

  According to the silicone rubber-sealed light emitting device and the manufacturing method thereof of the present invention, peeling of the hard resin coating layer and generation of cracks are effectively suppressed, and the tackiness of the surface of the cured silicone rubber that is a sealing body is effective. Is suppressed. Therefore, dust adhesion and the like can be prevented, which is useful in a light emitting diode sealing process. Further, since the cured silicone rubber is stable over time, the reliability of the light emitting device is increased.

  In the following description and claims, “type A hardness” means the hardness measured using the durometer A type specified in JISK6253, and “type D hardness” means the durometer D of the same standard. It means the hardness measured using the type.

[Sealed body]
In the light emitting device of the present invention, the sealing body of the light emitting diode has a double structure. That is, the sealing body includes a first sealing member that covers the light-emitting diode and a second sealing member that covers the surface of the first sealing member.
The first sealing member has a molar ratio of hydrogen atoms bonded to silicon atoms to alkenyl groups bonded to silicon atoms in the composition (hereinafter referred to as “Si—H / Si-alkenyl molar ratio”) of 1. It consists of a cured product of a curable silicone rubber composition that is 0 or more and has a type A hardness of 20 or less as defined in JISK6253 after curing.
The second sealing member is formed of a cured silicone resin layer having a type D hardness defined in JIS K6253 of 30 or more and a thickness of 0.5 mm or less.

<First sealing member>
As the curable silicone rubber composition that is the raw material of the first sealing member,
(i) Si—H / Si-alkenyl molar ratio in the composition is 1.0 or more, preferably 1.0 to 4.0, more preferably 1.0 to 3.0, still more preferably 1. 0-2.0,
(ii) forming a cured product surface having a type A hardness of 20 or less, preferably 18 or less after curing;
Any addition reaction curable silicone rubber composition can be used. In this case, the lower limit of the hardness is not particularly limited, and the type A hardness is usually 1 or more, preferably 2 or more, more preferably 5 or more.

  When the Si—H / Si-alkenyl molar ratio in the addition reaction curable silicone rubber composition is less than 1.0, the cured product surface of the silicone rubber composition is made of a cured product of a curable silicone resin (hard silicone resin). Even after coating, the crosslinker of the curable silicone resin penetrates into the hardened silicone rubber cured product and reacts with the alkenyl group remaining in the cured silicone rubber, resulting in the hardness of the cured soft silicone rubber over time. Will rise. When the type A hardness of the composition exceeds 20, there is a high risk of wire deformation and peeling from the substrate.

<Preferable addition reaction curable liquid silicone rubber composition>
In the present invention, as an example of a particularly preferable addition reaction curable liquid silicone rubber composition for forming the first sealing member (soft silicone rubber), the following composition can be mentioned. That is,
(A) an organopolysiloxane containing two alkenyl groups bonded to silicon atoms in one molecule;
(B) an organopolysiloxane containing three or more alkenyl groups bonded to silicon atoms in one molecule;
(C) An organohydrogenpolysiloxane containing two hydrogen atoms bonded to silicon atoms in one molecule, and (D) a platinum group metal catalyst, and bonded to silicon atoms in the composition This is an addition reaction curable liquid silicone rubber composition having a molar ratio of hydrogen atoms bonded to silicon atoms to alkenyl groups of 1.0 or more and a type A hardness specified in JIS K6253 after curing of 20 or less.

The above addition reaction curable liquid silicone rubber composition is useful as a light-emitting diode encapsulating material because the cured product exhibits high transparency and very good adhesion to packaging materials such as LCP. A sealed light emitting device can be obtained.
As described above, the present composition comprises the components (A) to (D) as essential components. Hereinafter, each component will be described.

(A) Alkenyl group-containing organopolysiloxane 1
This component (A) is an organopolysiloxane containing two alkenyl groups bonded to silicon atoms in one molecule, and is the main agent (base polymer component) in the present silicone rubber composition.

  The organopolysiloxane has, as an alkenyl group, two alkenyl groups bonded to a silicon atom having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms such as vinyl group and allyl group, in one molecule. The viscosity is preferably 10 to 1,000,000 mPa · s at 25 ° C., particularly 100 to 100,000 mPa · s from the viewpoint of workability and curability.

  Specifically, the main chain having one alkenyl group on each silicon atom at both ends of the molecular chain represented by the following general formula (1) consists of repeating diorganosiloxane units having no alkenyl group, A linear organopolysiloxane having both ends of a molecular chain blocked with a triorganosiloxy group and having a viscosity of 10 to 1,000,000 mPa · s at 25 ° C. as described above from the viewpoint of workability and curability. desirable. The linear organopolysiloxane may contain a small amount of a branched structure (trifunctional siloxane unit) in the molecular chain. In the general formula (1), the vinyl group bonded to the silicon atoms at both ends of the molecular chain may be substituted with another alkenyl group such as an allyl group or a propenyl group.

（式中、Ｒ¹は互いに同一又は異種の脂肪族不飽和結合を有さない非置換又は置換一価炭化水素基であり、Ｒ^２はアルケニル基であり、ｋはこのオルガノポリシロキサンの２５℃の粘度を１０〜１，０００，０００ｍＰａ・ｓとする０又は正の整数である。）

(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond, R ² is an alkenyl group, and k is 25 ° C. of the organopolysiloxane. Is 0 or a positive integer with a viscosity of 10 to 1,000,000 mPa · s.)

Here, as the unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond of R ¹ , for example, those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms are preferable, specifically Alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, phenyl Group, tolyl group, xylyl group, aryl group such as naphthyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, and part or all of hydrogen atoms of these groups are fluorine, bromine, chlorine, etc. Substituted with a halogen atom, cyano group, etc. Alkyl group, cyanoethyl group and the like. As the alkenyl group for R ² , for example, those having 2 to 6 carbon atoms, particularly 2 to 3 carbon atoms are preferable, and specifically, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group. And a cyclohexenyl group, and a vinyl group is preferable.

  In the general formula (1), k is generally 0 or a positive integer satisfying 0 ≦ k ≦ 10,000, preferably 5 ≦ k ≦ 2,000, more preferably 10 ≦ k ≦ 1. , 200 is an integer that satisfies 200.

  Specific examples of the organopolysiloxane (A) include the following.

（上記各式において、ｔは独立に８〜２，０００の整数である。）

(In the above formulas, t is independently an integer of 8 to 2,000.)

(B) Alkenyl group-containing organopolysiloxane 2
The organopolysiloxane of the component (B) has 3 or more alkenyl groups bonded to silicon atoms having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms such as vinyl groups and allyl groups in one molecule, usually 3 to 30. It is an organopolysiloxane having about 3, preferably about 20 pieces. The molecular structure may be any of linear, cyclic, branched, and three-dimensional network structures. Preferably, the main chain is composed of repeating diorganosiloxane units, and both ends of the molecular chain are blocked with triorganosiloxy groups, and the viscosity at 25 ° C. is 10 to 1,000,000 mPa · s, particularly 100 to 100, 000 mPa · s linear organopolysiloxane.

  Even if the alkenyl group is bonded to the silicon atom at the end of the molecular chain or bonded to the silicon atom at the non-end of the molecular chain (in the middle of the molecular chain), both types of alkenyl groups are mixed in one molecule. May be. Especially, it has 1 to 3 alkenyl groups on the silicon atoms at both ends of the molecular chain represented by the following general formula (2) (provided that the alkenyl group bonded to the silicon atoms at the molecular chain ends is If the total number of both ends is less than 3, a straight chain having at least one alkenyl group bonded to a silicon atom at the non-terminal end of the molecular chain (in the middle of the molecular chain) (for example, as a substituent in the diorganosiloxane unit) As mentioned above, it is preferable that the viscosity is 10 to 1,000,000 mPa · s at 25 ° C. from the viewpoint of workability, curability, etc. The linear organopolysiloxane is a small amount. The branched structure (trifunctional siloxane unit) may be contained in the molecular chain.

(In the formula, R ³ is the same or different unsubstituted or substituted monovalent hydrocarbon group, and at least one is an alkenyl group. R ⁴ has the same or different aliphatic unsaturated bond. Is an unsubstituted or substituted monovalent hydrocarbon group, R ⁵ is an alkenyl group, l and m are 0 or a positive integer, and l + m is the viscosity of the organopolysiloxane at 25 ° C. of 10 to 1,000. , 000 mPa · s.)

Here, as the monovalent hydrocarbon group of R ³ , those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms are preferable, and specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, Alkyl group such as isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl Groups, aralkyl groups such as phenylethyl group, phenylpropyl group, etc., alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, octenyl group, etc., and hydrogen of these groups Some or all of the atoms are substituted with halogen atoms such as fluorine, bromine and chlorine, cyano groups, etc., for example, chloromethyl Groups, halogen-substituted alkyl groups such as chloropropyl group, bromoethyl group, trifluoropropyl group, and cyanoethyl group.

Also, as the monovalent hydrocarbon group for R ⁴ , those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms are preferable, and the same examples as the specific examples of R ¹ can be exemplified, but an alkenyl group is not included. .

As the alkenyl group for R ⁵ , for example, those having 2 to 6 carbon atoms, particularly those having 2 to 3 carbon atoms are preferable, and specifically the same as R ^{2 in the} above formula (1) are exemplified, preferably vinyl group is there.

  l and m are generally 0 or a positive integer satisfying 0 <l + m ≦ 10,000, preferably 5 ≦ l + m ≦ 2,000, more preferably 10 ≦ l + m ≦ 1,200, <L / (l + m) ≦ 0.2, preferably an integer satisfying 0.001 ≦ l / (l + m) ≦ 0.1.

  Specific examples of the organopolysiloxane of component (B) include the following compounds.

（上記式において、ｌ，ｍは上述した通りである。）

(In the above formula, l and m are as described above.)

As the component (B), in addition to the above linear organopolysiloxane, an organopolysiloxane having a resin structure (that is, a three-dimensional network structure) can be used. Can be used in combination.

The above-mentioned organopolysiloxane having a resin structure (that is, a three-dimensional network structure) is an organopolysiloxane having a resin structure composed of SiO ₂ units, R ³⁰ _n R ⁴ _p SiO _0.5 units and R ³⁰ _q R ⁴ _r SiO _0.5 units (provided that In these formulas, R ³⁰ is an alkenyl group such as a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group containing no aliphatic unsaturated bond as described above, n is 2 or 3, and p is 0. Or 1, where n + p = 3, q is 0 or 1, r is 2 or 3, where q + r = 3.

Here, SiO ₂ unit is a unit,
R ³⁰ _n R ⁴ _p SiO _0.5 unit is b unit,
When R ³⁰ _q R ⁴ _r SiO _0.5 unit is c unit and the number of moles of each unit is also represented by a, b and c, the ratio of each unit is expressed as molar ratio,
It is preferable that (b + c) /a=0.3 to 3, particularly 0.7 to 1, c / a = 0.01 to 1, particularly 0.07 to 0.15. The organopolysiloxane as the component (B) preferably has a polystyrene-equivalent weight average molecular weight in the range of 500 to 10,000 by gel permeation chromatography (GPC).

  In addition to the a unit, b unit, and c unit, the resin-structured organopolysiloxane further includes a bifunctional siloxane unit and a trifunctional siloxane unit (that is, an organosilsesquioxane unit). It may be contained in a small amount within a range that does not impair the purpose.

  Such a resin-structured organopolysiloxane can be easily synthesized by combining each unit source compound at the required molar ratio by a well-known method, for example, by co-hydrolysis in the presence of an acid. can do. Here, examples of the a unit source include sodium silicate, alkyl silicate, polyalkyl silicate, silicon tetrachloride and the like. The following can be illustrated as a b unit source.

  Further, examples of the c unit source include the following.

  The organopolysiloxane of the component (B) is blended to adjust the hardness of the cured product, and as described above, at a ratio of 0.1 to 50 parts by mass per 100 parts by mass of the component (A). Blended. Preferably 1-30 mass parts is mix | blended.

(C) Organohydrogenpolysiloxane (C) The organohydrogenpolysiloxane of the component acts as a crosslinking agent, and includes an SiH group in the component, an alkenyl group in the component (A), and the component (B). Is subjected to an addition reaction (hydrosilylation) to form a cured product. The organohydrogenpolysiloxane may be any one as long as it has two hydrogen atoms bonded to silicon atoms (that is, SiH groups) in one molecule. The molecular structure of the organohydrogenpolysiloxane is: Any of linear, cyclic, branched, and three-dimensional network structures may be used, but the number of silicon atoms in one molecule (that is, the degree of polymerization) is about 2 to 1,000, particularly about 2 to 300. Can be used.

The position of the silicon atom to which the hydrogen atom is bonded is not particularly limited, and may be at the end of the molecular chain or at the non-terminal (midway). The organic groups bonded to silicon atoms other than hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group that does not have the same aliphatic unsaturation and R ¹ in the general formula (1).

  Examples of the organohydrogenpolysiloxane of component (C) include hydrogenorganosiloxanes having the following structure.

1,1,3,3-tetramethyldisiloxane,

(上記の式中、Ｒはエポキシ基、アクリロイル基、メタアクリロイル基、アルコキシ基の少なくとも１種を含む有機基である。Ｌは０〜1,000の整数、特には０〜300の整数であり、Ｍは１〜200の整数である。）

(In the above formula, R is an organic group containing at least one of an epoxy group, an acryloyl group, a methacryloyl group and an alkoxy group. L is an integer of 0 to 1,000, particularly an integer of 0 to 300; Is an integer from 1 to 200.)

Such organohydrogenpolysiloxanes can be obtained by known methods, for example, R ⁵ SiHCl ₂ , (R ⁵ ) ₃ SiCl, (R ⁵ ) ₂ SiCl ₂ , (R ⁵ ) ₂ SiHCl.
(Wherein R ⁵ is an alkyl group such as a methyl group or an ethyl group or an aryl group such as a phenyl group)
It can be obtained by hydrolytic condensation of chlorosilane as shown above or by equilibrating siloxane obtained by hydrolysis.

  The compounding amount of the organohydrogenpolysiloxane is such that the silicon-bonded hydrogen atoms contained in the organohydrogenpolysiloxane are in a molar ratio to the total amount of silicon-bonded alkenyl groups in the component (A) and the component (B) (that is, Si-H / Si-alkenyl molar ratio) of 1.0 or more, preferably 1.0 to 4.0, particularly preferably 1.0 to 3.0, and more preferably 1.0 to 2. 0. When the molar ratio is less than 1.0, a curable silicone resin that is cured by a hydrosilylation reaction is cured on the surface of the cured product (soft silicone rubber) of the silicone rubber composition to have a hardness of type D hardness of 30 or more. Even when coated with a curing agent of (hard silicone resin), the crosslinking agent of the curable silicone resin penetrates into the cured silicone rubber and reacts with the alkenyl group remaining inside the cured silicone rubber. Hardness increases over time. If this molar ratio is too high, a large amount of unreacted SiH groups remain in the cured silicone rubber, and the physical properties of the cured silicone rubber may change over time.

(D) Platinum group metal catalyst The platinum group metal catalyst of component (D) is blended to cause an addition curing reaction in the composition, and is known as a so-called hydrosilylation catalyst. Anything can be used. Examples of the catalyst include platinum-based, palladium-based, and rhodium-based catalysts. From the viewpoint of cost and the like, platinum-based catalysts such as platinum, platinum black, and chloroplatinic acid such as H ₂ PtCl ₆ · mH ₂ O, Platinum compounds such as K ₂ PtCl ₆ , KHPtCl ₆ · mH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ · mH ₂ O, PtO ₂ · mH ₂ O (m is a positive integer), and these platinum compounds Examples thereof include hydrocarbons such as olefins, alcohols, and complexes with vinyl group-containing organopolysiloxanes. These can be used alone or in combination of two or more.

  The compounding amount of the component (D) catalyst may be an effective amount, and is usually 0.1 to 1,000 ppm, preferably in terms of platinum group metal (on a mass basis) with respect to the total amount of the components (A) to (C). Is used in the range of 0.5 to 200 ppm.

-Other components Components other than the components (A) to (D) can be blended in the present composition as necessary. These optional components may be used alone or in combination of two or more. Representative optional components will be described.

.. Adhesion aid An adhesion aid can be added to improve the adhesion of the composition to the substrate. Preferable adhesion assistants include, for example, organosilicon compounds having a silicon atom-bonded alkoxy group and an alkenyl group or a silicon atom-bonded hydrogen atom (SiH group) in one molecule, and an organooxysilyl represented by the general formula (3) Examples thereof include a modified isocyanurate compound and / or a hydrolysis condensate thereof (that is, an organosiloxane-modified isocyanurate compound).

〔式中、Ｒ⁶は独立に下記式（４）：

[Wherein R ⁶ is independently the following formula (4):

(Here, R ⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and s is an integer of 1 to 6, particularly 1 to 4.)
Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, at least one of which is an organic group of the formula (4). ]

In the formula (3), examples of the monovalent hydrocarbon group containing an aliphatic unsaturated bond represented by R ⁶ include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, Examples thereof include alkenyl groups having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, such as hexenyl group and cyclohexenyl group. Examples of the monovalent hydrocarbon group for R ⁷ include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, hexyl groups, cyclohexyl groups, and other alkyl groups, vinyl A monovalent hydrocarbon having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms such as an aryl group such as an alkenyl group and a phenyl group similar to those exemplified for R ⁶ such as a group, an allyl group, a propenyl group and an isopropenyl group. Group, and an alkyl group is preferable.

  Specific examples of the compound used as the adhesion aid include the following compounds.

（式中、ｍ及びｎはそれぞれ独立に０〜200の整数であって、但しｍ＋ｎが２〜５０、好ましくは４〜２０を満足する整数である。）

(In the formula, m and n are each independently an integer of 0 to 200, provided that m + n is an integer satisfying 2 to 50, preferably 4 to 20.)

  Among such organosilicon compounds, organosilicon having a silicon atom-bonded alkoxy group and an alkenyl group or a silicon atom-bonded hydrogen atom (SiH group) in one molecule because the obtained cured product has particularly excellent adhesion. Compounds are preferred.

  The amount of the above-mentioned adhesion assistant is usually 10 parts by mass or less (that is, 0 to 10 parts by mass), preferably 0 with respect to 100 parts by mass in total of the components (A), (B) and (C). 0.01 to 5 parts by mass, more preferably about 0.1 to 1 part by mass. If the amount of the adhesion aid is too large, the hardness and surface tackiness of the cured product may be adversely affected.

-Curing inhibitor A curing inhibitor can be added to this composition as needed. As the curing inhibitor, any compound known as a hydrosilylation reaction inhibitor can be used, and examples thereof include acetylene alcohol. A small amount of such a curing inhibitor may be added to the present composition to prepare the composition as a one-pack type.

・ ・ Inorganic fillers When blended with inorganic fillers, there are effects such as light scattering of the cured product and fluidity of the composition within an appropriate range, and the use of the composition to increase the strength. is there. The inorganic filler is not particularly limited, but is preferably in the form of fine particles that do not deteriorate the optical properties, such as alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, talc. , Calcium carbonate, barium sulfate and the like.

..Phosphors As phosphors, for example, yttrium, aluminum, garnet-based YAG phosphors, ZnS phosphors, Y ₂ O ₂ S phosphors, red light emitting phosphors widely used in LEDs, A blue light emitting phosphor, a green light emitting phosphor and the like can be mentioned. Hereinafter, typical phosphors will be described in more detail.
First, phosphors based on yttrium-aluminum oxide phosphors activated with cerium that can emit light by exciting light emitted from the light-emitting diodes.
Specific examples of the yttrium / aluminum oxide phosphor include YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce (YAG: Ce), Y ₄ Al ₂ O ₉ : Ce, and a mixture thereof. It is done. The yttrium / aluminum oxide phosphor may contain at least one of Ba, Sr, Mg, Ca, and Zn. Moreover, by containing Si, the reaction of crystal growth can be suppressed and phosphor particles can be aligned.

  In this specification, the yttrium-aluminum oxide phosphor activated with Ce is to be interpreted in a broad sense, and a part or the whole of yttrium is derived from the group consisting of Lu, Sc, La, Gd and Sm. It is substituted by at least one selected element, or a part or all of aluminum is used in a broad sense including a phosphor having a fluorescent action in which any one or both of Ba, Tl, Ga, and In are substituted.

More specifically, the general formula _{(Y z Gd 1-z)} 3 Al 5 O 12: Ce ( where, 0 <z ≦ 1) photoluminescence phosphor and the general formula represented by _{(Re 1-a Sm a)} 3 Re ' ₅ O ₁₂ : Ce (where 0 ≦ a <1, 0 ≦ b ≦ 1, Re is at least one selected from Y, Gd, La, and Sc, and Re ′ is selected from Al, Ga, and In. At least one kind of photoluminescent phosphor.

  Since this phosphor has a garnet structure (garnet-type structure), it is resistant to heat, light, and moisture, and the peak of the excitation spectrum can be made around 450 nm. The emission peak is also in the vicinity of 580 nm and has a broad emission spectrum that extends to 700 nm.

  Further, the photoluminescence phosphor can increase the excitation light emission efficiency in a long wavelength region of 460 nm or more by containing Gd (gadolinium) in the crystal. As the Gd content increases, the emission peak wavelength shifts to a longer wavelength, and the entire emission wavelength also shifts to the longer wavelength side. That is, when a strong reddish emission color is required, it can be achieved by increasing the amount of Gd substitution. On the other hand, as Gd increases, the emission luminance of photoluminescence by blue light tends to decrease. Furthermore, in addition to Ce, Tb, Cu, Ag, Au, Fe, Cr, Nd, Dy, Co, Ni, Ti, Eu, and the like can be contained as desired.

  Moreover, in the composition of the yttrium / aluminum / garnet (garnet) phosphor having a garnet structure, the emission wavelength is shifted to the short wavelength side by substituting part of Al with Ga. Further, by substituting part of Y in the composition with Gd, the emission wavelength is shifted to the longer wavelength side.

  When substituting a part of Y with Gd, it is preferable that the substitution with Gd is less than 10%, and the Ce content (substitution) is 0.03 to 1.0. If the substitution with Gd is less than 20%, the green component is large and the red component is small. However, by increasing the Ce content, the red component can be supplemented and a desired color tone can be obtained without lowering the luminance. With such a composition, the temperature characteristics are good and the reliability of the light emitting diode can be improved. In addition, when a photoluminescent phosphor adjusted to have a large amount of red component is used, a light emitting device capable of emitting an intermediate color such as pink can be formed.

  Such photoluminescent phosphors use oxides or compounds that easily become oxides at high temperatures as raw materials for Y, Gd, Al, and Ce, and mix them well in a stoichiometric ratio. Get raw materials. Alternatively, a mixed raw material obtained by mixing a coprecipitation oxide obtained by firing a solution obtained by coprecipitation of a solution obtained by dissolving a rare earth element of Y, Gd, and Ce in an acid in a stoichiometric ratio with oxalic acid and aluminum oxide. Get. An appropriate amount of fluoride such as barium fluoride or ammonium fluoride is mixed as a flux and packed in a crucible, and baked in air at a temperature range of 1350 ° C. to 1450 ° C. for 2 to 5 hours to obtain a fired product, and then fired. The product can be obtained by ball milling in water, washing, separating, drying and finally passing through a sieve.

  Such a photoluminescent phosphor may be a mixture of yttrium, aluminum, garnet (garnet) phosphor activated by two or more kinds of cerium, and other phosphors.

  The particle size of the phosphor is preferably in the range of 1 μm to 50 μm, more preferably 3 μm to 30 μm. A phosphor having a particle size of less than 3 μm is relatively easy to form an aggregate, and is likely to become dense and settle in the liquid resin, thus reducing the light transmission efficiency. When the particle diameter is in the above preferred range, the light concealment by such a phosphor can be suppressed and the output of the light emitting device is improved. In addition, phosphors in the same particle size range have high light absorptivity and conversion efficiency and a wide excitation wavelength range. Thus, by including a large particle size phosphor having optically excellent characteristics, light around the main wavelength of the light emitting diode can be converted well and emitted.

  Here, the particle size is a value obtained from a volume-based particle size distribution curve. The volume-based particle size distribution curve is obtained by measuring the particle size distribution by a laser diffraction / scattering method. Specifically, in an environment of an air temperature of 25 ° C. and a humidity of 70%, hexametalin having a concentration of 0.05%. Each substance was dispersed in an aqueous sodium acid solution and measured with a laser diffraction particle size distribution analyzer (SALD-2000A) in a particle size range of 0.03 μm to 700 μm. In this volume-based particle size distribution curve, it is a particle size value when the integrated value is 50%, and the center particle size of the phosphor used in the composition is preferably in the range of 3 μm to 30 μm. Moreover, it is preferable that the fluorescent substance which has this center particle size value is contained with high frequency, and the frequency value is preferably 20% to 50%. By using a phosphor having a small variation in particle size in this way, a light emitting device having a good color tone can be obtained with reduced chromaticity variation for each product.

  The phosphor is preferably dispersed uniformly in the resin layer, but may be precipitated in the resin layer.

Moreover, it is not restricted to the said YAG fluorescent substance, Various fluorescent substance can be used. For example, M ₂ Si ₅ N ₈ : Eu (M is an alkaline earth metal such as Ca, Sr and Ba) and MSi ₂ O ₂ N ₂ : Eu (M is an alkali such as Ca, Sr and Ba). An earth metal), La ₂ O ₂ S: Eu, SrAl ₂ O ₄ : R, M ₅ (PO ₄ ) ₃ X: R (M is at least selected from Sr, Ca, Ba, Mg, Zn) X is at least one selected from F, Cl, Br, and I. R is Eu, Mn, or any one of Eu and Mn. Can do.
As other phosphors, alkaline earth metal silicates activated with europium can also be contained. The alkaline earth metal silicate is preferably an alkaline earth metal orthosilicate represented by the following general formula.

(2-x-y) SrO · x (Ba, Ca) O · (1-a-b-c-d) SiO 2 · aP 2 O 5 bAl 2 O 3 cB 2 O 3 dGeO 2: yEu 2+ ( Equation Medium, 0 <x <1.6, 0.005 <y <0.5, 0 <a, b, c, d <0.5.)
(2-x-y) BaO · x (Sr, Ca) O · (1-a-b-c-d) SiO 2 · aP 2 O 5 bAl 2 O 3 cB 2 O 3 dGeO 2: yEu 2+ ( Equation (Inside, 0.01 <x <1.6, 0.005 <y <0.5, 0 <a, b, c, d <0.5.)
Here, preferably, at least one of the values of a, b, c and d is greater than 0.01.

As a phosphor composed of an alkaline earth metal salt, in addition to the alkaline earth metal silicate described above, an alkaline earth metal aluminate or Y (V, P, Si) O ₄ activated with europium and / or manganese is used. : Eu or an alkaline earth metal-magnesium-disilicate represented by the following formula can also be contained.

Me (3-xy) MgSi ₂ O ₃ : xEu, yMn (wherein 0.005 <x <0.5, 0.005 <y <0.5, Me represents Ba and / or Sr and / or Or Ca.)
The phosphor made of the above alkaline earth metal silicate is manufactured as follows. Depending on the alkaline earth metal silicate of the desired composition of interest, the stoichiometric amounts of the starting alkaline earth metal carbonate, silicon dioxide and europium oxide are intimately mixed and used routinely for the production of phosphors. It is a solid reaction and is converted to the desired phosphor at temperatures of 1100 ° C. and 1400 ° C. under a reducing atmosphere. At this time, it is preferable to add less than 0.2 mol of ammonium chloride or other halide. If necessary, part of silicon can be replaced with germanium, boron, aluminum, and phosphorus, and part of europium can be replaced with manganese.

One of the phosphors as described above, ie, alkaline earth metal aluminates activated with europium and / or manganese, Y (V, P, Si) O ₄ : Eu, Y ₂ O ₂ S: Eu ³⁺ By combining one or these phosphors, an emission color having a desired color temperature and high color reproducibility can be obtained.

  The blending amount of the phosphor is appropriately adjusted according to the required color tone.

.. Diffusing agent Another optional component that may be added to the curable silicone resin is a diffusing agent. By containing a diffusing agent, a light diffusing effect, a thickening effect, a stress diffusing effect, and the like can be obtained. As a specific diffusing agent, barium titanate, titanium oxide, aluminum oxide, silicon oxide or the like is preferably used. As a result, a light emitting device having good directivity can be obtained.
The diffusing agent preferably has a center particle size of 1 nm or more and less than 5 μm. A diffusing agent having a center particle diameter of about 400 nm or more can diffuse irregularly the light from the light-emitting diode and the phosphor, and suppress color unevenness that tends to occur when a phosphor having a large particle diameter is used. On the other hand, a diffusing agent having a center particle diameter of less than about 400 nm has a low interference effect on the light wavelength from the light emitting diode, and thus has high transparency and can increase the resin viscosity without lowering the light intensity. Thus, when the color conversion member is arranged by potting or the like, it becomes possible to disperse the phosphor in the resin composition almost uniformly in the syringe and maintain the state, and the particle size is relatively difficult to handle. Even when a large phosphor is used, it is possible to produce with high yield. Thus, since the action of the diffusing agent varies depending on the particle size range, it is desirable to select or use it in combination with the method of use.

..Other optional components Other optional components include, for example, anti-aging agents, radical inhibitors, UV absorbers, adhesion improvers, flame retardants, surfactants, storage stability improvers, ozone degradation inhibitors, light Stabilizer, thickener, plasticizer, coupling agent, antioxidant, heat stabilizer, conductivity imparting agent, antistatic agent, radiation blocking agent, nucleating agent, phosphorus peroxide decomposing agent, lubricant, pigment, Examples thereof include metal deactivators, physical property modifiers, and organic solvents.
.. Preparation and curing of composition The above composition can be prepared by mixing the components (A) to (D) and optional components optionally contained by any method. The composition can be appropriately prepared as a one-component type or a two-component type by a method well known to those skilled in the art. The composition can be cured by heating to room temperature (23 ° C.) to 200 ° C., preferably 60 to 180 ° C., more preferably about 80 to 160 ° C. after being placed at a predetermined location of the package. .

Second sealing member:
The curable silicone resin that is the raw material of the second sealing member is any curable silicone resin that has a type D hardness of 30 or more, preferably 40 or more, more preferably 50 or more after curing. Can be used. When the type D hardness is less than 30, the surface tackiness of the mold resin is increased. In this case, the upper limit of the hardness is not particularly limited, but is usually 90 or less, particularly 80 or less in type D hardness.

  The surface is remarkably tacky only by forming the first sealing member with a cured product (soft silicone rubber) of the curable silicone rubber composition, but the tack can be significantly reduced by the second sealing member, It is possible to effectively prevent dust from adhering to the surface of the sealing material produced in the light emitting device manufacturing process and the mold resin from adhering to the parts feeder, and the second sealing member has high stability over time. Have

The curable silicone resin having a cured type D hardness of 30 or more used for coating to reduce the surface tackiness of the cured silicone rubber may be a silicone resin that cures by a hydrosilylation reaction that satisfies the hardness requirement. Anything can be used. Among these, alkenyl group (preferably vinyl group) -containing silicone resins are desirable. As the alkenyl group- containing silicone resin, a silicone resin having a three-dimensional structure as a main component can be used.

Among them, as a representative example, at least the formula:
(R ⁸ ₃ SiO _1/2 ) _d (R ⁸ ₂ SiO) _e (R ⁸ ₁ SiO _3/2 ) _f
[Wherein R ⁸ represents the same or different substituted or unsubstituted monovalent hydrocarbon group, and 2.0 to 45.0 mol% of the total number of monovalent hydrocarbon groups is an alkenyl group (preferably a vinyl group). And 25-60 mol% is a phenyl group, d, e, and f represent the relative number of moles of each siloxane unit, d / d + e + f = 0.65-0.95, e / d + e + f = 0 0.05 to 0.35, f / d + e + f = 0 to 0.05]
It is an alkenyl group containing organopolysiloxane represented by these.

As the crosslinking agent for the alkenyl group-containing organopolysiloxane, the organohydrogensiloxane described as the component (C) and the curing catalyst described as the component (D) can be used.
[Light emitting diode]
In the present invention, the light emitting diode is not particularly limited in terms of light emission color, and is not limited to a light emitting diode that emits red or green light, and a light emitting diode that emits blue light can also be used. In addition to these light emitting diodes that emit visible light, a light emitting diode that emits light in the ultraviolet region from the short wavelength region of visible light, for example, a light emitting diode that emits light in the ultraviolet region near 360 nm can be used. However, when a phosphor is used for the light emitting device, a semiconductor light emitting diode having a light emitting layer capable of emitting a light emission wavelength capable of exciting the phosphor is preferable. Examples of such semiconductor light emitting diodes include various semiconductors such as ZnSe and GaN, but nitride semiconductors capable of emitting short wavelengths that can excite phosphors efficiently (In _X Al _Y Ga _1- XYN, Preferred examples include 0 ≦ X, 0 ≦ Y, and X + Y ≦ 1). If desired, the nitride semiconductor may contain boron or phosphorus. Examples of the semiconductor structure include a homostructure having a MIS junction, a PIN junction, and a pn junction, a heterostructure, and a double heterostructure. Various emission wavelengths can be selected depending on the material of the semiconductor layer and the degree of mixed crystal. In addition, a single quantum well structure or a multiple quantum well structure in which the semiconductor active layer is formed in a thin film in which a quantum effect is generated can be used.

  When a nitride semiconductor is used, materials such as sapphire, spinel, SiC, Si, ZnO, and GaN are preferably used for the semiconductor substrate. In order to form a nitride semiconductor with good crystallinity with high productivity, it is preferable to use a sapphire substrate. A nitride semiconductor can be formed on the sapphire substrate by MOCVD or the like. A buffer layer made of GaN, AlN, GaAIN or the like is formed on the sapphire substrate, and a nitride semiconductor having a pn junction is formed thereon.

  As an example of a light emitting diode having a pn junction using a nitride semiconductor, a first contact layer formed of n-type gallium nitride, a first cladding layer formed of n-type aluminum nitride / gallium on a buffer layer, nitrided Examples include a double hetero structure in which an active layer formed of indium gallium, a second cladding layer formed of p-type aluminum nitride / gallium, and a second contact layer formed of p-type gallium nitride are sequentially stacked.

  Nitride semiconductors exhibit n-type conductivity without being doped with impurities. When forming a desired n-type nitride semiconductor, for example, to improve luminous efficiency, it is preferable to appropriately introduce Si, Ge, Se, Te, C, etc. as an n-type dopant. On the other hand, when forming a p-type nitride semiconductor, the p-type dopants such as Zn, Mg, Be, Ca, Sr, and Ba are doped. Since nitride semiconductors are not easily converted to p-type by simply doping with a p-type dopant, it is preferable to reduce resistance by heating in a furnace or plasma irradiation after introducing the p-type dopant. After the electrodes are formed, a light emitting diode made of a nitride semiconductor can be formed by cutting the semiconductor wafer into chips.

  In the light emitting device, in order to emit white light, the emission wavelength of the light emitting diode is preferably 400 nm or more and 530 nm or less, and 420 nm or more in consideration of the complementary color relationship with the emission wavelength from the phosphor and the deterioration of the translucent resin. 490 nm or less is more preferable. In order to further improve the excitation and light emission efficiency of the light emitting diode and the phosphor, 450 nm or more and 475 nm or less are more preferable.

〔package〕
The package used in the present invention is a package having a recess having a bottom surface and a side surface. The entire package may be made of metal, or may be composed of a metal part and a non-metal part (eg, synthetic resin or ceramic). Examples of the metal material used include cobalt, nickel, silver alloy, and copper. Examples of the synthetic resin include polyamide resin, epoxy resin, and nylon. Silver plating or the like may be applied to a substrate made of a metal material, synthetic resin, ceramic, or a combination of two or more thereof. If the surface of the package is silver-plated, for example, the light emitted from the GaN-based compound semiconductor that emits blue light can be reflected and efficiently emitted to the outside. it can. In addition, the use of gold and tin die bond members can contribute to the same effect.

[Method of Manufacturing Silicone Rubber Sealed Light Emitting Device]
According to the method for manufacturing a light-emitting device of the present invention, first, the light-emitting diode placed on the bottom surface of the recess of the package is sealed with the cured product (first sealing member) of the curable silicone rubber composition described above. . This sealing is performed by applying a liquid curable silicone rubber composition to the recess of the package and then curing the composition at a predetermined temperature. The composition can be applied to the package recess by, for example, a method such as screen printing, metal mask printing, potting, spray coating, or ink jet discharge. The composition may have no solvent depending on the coating method, or may be diluted with an organic solvent and used as a varnish. The thickness of the first sealing member layer formed in this way is typically 10 μm to 3 mm, more typically 100 μm to 3 mm.
Next, the aforementioned curable silicone resin is applied to the surface of the rubber cured product.
Next, the coating film of the curable silicone resin is cured to form a cured silicone resin layer (second sealing member) having a thickness of 0.5 mm or less.

  Since the hard silicone resin layer has a thickness of 0.5 mm or less and needs to cover the surface of the first sealing member, the curable silicone resin composition is usually dissolved in an organic solvent having a boiling point of 150 ° C. or less. Use in state. Any solvent can be used as long as it can be wetted even when applied to the surface of the cured silicone rubber. Among these solvents, aromatic hydrocarbons such as toluene and xylene, and silicon solvents such as trimethyldisiloxane are preferable. The concentration of the silicone resin composition solution is desirably in the range of 10 to 90% by mass for controlling the coating thickness.

  The film thickness of the coating is preferably 50 μm or more and 0.5 mm or less, more preferably 50 μm or more and 300 μm or less. More preferably, it is 50 μm or more and 200 μm or less.

  When the hardness of the cured silicone rubber used as the substrate is low, if the coating thickness exceeds 0.5 mm, the coated silicone resin is easily cracked. On the other hand, if it is too thin, the coating is easily broken.

  The method of applying the solution of the curable silicone resin composition diluted in the solvent as described above to the surface of the cured silicone rubber cured product (first sealing member) is not limited. For example, potting (dropping), spray spraying It can be applied uniformly by applying by ink jetting, brushing or the like. After coating, a sealing body in which surface tackiness is reduced by curing a curable silicone resin under a predetermined temperature condition (that is, a specific composition whose surface is coated with a silicone resin layer having a specific thickness and a specific hardness) A cured silicone rubber having a cross-linked structure consisting of

Hereinafter, the present invention will be specifically described by way of examples. In the following description, “part” means “part by mass”, and the viscosity indicates a value measured at 23 ° C.
Example 1
Preparation of composition 80 parts of dimethylpolysiloxane (VF1) having a viscosity of 1 Pa.s with both ends of a molecular chain sealed with vinyldimethylsiloxy groups, and a viscosity of 5 Pa with both ends of a molecular chain sealed with vinyldimethylsiloxy groups .s of 15 parts of dimethylpolysiloxane (VF2), 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi ₃ SiO _0.5 units 5 parts of siloxane (VMQ), and the following formula (5) in which the amount of SiH groups is 1.5 times mol per the total amount of vinyl groups in the VF1, VF2 and VMQ components:

で示されるオルガノハイドロジェンポリシロキサン12.8部、並びに塩化白金酸のオクチルアルコール変性溶液０．０５部を配合して組成物を調製した。
該組成物を以下のようにして評価した。

A composition was prepared by blending 12.8 parts of the organohydrogenpolysiloxane represented by the above formula and 0.05 part of an octyl alcohol-modified solution of chloroplatinic acid.
The composition was evaluated as follows.

Measurement of physical properties of uncoated cured rubber The composition obtained above was heat-molded at 150 ° C./1 hr to obtain a cured silicone rubber of 10 mm × 50 mm × 2 mm (thickness). In accordance with JIS K 6301, the tensile strength and elongation of the cured product were measured. Type A hardness was measured in accordance with JISK6253.

・ Formation of hard resin coating Further, the above cured product is treated with KJR-632 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., type D hardness after curing: 70), which is a curable silicone resin that produces a transparent hard resin. It was immersed in a 20% by mass solution dissolved in 1 and applied to the surface of the cured product. Thereafter, the coating film was dried at room temperature for 1 hour and then heated at 120 ° C. for 1 hour to be cured. The resulting hard resin coating had a thickness of 200 μm.

Measurement of physical properties of coated cured rubber The type A hardness of the cured silicone rubber after 24 hours from coating with a hard resin was also measured in the same manner as described above.

-Bending resistance test Even if the cured product having the above-mentioned shape whose surface was coated with a hard resin was bent by 90 degrees, the hard resin layer coated did not crack.

・ Tack property test After spraying silver powder on the surface of hardened resin coated with hard resin and uncovered hardened material, we tried to remove the silver powder by blowing air. However, most of the silver powder remained unattached on the surface.

-Example 2-
In Example 1, the amount of VF1 (1 Pa.s) was changed to 87.5 parts, the addition amount of VMQ was changed to 2.5 parts, the amount of organohydrogenpolysiloxane represented by formula (5) was changed to 8 parts, and The following structural formula (6):

（式中、Ｒ^８は

(Where R ⁸ is

）で示されるエポキシ基含有オルガノハイドロジェンポリシロキサンを1部添加した以外は、実施例1と同様にして組成物を調製した。

The composition was prepared in the same manner as in Example 1 except that 1 part of the epoxy group-containing organohydrogenpolysiloxane represented by (1) was added.

Measurement of physical properties of uncoated cured rubber A silicone rubber cured product was obtained in the same manner as in Example 1 for the obtained composition, and the tensile strength, elongation and type A hardness were measured. The results are shown in Table 1.

-Formation of hard resin coating The hard resin coating was formed on the surface of the cured product in the same manner as in Example 1 except that a 20% solution of KJR632 was sprayed instead of dipping. The coating thickness of the hard resin was 150 μm.

  The type A hardness of the cured silicone rubber 24 hours after the hard resin coating was measured in the same manner as in Example 1. The results are shown in Table 1.

  Moreover, when the bending resistance test was done about the hard rubber coated hard resin, the hard resin layer did not crack.

  Further, when the tack property test was performed in the same manner as in Example 1 for the hard rubber coated hard rubber and the uncovered hard rubber surface, the silver powder was completely removed from the hard resin coated one. A large amount of silver powder remained on the uncoated surface.

Example 3
Instead of the epoxy-containing siloxane represented by the formula (5) used in Example 2, the following structural formula (7):

（式中、Ｒ^９：

(Wherein R ⁹ :

）で示されるエポキシ基含有オルガノハイドロジェンポリシロキサン１部を使用した以外は、実施例2と同様にして組成物を調製した。

A composition was prepared in the same manner as in Example 2 except that 1 part of the epoxy group-containing organohydrogenpolysiloxane represented by formula (1) was used.

Measurement of physical properties of uncoated cured rubber A silicone rubber cured product was obtained in the same manner as in Example 1 for the obtained composition, and the tensile strength, elongation and type A hardness were measured. The results are shown in Table 1.

-Formation of hard resin coating The hard resin coating was formed on the surface of the cured product in the same manner as in Example 1 except that a 20% solution of KJR632 was sprayed instead of dipping. The coating thickness of the hard resin was 150 μm.

  The type A hardness of the cured silicone rubber 24 hours after the hard resin coating was measured in the same manner as in Example 1. The results are shown in Table 1.

  Moreover, when the bending resistance test was done about the hard rubber coated hard resin, the hard resin layer did not crack.

  Further, when the tack property test was performed in the same manner as in Example 1 for the hard rubber coated hard rubber and the uncovered hard rubber surface, the silver powder was completely removed from the hard resin coated one. A large amount of silver powder remained on the uncoated surface.

-Example 4-
In Example 1, the following formula (8):

（８）

(8)

A composition was prepared in the same manner as in Example 1 except that 0.5 part by mass of the adhesion-imparting agent composed of the compound represented by

Measurement of physical properties of uncoated cured rubber A silicone rubber cured product was obtained in the same manner as in Example 1 for the obtained composition, and the tensile strength, elongation and type A hardness were measured. The results are shown in Table 1.

-Formation of hard resin coating The hard resin coating was formed on the surface of the cured product in the same manner as in Example 1 except that a 20% solution of KJR632 was sprayed instead of dipping. The coating thickness of the hard resin was 150 μm.

  The type A hardness of the cured silicone rubber 24 hours after the hard resin coating was measured in the same manner as in Example 1. The results are shown in Table 1.

  Moreover, when the bending resistance test was done about the hard rubber coated hard resin, the hard resin layer did not crack.

  Further, when the tack property test was performed in the same manner as in Example 1 for the hard rubber coated hard rubber and the uncovered hard rubber surface, the silver powder was completely removed from the hard resin coated one. A large amount of silver powder remained on the uncoated surface.

-Example 5-
In Example 2, the following formula (9):

（９）
で表される化合物からなる接着付与剤1.0質量部を添加した以外は、実施例2と同様にして組成物を調製した。

(9)
A composition was prepared in the same manner as in Example 2 except that 1.0 part by mass of an adhesion-imparting agent composed of the compound represented by

  About the obtained composition, the silicone rubber hardened | cured material was obtained like Example 1, and tensile strength, elongation, and type A hardness were measured. The results are shown in Table 1.

-Formation of hard resin coating The hard resin coating was formed on the surface of the cured product in the same manner as in Example 1 except that a 20% solution of KJR632 was sprayed instead of dipping. The coating thickness of the hard resin was 150 μm.

  The type A hardness of the cured silicone rubber 24 hours after the hard resin coating was measured in the same manner as in Example 1. The results are shown in Table 1.

  Moreover, when the bending resistance test was done about the hard rubber coated hard resin, the hard resin layer did not crack.

  Further, when the tack property test was performed in the same manner as in Example 1 for the hard rubber coated hard rubber and the uncovered hard rubber surface, the silver powder was completely removed from the hard resin coated one. A large amount of silver powder remained on the uncoated surface.

−Comparative Example 1−
In Example 1, the amount of the organohydrogenpolysiloxane represented by the formula (5) is changed to 2.7 parts, and the amount of silicon-bonded hydrogen atoms (SiH) in the composition is included in VF1, VF2, and VMQ. A composition was prepared in the same manner as in Example 1 except that the molar amount was 0.8 times the total amount of vinyl groups.

Measurement of physical properties of uncoated cured rubber A silicone rubber cured product was obtained in the same manner as in Example 1 for the obtained composition, and the tensile strength, elongation and type A hardness were measured. The results are shown in Table 2.

-Formation of hard resin coating The hard resin coating was formed on the surface of the cured product in the same manner as in Example 1 except that a 20% solution of KJR632 was sprayed instead of dipping. The coating thickness of the hard resin was 150 μm.

  The type A hardness of the cured silicone rubber 24 hours after the hard resin coating was measured in the same manner as in Example 1. The results are shown in Table 2.

  Moreover, when the bending resistance test was done about the hard rubber coated hard resin, the hard resin layer did not crack.

  Further, when the tack property test was performed in the same manner as in Example 1 for the hard rubber coated hard rubber and the uncovered hard rubber surface, the silver powder was completely removed from the hard resin coated one. A large amount of silver powder remained on the uncoated surface.

-Comparative Example 2-
In Example 1, instead of the organohydrogenpolysiloxane represented by the formula (5), the formula (10):

で表される化合物を4.6部使用した以外は、実施例１と同様にして組成物を調製した。

A composition was prepared in the same manner as in Example 1 except that 4.6 parts of the compound represented by formula (1) was used.

Measurement of physical properties of uncoated cured rubber A silicone rubber cured product was obtained in the same manner as in Example 1 for the obtained composition, and the tensile strength, elongation and type A hardness were measured. The results are shown in Table 2.
-Formation of hard resin coating The hard resin coating was formed on the surface of the cured product in the same manner as in Example 1 except that a 20% solution of KJR632 was sprayed instead of dipping. The coating thickness of the hard resin was 150 μm.

  The type A hardness of the cured silicone rubber 24 hours after the hard resin coating was measured in the same manner as in Example 1. The results are shown in Table 2.

  Moreover, when the bending resistance test was done about the hard rubber coated hard resin, the hard resin layer did not crack.

  Further, when the tack property test was performed in the same manner as in Example 1 for the hard rubber coated hard rubber and the uncovered hard rubber surface, the silver powder was completely removed from the hard resin coated one. A large amount of silver powder remained on the uncoated surface.

-Comparative Example 3-
In Example 1, when the cured product of the obtained composition was coated with a hard resin, a 75% by weight toluene solution was used as a KJR-632 toluene solution instead of 20% by weight, whereby a thickness of 550 μm was used. A hard resin coating was formed in the same manner as in Example 1 except that a hard resin coating was formed. Thus, when the crack resistance of the hardened | cured rubber material coat | covered with the hard resin was measured like Example 1, the hard resin layer cracked.

（注）＊１：硬化性シリコーンゴム組成物中のケイ素原子結合水素原子／ケイ素原子結合ビニル基のモル比
＊２：硬化性シリコーンゴム組成物の硬化物（硬質レジン被覆前）の外観

(Note) * 1: Molar ratio of silicon atom-bonded hydrogen atom / silicon atom-bonded vinyl group in curable silicone rubber composition * 2: Appearance of cured product of curable silicone rubber composition (before hard resin coating)

（注）＊１及び＊２については表１と同じ。

(Note) * 1 and * 2 are the same as in Table 1.

-Example 6-
FIG. 1 is a longitudinal sectional view showing a state in which an LED chip 2 is sealed in a package 1 (consisting of 1a and 1b). The package 1 has a concave portion in the upper central portion, and the concave portion has a shape having a bottom surface and a side surface which is formed so as to surround the bottom surface and spreads upward in a mortar shape. The package 1 is composed of a member 1a made of a copper-based material plated with silver at the center and having a concave portion on the upper side and also serving as a heat sink, and a nylon resin member 1b integrally formed around the member 1a. It is configured. The LED chip 2 is placed in the recess of the package 1, the wire 3 is bonded to the cathode electrode 5, and the wire 4 is bonded to the anode electrode 6, and then an addition-curable liquid silicone rubber composition is injected into the recess and filled and cured. Thus, a cured silicone rubber (first sealing member) 7 is formed. A hard resin layer (second sealing member) 8 is formed by applying and curing a curable silicone resin solution on the silicone rubber cured product 7. Thus, the silicone rubber-sealed light emitting device of the present invention is produced.

Using the silicone rubber composition prepared in Examples 1 to 5 and Comparative Examples 1 and 2 as the curable silicone rubber composition, spraying a toluene solution of KJR-632 as the curable silicone resin solution by spraying about 200 μm The thin film was applied and cured. The package was subjected to a humidified reflow test in accordance with MSL level 2.
Those in which cracks occurred in the cured cured product and those in which the cured cured product was peeled off from the package or chip surface were evaluated as defective. Moreover, what deformed the wire was also evaluated as bad. The results are shown in Table 3.

Number of defects / n = 20

It is a longitudinal cross-sectional view which shows the state which sealed the LED chip in the package.

Explanation of symbols

1a. One member constituting the package 1b. 1. another member constituting the package LED chip 5. Cathode electrode 6. Anode electrode 7. 7. Silicone rubber cured product as the first sealing member Coating made of cured silicone resin as second sealing member

Claims (2)

A package having a recess having a bottom surface and a side surface;
A light emitting diode placed on the bottom surface of the recess of the package;
A sealing body disposed in the recess of the package and sealing the light emitting diode;
A light emitting device comprising
The sealing body includes a first sealing member that covers the light emitting diode, and a second sealing member that covers the surface of the first sealing member,
The first sealing member is
(A) The following formula (1)

(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond, R ² is an alkenyl group, and k is 25 ° C. of the organopolysiloxane. Is 0 or a positive integer with a viscosity of 10 to 1,000,000 mPa · s.)
An organopolysiloxane containing two alkenyl groups bonded to a silicon atom in one molecule,
(B) The following formula (2):

(In the formula, R ³ is the same or different unsubstituted or substituted monovalent hydrocarbon group, and at least one is an alkenyl group. R ⁴ has the same or different aliphatic unsaturated bond. Is an unsubstituted or substituted monovalent hydrocarbon group, R ⁵ is an alkenyl group, l and m are 0 or a positive integer, and l + m is the viscosity of the organopolysiloxane at 25 ° C. of 10 to 1,000. , 000 mPa · s.)
An organopolysiloxane containing 3 or more alkenyl groups bonded to silicon atoms in one molecule,
(C) an organohydrogenpolysiloxane containing two hydrogen atoms bonded to silicon atoms in one molecule; and
(D) a platinum group metal-based catalyst , wherein the molar ratio of hydrogen atoms bonded to silicon atoms to alkenyl groups bonded to silicon atoms in the composition is 1.0 or more; It consists of a cured product of a curable silicone rubber composition whose type A hardness specified in JIS K6253 is 20 or less,
The second sealing member is a silicone rubber-sealed light emitting device characterized by comprising a cured silicone resin layer having a type D hardness of 30 or more as defined in JIS K6253 and a thickness of 0.5 mm or less. A light emitting diode disposed on the bottom surface of the recess of the package having a recess having a bottom surface and a side surface;
(A) The following formula (1)

(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond, R ² is an alkenyl group, and k is 25 ° C. of the organopolysiloxane. Is 0 or a positive integer with a viscosity of 10 to 1,000,000 mPa · s.)
An organopolysiloxane containing two alkenyl groups bonded to a silicon atom in one molecule,
(B) The following formula (2):

(In the formula, R ³ is the same or different unsubstituted or substituted monovalent hydrocarbon group, and at least one is an alkenyl group. R ⁴ has the same or different aliphatic unsaturated bond. Is an unsubstituted or substituted monovalent hydrocarbon group, R ⁵ is an alkenyl group, l and m are 0 or a positive integer, and l + m is the viscosity of the organopolysiloxane at 25 ° C. of 10 to 1,000. , 000 mPa · s.)
An organopolysiloxane containing 3 or more alkenyl groups bonded to silicon atoms in one molecule,
(C) an organohydrogenpolysiloxane containing two hydrogen atoms bonded to silicon atoms in one molecule; and
(D) a platinum group metal-based catalyst , wherein the molar ratio of hydrogen atoms bonded to silicon atoms to alkenyl groups bonded to silicon atoms in the composition is 1.0 or more; Sealed with a cured product of a curable silicone rubber composition whose type A hardness specified in JIS K6253 is 20 or less,
A curable silicone resin having a specified type D hardness of 30 or more is applied to the cured JISK6253 on the surface of the cured product formed for the sealing,
Curing the coating film coated with the curable silicone resin to form a cured silicone resin layer having a thickness of 0.5 mm or less;
A method for producing a silicone rubber-sealed light emitting device, comprising a step.

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