JP2010123769A - Light emitting device and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light emitting device for suppressing reflection of light emitted by an LED chip on an interface with a translucent resin and also improving light extraction efficiency, and a method of manufacturing the same. <P>SOLUTION: The light emitting device includes a semiconductor light emitting element (LED chip) coated with a first translucent resin portion 5 and further includes the first translucent resin portion coated with a second translucent resin portion 6, the first translucent resin portion being made of an epoxy resin or silicone resin and the second translucent resin portion being made of a fluorine-containing resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a light emitting device formed by sealing a semiconductor light emitting element (LED chip) and a method for manufacturing the same.

  An LED (Light Emitting Diode) is a light-emitting element having features such as low power consumption, small size, light weight, and long life. In recent years, since the development of GaN-based blue LEDs, various technological developments have been carried out. Especially when white LEDs that combine blue LEDs and YAG phosphors have been realized, they can be used as next-generation energy-saving light sources. Has spread significantly.

  Light emitting devices using an LED chip as a light source (hereinafter referred to as “light emitting device”) include a shell type and a surface mount type. In any case, the LED chip is an external force, dust, heat, moisture, etc. In order to protect it from light, it is sealed with a translucent resin.

  According to Snell's law, the light-transmitting resin has a smaller reflection ratio of light emitted from the LED chip at the interface between the light-transmitting resin and the LED chip as the difference in refractive index from the LED chip is smaller. It is considered that the efficiency of extracting the light to the outside (hereinafter referred to as “light extraction efficiency”) can be increased. The refractive index of the LED chip varies depending on the semiconductor material. For example, it is 2.0 for ZnO, 2.7 for GaN, and about 3.5 for GaAs. For this reason, as this sealing resin, what has as high a refractive index as possible is desirable.

  Therefore, an epoxy resin is conventionally used as the translucent resin, and recently, a silicone resin is also used as a resin excellent in heat resistance and light resistance (Patent Document 1: Japanese Patent Application Laid-Open No. 10-228249). Patent Document 2: Japanese Patent No. 2927279 and Patent Document 3: Japanese Patent No. 4112443).

  The refractive index of these resins is usually about 1.40 to 1.65. In order to further increase the refractive index, a method of dispersing a metal oxide in the resin has been proposed (Patent Document 4). : JP-A-2007-53170).

  However, when the refractive index of the translucent resin is increased in this way, the difference in refractive index between the translucent resin, which is the outermost layer, and air (refractive index: 1.00) increases. The ratio of reflected light at the interface between the translucent resin and air is increased, and the light extraction efficiency is reduced.

Japanese Patent Laid-Open No. 10-228249 Japanese Patent No. 2927279 Japanese Patent No. 4112443 JP 2007-53170 A

  The present invention has been made in view of the above circumstances, and a light emitting device capable of improving light extraction efficiency by suppressing light emitted from an LED chip from being reflected at an interface between a light-transmitting resin and air. And it aims at providing the manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventors first coated an LED chip with a cured product of an epoxy resin composition or a silicone resin composition having translucency, and further translucent it. The present inventors have found that the above-mentioned problems can be solved by coating with a fluorine-containing resin composition having the present invention.

［式中、Ｘは−ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＨ₂ＯＣＨ₂−又は−Ｙ−ＮＲ²−ＣＯ−（Ｙは−ＣＨ₂−又は下記構造式（２）

（Ｒ¹はアルケニル基、Ｒ³は置換もしくは非置換の一価の飽和炭化水素基、ａは０、１又は２である）で示されるｏ，ｍ又はｐ−シリルフェニレン基）で表される基、Ｒ²は水素原子、又は置換もしくは非置換の一価炭化水素基、Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²−Ｙ’−（Ｙ’は−ＣＨ₂−又は下記構造式（３）

（Ｒ¹及びＲ³は上記と同じ基である。ｂは０、１又は２である）で示されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基であり、Ｒ²は上記と同じ基である。ｐは独立に０又は１、ｒは２〜６の整数、ｍ及びｎはそれぞれ１〜９０の整数であり、かつｍとｎの和は２〜１８０である。］
で表される直鎖状ポリフルオロ化合物である請求項５〜１２のいずれか１項に記載の発光装置。
請求項１４：
（Ｂ）成分の含フッ素オルガノ水素シロキサンが、１分子中に１個以上の一価のパーフルオロアルキル基、一価のパーフルオロオキシアルキル基、二価のパーフルオロアルキレン基、又は二価のパーフルオロオキシアルキレン基を有するものであることを特徴とする請求項５〜１３のいずれか１項に記載の発光装置。
請求項１５：
前記第一の透光性樹脂部で半導体発光素子を被覆し、さらにこの第一の透光性樹脂部を前記第二の透光性樹脂部で被覆することを特徴とする請求項１〜１４のいずれか１項に記載の発光装置の製造方法。 That is, this invention provides the following light-emitting device and its manufacturing method.
Claim 1:
A semiconductor light-emitting element, a first light-transmitting resin portion made of a cured product of a silicone resin composition and / or an epoxy resin composition, which is provided so as to cover the semiconductor light-emitting element; A light emitting device comprising: a second translucent resin portion made of a cured product of a fluororesin composition.
Claim 2:
The refractive index of the first translucent resin part at 25 ° C. and 589 nm (sodium D line) is 1.40 or more, and the second translucent resin part has a refractive index of 25 ° C. and 589 nm (sodium The light-emitting device according to claim 1, wherein the refractive index at D-line is less than 1.40.
Claim 3:
3. The light-emitting device according to claim 1, wherein a total light transmittance at 6 mm thickness of the first translucent resin portion is 80% or more.
Claim 4:
4. The light emitting device according to claim 1, wherein the total light transmittance at 6 mm thickness of the second translucent resin portion is 80% or more. 5.
Claim 5:
The fluorine-containing resin composition forming the second translucent resin is
(A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain: 100 parts by mass;
(B) Fluorine-containing organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule: 0.5 to 3.0 moles of SiH group per mole of alkenyl group of component (A) amount,
(C) Platinum group metal catalyst: 0.1 to 500 ppm in terms of platinum group metal atom
The light-emitting device according to claim 1, wherein the light-emitting device is a curable perfluoropolyether rubber composition containing
Claim 6:
The curable perfluoropolyether rubber composition further has, as component (D), an organosilicon compound having at least one epoxy group and / or alkoxy group directly bonded to a silicon atom in one molecule: (A) component 100 mass It contains 0.01-10.0 mass parts with respect to a part, The light-emitting device of Claim 5 characterized by the above-mentioned.
Claim 7:
The organosilicon compound of component (D) is one or more monovalent perfluoroalkyl groups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylene groups, or divalent perfluorooxy groups in one molecule. The light emitting device according to claim 6, wherein the light emitting device has an alkylene group.
Claim 8:
The light-emitting device according to claim 6 or 7, wherein the organosilicon compound as component (D) has a hydrogen atom directly bonded to one or more silicon atoms in one molecule.
Claim 9:
The curable perfluoropolyether rubber composition further comprises, as component (E), 1 epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom in one molecule. The light emitting device according to any one of claims 5 to 8, wherein the light emitting device comprises 0.01 to 10.0 parts by mass with respect to 100 parts by mass of the organosiloxane: component (A).
Claim 10:
The (E) component organosiloxane has at least one monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom. The light-emitting device according to claim 9.
Claim 11:
The light-emitting device according to claim 9 or 10, wherein the organosiloxane of component (E) has hydrogen atoms directly bonded to one or more silicon atoms in one molecule.
Claim 12:
The alkenyl group content of the linear polyfluoro compound (A) is 0.002 to 0.3 mol / 100 g, The light-emitting device according to claim 5.
Claim 13:
(A) component is the following general formula (1)

[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ² -CO- (Y is -CH ₂ - or the following structural formula (2)

(Wherein R ¹ is an alkenyl group, R ³ is a substituted or unsubstituted monovalent saturated hydrocarbon group, a is 0, 1 or 2), o, m or p-silylphenylene group) Group, R ² is a hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group, X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y ′ — ( Y ′ represents —CH ₂ — or the following structural formula (3)

A group (R ¹ and R ³ are .b is the same group as the above 0,1 or 2) represented by o represented by, m or p- dimethylsilylphenylene group), R ² is the Is the same group. p is independently 0 or 1, r is an integer of 2 to 6, m and n are each an integer of 1 to 90, and the sum of m and n is 2 to 180. ]
The light-emitting device according to claim 5, wherein the light-emitting device is a linear polyfluoro compound represented by the formula:
Claim 14:
The component (B) fluorine-containing organohydrogensiloxane is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent perfluoroalkyl group in one molecule. It has a fluoro oxyalkylene group, The light-emitting device of any one of Claims 5-13 characterized by the above-mentioned.
Claim 15:
15. The semiconductor light-emitting element is covered with the first light-transmitting resin portion, and the first light-transmitting resin portion is further covered with the second light-transmitting resin portion. The manufacturing method of the light-emitting device of any one of these.

  According to the present invention, a semiconductor light emitting device (LED chip) is coated with a cured product of an epoxy resin composition or a silicone resin composition, and further coated with a cured product of a fluororesin composition having a refractive index smaller than these, By reducing the difference in refractive index between the resin part of the outermost layer and the air, the ratio of the light emitted from the LED chip reflected at the interface between the resin part of the outermost layer and the air can be suppressed. Can be improved.

  Hereinafter, although embodiment of this invention is described, this invention does not receive any restrictions by the following description.

  A typical cross-sectional structure of the light-emitting device of the present invention is shown in FIGS.

  In the light emitting device of FIG. 1, a mortar-shaped concave portion 2 ′ whose diameter gradually increases from the bottom surface to the top portion 2 a of the first lead frame 2 is provided, and an LED chip is formed on the bottom surface of the concave portion 2 ′. The first lead frame 2 and one electrode (not shown) on the bottom surface of the LED chip 1 are electrically connected to each other by connecting and fixing 1 with a die paste through silver paste or the like. Further, the distal end portion 3 a of the second lead frame 3 and the other electrode (not shown) on the upper surface of the LED chip 1 are electrically connected via a bonding wire 4.

  Further, in the recess 2 ′, the LED chip 1 is covered with the first light-transmitting resin portion 5, and the first light-transmitting resin portion 5 is further covered with the second light-transmitting resin portion 6. .

  The LED chip 1, the top end 2 a of the first lead frame 2 and the top end of the terminal portion 2 b, and the top end 3 a of the second lead frame 3 and the top end of the terminal portion 3 b have a translucent lens portion 7 at the tip. Covered and sealed by the conductive resin portion 8. Further, the lower end of the terminal portion 2 b of the first lead frame 2 and the lower end of the terminal portion 3 b of the second lead frame 3 penetrate the lower end portion of the translucent resin portion 8 and protrude outside.

  In the light emitting device of FIG. 2, a mortar-shaped concave portion 9 ′ whose hole diameter gradually increases upward from the bottom surface is provided on the upper portion of the package substrate 9, and the LED chip 1 is formed on the bottom surface of the concave portion 9 ′ with a die bond material. The electrodes of the LED chip 1 are bonded and fixed, and are electrically connected to the electrodes 10 and 10 provided on the package substrate 9 by bonding wires 4.

  Further, in the concave portion 9 ′, the LED chip 1 is covered with the first translucent resin portion 5 and further covered with the second translucent resin portion 6.

  Here, the LED chip 1 is not particularly limited, and a light emitting element used in a conventionally known LED chip can be used. Such a light-emitting element is manufactured by stacking a semiconductor material on a substrate provided with a buffer layer of GaN, AlN, or the like, if necessary, by various methods such as MOCVD, HDVPE, and liquid phase growth. Things. Various materials can be used as the substrate in this case, and examples thereof include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Of these, sapphire is preferably used from the viewpoint that GaN having good crystallinity can be easily formed and has high industrial utility value.

Examples of laminated semiconductor materials include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaN, InGaAlN, and SiC. Of these, nitride-based compound semiconductors (In _x Ga _y Al _z N) are preferable from the viewpoint of obtaining high luminance. Such a material may contain an activator or the like.

  Examples of the structure of the light emitting element include a MIS junction, a pn junction, a homojunction having a PIN junction, a heterojunction, a double heterostructure, and the like. A single or multiple quantum well structure can also be used.

  A light-emitting element may or may not be provided with a passivation layer.

  Various light emission wavelengths from the ultraviolet region to the infrared region can be used, but the effect of the present invention is particularly remarkable when the main light emission peak wavelength is 550 nm or less.

  One type of light emitting element may be used for monochromatic light emission, or a plurality of light emitting elements may be used for single color or multicolor light emission.

  An electrode can be formed on the light emitting element by a conventionally known method.

  The electrode on the light emitting element can be electrically connected to the lead terminal or the like by various methods. As the electrical connection member, a material having good ohmic mechanical connectivity with the electrode of the light emitting element is preferable. For example, gold, silver, copper, platinum, aluminum, and those as described in FIG. 1 and FIG. An example of the bonding wire 4 is an alloy. Alternatively, a conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can be used. Of these, it is preferable to use an aluminum wire or a gold wire from the viewpoint of good workability.

  The first lead frame 2 and the second lead frame 3 are made of copper, a copper zinc alloy, an iron nickel alloy, or the like.

  Furthermore, the material for forming the translucent resin portion 8 is not particularly limited as long as it is a translucent material, but an epoxy resin or a silicone resin is mainly used.

  The package substrate 9 can be manufactured using various materials, for example, polycarbonate resin, polyphenylene sulfide resin, polybutylene terephthalate resin, polyamide resin, liquid crystal polymer, epoxy resin, acrylic resin, silicone resin, ABS resin. , BT resin, ceramic and the like. Further, it is preferable that the package substrate 9 is mixed with a white pigment such as barium titanate, titanium oxide, zinc oxide or barium sulfate to improve the light reflectance.

  Next, as the 1st translucent resin part 5 which coat | covers LED chip 1, the hardened | cured material of an epoxy resin composition is preferable from the point that transparency is high and it is excellent in practical characteristics, such as adhesiveness. The epoxy resin of such an epoxy resin composition is not particularly limited. For example, bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4 -Epoxy cyclohexyl) Adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, and other epoxy resins can be used, which are hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydroanhydride. Le acids include those cured with aliphatic acid anhydrides such as hydrogenated methylnadic anhydride. Among these, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, from the viewpoint of better properties in covering the LED chip, such as transparency, Those in which triglycidyl isocyanurate and the like are cured with methylhexahydrophthalic anhydride are preferable, and those in which 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is cured with methylhexahydrophthalic anhydride are more preferable. . In addition, as such an epoxy resin composition, a well-known thing is used.

  Moreover, as the 1st translucent resin part 5, the hardened | cured material of a silicone resin composition is preferable from the point of being highly transparent and excellent in heat resistance and light resistance. In this case, the silicone resin used in this case has a siloxane bond in which an organic group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and an epoxy group, a hydrogen atom, and a silicon atom directly bonded to a hydroxyl group are alternately bonded to an oxygen atom. As a resin.

  Examples of such a silicone resin composition include curable compositions described in JP-A No. 2004-186168, JP-A No. 4071639, JP-A No. 2004-292807, JP-A No. 2005-171021, and the like. However, it is not particularly limited to these.

  In the present invention, the “silicone resin” includes a resin in which the siloxane bond and an epoxy resin or an organic compound having an addition-reactive carbon-carbon double bond are connected to form a skeleton.

  Examples of such a silicone resin composition include curable compositions described in JP-A No. 2002-338833, JP-A No. 2005-314591 and JP-A No. 4112443, but are particularly limited thereto. It is not a thing.

  The refractive index at 25 ° C. and 589 nm (D-line of sodium) of the cured product of the epoxy resin composition and the silicone resin composition is the ratio of the light emitted from the LED chip reflected at the interface between the LED chip and the resin part. In order to make it small, the one where the difference with the refractive index of a LED chip is small is preferable, and specifically, it is preferable that it is 1.40 or more.

  The total light transmittance at 6 mm thickness of the cured product of the epoxy resin composition and the silicone resin composition is preferably 80% or more, and more preferably 85% or more. When the total light transmittance is less than 80%, the light extraction efficiency may be insufficient. The total light transmittance is measured according to JIS K7361-1.

  You may add various additives to the said epoxy resin composition and a silicone resin composition as needed. Examples of additives include phosphors such as yttrium, aluminum, and garnet phosphors activated with cerium, which absorbs light from the light emitting element and emits longer wavelength fluorescence, perylene derivatives, and copper. Activated zinc selenide, etc., coloring agents such as bluing agents that absorb specific wavelengths, titanium oxide, aluminum oxide, silica, quartz glass and other silicon oxides to diffuse light, talc, calcium carbonate, melamine Examples thereof include various inorganic or organic diffusion materials such as resins, CTU guanamine resins, and benzoguanamine resins, metal oxides such as glass and aluminosilicate, and thermally conductive fillers such as metal nitrides such as aluminum nitride and boron nitride.

  When hardening the said epoxy resin composition and a silicone resin composition, you may heat from the point of workability | operativity.

  Although various settings can be made as the heating temperature, for example, a temperature of 20 to 200 ° C. can be applied, and 50 to 180 ° C. is more preferable. If the reaction temperature is low, the reaction time for sufficient reaction will be long, and if the reaction temperature is high, various members constituting the light emitting device of the present invention may be deteriorated. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

  The curing time may be appropriately selected as long as the curing reaction is completed, but in general, curing is preferably performed in a time of about 10 minutes to 10 hours, and more preferably about 30 minutes to 8 hours.

  Next, as the 2nd translucent resin part 6, the cured | curing material of a fluorine-containing resin composition is preferable from the point that transparency is high and a refractive index is lower than the 1st translucent resin part 5. FIG. The base resin of such a fluorine-containing resin composition is not particularly limited. For example, vinylidene fluoride (VdF), hexafluoropropylene (HFP), pentafluoropropylene, trifluoroethylene, trifluorochloroethylene (CTFE) In addition to homopolymers or copolymers of fluorine-containing monomers such as tetrafluoroethylene (TFE), vinyl fluoride, perfluoro (methyl vinyl ether), perfluoro (propylvinylidene), etc., the fluorine-containing monomer and an acrylate ester Examples of such a copolymer include a vinyl compound such as propylene, an olefin compound such as propylene or a diene compound, a halogenated vinyl compound containing chlorine, bromine or iodine, and a specific example thereof is VdF-HFP copolymer. Coalescence, VdF-T E copolymer, VdF-CTFE copolymer, TFE-propylene-VdF terpolymer, TFE-HFP-VdF terpolymer, HFP-ethylene-VdF copolymer, fluoro (alkyl vinyl ether) -olefin Examples include copolymers (for example, VdF-TFE-perfluoro (alkyl vinyl ether) copolymers), THF-propylene copolymers, and the like. In addition, “Cytop” manufactured by Asahi Glass Co., Ltd. can be used as a commercially available product.

In particular, as the second translucent resin portion 6,
(A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain: 100 parts by mass;
(B) Fluorine-containing organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule: 0.5 to 3.0 moles of SiH group per mole of alkenyl group of component (A) amount,
(C) Platinum group metal catalyst: 0.1 to 500 ppm in terms of platinum group metal atom
It is also possible to use a cured product obtained by curing a curable perfluoropolyether rubber composition containing. Below, the detail of these compounding components is demonstrated.

[(A) component]
The component (A) of the curable perfluoropolyether rubber composition is a linear polyfluoro compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain. Yes, what is represented by the following general formula (1) is preferable.

［式中、Ｘは−ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＨ₂ＯＣＨ₂−又は−Ｙ−ＮＲ²−ＣＯ−（Ｙは−ＣＨ₂−又は下記構造式（２）

（Ｒ¹はアルケニル基、Ｒ³は置換もしくは非置換の一価の飽和炭化水素基、ａは０、１又は２である）で示されるｏ，ｍ又はｐ−シリルフェニレン基）で表される基、Ｒ²は水素原子、又は置換もしくは非置換の一価炭化水素基、Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²−Ｙ’−（Ｙ’は−ＣＨ₂−又は下記構造式（３）

（Ｒ¹及びＲ³は上記と同じ基である。ｂは０、１又は２である）で示されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基であり、Ｒ²は上記と同じ基である。ｐは独立に０又は１、ｒは２〜６の整数、ｍ及びｎはそれぞれ１〜９０の整数であり、かつｍとｎの和は２〜１８０である。］

[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ² -CO- (Y is -CH ₂ - or the following structural formula (2)

(Wherein R ¹ is an alkenyl group, R ³ is a substituted or unsubstituted monovalent saturated hydrocarbon group, a is 0, 1 or 2), o, m or p-silylphenylene group) group, R ² represents a hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group, X 'is _{-CH 2 -, - OCH 2 -} , - CH 2 OCH 2 - or -CO-NR ² -Y' - ( Y ′ represents —CH ₂ — or the following structural formula (3)

A group (R ¹ and R ³ are .b is the same group as the above 0,1 or 2) represented by o represented by, m or p- dimethylsilylphenylene group), R ² is the Is the same group. p is independently 0 or 1, r is an integer of 2 to 6, m and n are each an integer of 1 to 90, and the sum of m and n is 2 to 180. ]

Here, as the alkenyl group for R ¹ , those having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and having a CH ₂ ═CH— structure at the terminal are preferable, for example, vinyl group, allyl group, propenyl group, isopropenyl. Group, butenyl group, hexenyl group and the like, among which vinyl group and allyl group are preferable.

R ² is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. The substituted or unsubstituted monovalent hydrocarbon group is a monovalent carbon group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms. A hydrogen group is preferable. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group; an aryl group such as a phenyl group and a tolyl group; a benzyl group and a phenylethyl group Examples thereof include aralkyl groups such as groups, and substituted monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine.

Further, the substituted or unsubstituted monovalent saturated hydrocarbon group for R ³ is preferably a group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, and butyl. Group, hexyl group, cyclohexyl group, octyl group and other alkyl groups; phenyl group, tolyl group and other aryl groups; benzyl group, phenylethyl group and other aralkyl groups, and some or all of hydrogen atoms of these groups And a substituted monovalent hydrocarbon group substituted with a halogen atom such as fluorine. Of these, a methyl group and an ethyl group are preferable.

  Specific examples of the linear polyfluoro compound represented by the general formula (1) include those represented by the following formula. In the following formulae, Me represents a methyl group.

（式中、ｍ及びｎはそれぞれ１〜９０の整数であり、かつｍとｎの和は２〜１８０である。）

(In the formula, m and n are each an integer of 1 to 90, and the sum of m and n is 2 to 180.)

  These linear polyfluoro compounds can be used singly or in combination of two or more.

  The alkenyl group content contained in the linear polyfluoro compound of the above formula (1) is preferably 0.002 to 0.3 mol / 100 g, and more preferably 0.008 to 0.2 mol / 100 g. When the alkenyl group content contained in the linear fluoropolyether compound is less than 0.002 mol / 100 g, there is a possibility that the degree of cross-linking will be insufficient and a curing failure will occur. When it exceeds 3 mol / 100 g, the mechanical properties of the cured product as a rubber elastic body may be impaired.

[Component (B)]
The component (B) of the curable perfluoropolyether rubber composition is a fluorine-containing organohydrogensiloxane having 2 or more, preferably 3 or more, hydrogen atoms directly bonded to silicon atoms in one molecule. The component (B) functions as a crosslinking agent or chain extender for the component (A), and from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like. Having one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group or divalent perfluorooxyalkylene group in one molecule Is preferred.

Examples of the fluorine-containing group include those represented by the following general formula.
C _g F _{2g + 1} −
−C _g F _2g −
(In the formula, g is an integer of 1 to 20, preferably 2 to 10.)

（式中、ｆは２〜２００、好ましくは２〜１００の整数であり、ｈは１〜３の整数である。）

(In the formula, f is an integer of 2 to 200, preferably 2 to 100, and h is an integer of 1 to 3.)

（式中、ｉ及びｊは１以上の整数、ｉ＋ｊの平均は２〜２００、好ましくは２〜１００である。）
−（ＣＦ₂Ｏ）_r−（ＣＦ₂ＣＦ₂Ｏ）_s−ＣＦ₂−
（式中、ｒ及びｓはそれぞれ１〜５０の整数である。）

(In the formula, i and j are integers of 1 or more, and the average of i + j is 2 to 200, preferably 2 to 100.)
_{- (CF 2 O) r -} (CF 2 CF 2 O) s -CF 2 -
(In the formula, r and s are each an integer of 1 to 50.)

In addition, as the divalent linking group that connects the perfluoroalkyl group, perfluorooxyalkyl group, perfluoroalkylene group or perfluorooxyalkylene group and the silicon atom, an alkylene group, an arylene group and a combination thereof, or these In this group, an ether bond oxygen atom, an amide bond, a carbonyl bond, etc. may be interposed.
-CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ -,
_{-CH 2 CH 2 CH 2 OCH 2} -,
_{-CH 2 CH 2 CH 2 -NH-} CO-,
_{-CH 2 CH 2 CH 2 -N (} Ph) -CO- ( where, Ph is a phenyl group.),
_{-CH 2 CH 2 CH 2 -N (} CH 3) -CO-,
—CH ₂ CH ₂ CH ₂ —O—CO—
And those having 2 to 12 carbon atoms.

  Further, it contains a monovalent or divalent fluorine-containing substituent in the fluorine-containing organohydrogensiloxane of component (B), that is, a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, or a perfluorooxyalkylene group. Examples of monovalent substituents bonded to silicon atoms other than organic groups include, for example, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, and decyl groups; vinyl groups, Alkenyl groups such as allyl groups; aryl groups such as phenyl groups, tolyl groups, and naphthyl groups; aralkyl groups such as benzyl groups and phenylethyl groups, and at least some of the hydrogen atoms of these groups are substituted with chlorine atoms, cyano groups, or the like For example, chloromethyl group, chloropropyl group, cyanoethyl group, etc. Or unsubstituted hydrocarbon group but having no aliphatic unsaturated bonds such as alkenyl groups are preferred.

  The fluorine-containing organohydrogensiloxane as the component (B) may be any of cyclic, chain, three-dimensional network, or a combination thereof. The number of silicon atoms in the fluorine-containing organohydrogensiloxane is not particularly limited, but is usually 2 to 200, preferably 3 to 150, and more preferably 3 to 100.

  Examples of the component (B) having such a fluorine-containing group include the following compounds. These compounds may be used alone or in combination of two or more. In the following formulae, Me represents a methyl group.

  The blending amount of the component (B) is an effective amount for curing the component (A), and is usually (1 mol of an alkenyl group such as vinyl group, allyl group, cycloalkenyl group, etc. contained in the component (A) ( Component B) is an amount such that the hydrosilyl group of the component, that is, SiH group is 0.5 to 3.0 mol, more preferably 0.8 to 2.0 mol. If the amount of hydrosilyl groups (≡SiH) is too small, the degree of cross-linking may be insufficient. As a result, a cured product may not be obtained. If the amount is too large, foaming may occur during curing.

[Component (C)]
The platinum group metal catalyst which is the component (C) of the curable perfluoropolyether rubber composition is a hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst is a catalyst that promotes the addition reaction between the alkenyl group in component (A) and the hydrosilyl group in component (B). This hydrosilylation reaction catalyst is generally a noble metal or a compound thereof and is expensive, and thus platinum or platinum compounds that are relatively easily available are often used.

Examples of the platinum compound include chloroplatinic acid or a complex of chloroplatinic acid and an olefin such as ethylene, a complex of an alcohol or vinyl siloxane, metal platinum supported on silica, alumina, carbon, or the like. Rhodium, ruthenium, iridium, and palladium compounds are also known as platinum group metal catalysts other than platinum or its compounds. For example, RhCl (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , Ru ₃ (CO ) ₁₂ , IrCl (CO) (PPh ₃ ) ₂ , Pd (PPh ₃ ) _{4 and the} like. In the above formula, Ph is a phenyl group.

  When these catalysts are used, they can be used in solid form when they are solid catalysts, but in order to obtain a more uniform cured product, chloroplatinic acid or a complex dissolved in an appropriate solvent. Is preferably used by being dissolved in the linear polyfluoro compound of component (A).

  The compounding amount of the component (C) may be an effective amount as a hydrosilylation reaction catalyst, but can be appropriately increased or decreased depending on the desired curing rate. Usually, 0.1 to 500 ppm (in terms of platinum group metal atoms) is blended with respect to 100 parts by mass of component (A).

[(D) component]
Various additives can be added to the curable perfluoropolyether rubber composition as necessary in order to enhance its practicality. In particular, for the purpose of imparting self-adhesive properties to the curable perfluoropolyether rubber composition, organosilicon having at least one epoxy group and / or alkoxy group directly bonded to a silicon atom in one molecule as the component (D) It is preferable to add a compound.

  The component (D) is the same as the monovalent and divalent fluorine-containing groups described in the component (B) from the viewpoints of compatibility with the component (A), dispersibility, and uniformity after curing. Those having one or more monovalent perfluoroalkyl groups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylene groups, or divalent perfluorooxyalkylene groups in one molecule are more preferred.

  In addition, as the component (D), one having a hydrogen atom directly bonded to one or more silicon atoms in one molecule is useful in that the curable perfluoropolyether rubber composition is provided with self-adhesiveness. is there.

Specific examples of the component (D) include the following compounds. In the following formulae, Me represents a methyl group.

  0.01-10.0 mass parts is preferable with respect to 100 mass parts of said (A) component, and, as for the compounding quantity of the said (D) component, 0.1-5.0 mass parts is more preferable. When the amount is less than 0.01 parts by mass, sufficient adhesiveness cannot be obtained, and when the amount exceeds 10.0 parts by mass, the fluidity of the curable perfluoropolyether rubber composition is deteriorated and obtained from the composition. There is a possibility that the physical strength of the cured product to be reduced.

[(E) component]
In addition, for the same purpose as the component (D), together with or in addition to the component (D), as a component (E), bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom in one molecule It is also preferable to add an organosiloxane having one or more epoxy groups and / or trialkoxysilyl groups.

  As the component (E), from the viewpoint of compatibility with the component (A), dispersibility, uniformity after curing, etc., one molecule is bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom. Those having at least one monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group are more preferred.

  In addition, as the component (E), those having hydrogen atoms directly bonded to one or more silicon atoms in one molecule are useful in that the curable perfluoropolyether rubber composition is provided with self-adhesiveness. is there.

  The siloxane skeleton of the organosiloxane of the component (E) may be any of cyclic, chain, branched, etc., or a mixed form thereof. As the (E) component organosiloxane, those represented by the following general formula can be used.

（上記一般式中、Ｒ⁴はハロゲン置換又は非置換の一価炭化水素基であり、Ｌ、Ｍは下記に示す。ｗは０≦ｗ≦５０、より好ましくは０≦ｗ≦２０の整数であり、ｘは１≦ｘ≦５０、より好ましくは１≦ｘ≦２０の整数であり、ｙは１≦ｙ≦５０、より好ましくは１≦ｙ≦２０の整数であり、ｚは０≦ｚ≦５０、より好ましくは０≦ｚ≦２０の整数である。またｗ＋ｘ＋ｙ＋ｚは、ＧＰＣによるポリスチレン換算重量平均分子量２，０００〜２０，０００を満たすような整数である。）

(In the above general formula, R ⁴ is a halogen-substituted or unsubstituted monovalent hydrocarbon group, L and M are shown below. W is an integer of 0 ≦ w ≦ 50, more preferably 0 ≦ w ≦ 20. X is an integer of 1 ≦ x ≦ 50, more preferably 1 ≦ x ≦ 20, y is an integer of 1 ≦ y ≦ 50, more preferably 1 ≦ y ≦ 20, and z is 0 ≦ z ≦ 20. 50, more preferably an integer of 0 ≦ z ≦ 20, and w + x + y + z is an integer that satisfies a polystyrene-reduced weight average molecular weight of 2,000 to 20,000 by GPC.)

The halogen-substituted or unsubstituted monovalent hydrocarbon group represented by R ⁴ is preferably a group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group. Alkyl groups such as cyclohexyl group and octyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenylethyl group; and some or all of hydrogen atoms of these groups are halogen such as fluorine. Examples thereof include a substituted monovalent hydrocarbon group substituted with an atom, and among these, a methyl group is particularly preferable.

  L represents an epoxy group and / or a trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and specific examples thereof include the following groups.

（式中、Ｒ⁵は酸素原子が介在してもよい炭素数１〜１０、特に１〜５の二価炭化水素基で、具体的にはメチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、シクロヘキシレン基、オクチレン基等のアルキレン基等を示す。）
−Ｒ⁶−Ｓｉ（ＯＲ⁷）₃
（式中、Ｒ⁶は炭素数１〜１０、特に１〜４の二価炭化水素基、具体的にはメチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、シクロヘキシレン基、オクチレン基等のアルキレン基等を示し、Ｒ⁷は炭素数１〜８、特に１〜４の一価炭化水素基、具体的にはメチル基、エチル基、ｎ−プロピル基等のアルキル基を示す。）

(In the formula, R ⁵ is a divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms in which an oxygen atom may intervene, specifically methylene group, ethylene group, propylene group, butylene group, hexylene. Group, alkylene group such as cyclohexylene group, octylene group and the like.
-R ⁶ -Si (OR ⁷ ) ₃
(In the formula, R ⁶ is a divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms, specifically methylene group, ethylene group, propylene group, butylene group, hexylene group, cyclohexylene group, octylene group, etc. R ⁷ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, specifically an alkyl group such as a methyl group, an ethyl group, or an n-propyl group.

（式中、Ｒ⁸は炭素数１〜８、特に１〜４の一価炭化水素基（アルキル基等）を示し、Ｒ⁹は水素原子又はメチル基、ｋは２〜１０の整数を示す。）

(In the formula, R ⁸ represents a monovalent hydrocarbon group (alkyl group or the like) having 1 to 8, particularly 1 to 4 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group, and k represents an integer of 2 to 10. )

As the structure of M, one represented by the following general formula (4) is preferable.
-Z-Rf (4)
[In Formula (4), Z _{- (CH 2) t -X "} - is preferably one represented by, X" is -OCH ₂ -, or -Y "-NR ¹⁰ -CO- (Y" is - CH ₂ — or the following structural formula (5)

（式中、Ｒ¹¹及びＲ¹²は水素原子、置換もしくは非置換の一価の飽和炭化水素基、又は置換もしくは非置換の一価の不飽和炭化水素基）で示されるｏ，ｍ又はｐ−シリルフェニレン基であり、Ｒ¹⁰は水素原子、置換もしくは非置換の好ましくは炭素数１〜１２、特に１〜１０の一価炭化水素基である。）で表される基であり、ｔは１〜１０、より好ましくは１〜５の整数である。］

Wherein R ¹¹ and R ¹² are a hydrogen atom, a substituted or unsubstituted monovalent saturated hydrocarbon group, or a substituted or unsubstituted monovalent unsaturated hydrocarbon group. A silylphenylene group, and R ¹⁰ is a hydrogen atom, a substituted or unsubstituted, preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms. ), And t is an integer of 1 to 10, more preferably 1 to 5. ]

Rf represents a monovalent perfluoroalkyl group or a perfluorooxyalkyl group. Examples of the monovalent perfluoroalkyl group or perfluorooxyalkyl group include the same groups as those exemplified as the monovalent fluorine-containing group of the component (B), specifically, the following general formula: And the like.
C _g F _{2g + 1} −

（式中、ｇは１〜２０、好ましくは２〜１０の整数である。またｆは２〜２００、好ましくは２〜１００の整数であり、ｈは１〜３の整数である。）

(In the formula, g is an integer of 1 to 20, preferably 2 to 10. f is an integer of 2 to 200, preferably 2 to 100, and h is an integer of 1 to 3.)

  These organosiloxanes are organohydrogenpolysiloxanes having 3 or more hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, aliphatic unsaturated groups such as vinyl groups and allyl groups, epoxy groups and / or A compound containing a trialkoxysilyl group, and if necessary, a compound containing the aliphatic unsaturated group and a perfluoroalkyl group or a perfluorooxyalkyl group can be obtained by partial addition reaction according to a conventional method. . The number of aliphatic unsaturated groups needs to be smaller than the number of SiH groups.

  In the production of the organosiloxane of the component (E) in the present invention, the target substance may be isolated after completion of the reaction, but a mixture in which the unreacted product and the addition reaction catalyst are simply removed can also be used.

  Specific examples of the organosiloxane used as the component (E) include those represented by the following structural formula. In addition, these compounds may be used independently and may use 2 or more types together. In the following formulae, Me represents a methyl group.

  (E) 0.01-10.0 mass parts is preferable with respect to 100 mass parts of said (A) component, and, as for the usage-amount of (A) component, 0.1-5.0 mass parts is more preferable. When the amount is less than 0.01 parts by mass, sufficient adhesiveness cannot be obtained, and when the amount exceeds 10.0 parts by mass, the fluidity of the curable perfluoropolyether rubber composition is deteriorated and obtained from the composition. There is a possibility that the physical strength of the cured product to be reduced.

[Other ingredients]
In addition to the above components (A) to (E), the curable perfluoropolyether rubber composition includes a plasticizer, a viscosity modifier, a flexibility imparting agent, and an inorganic filler in order to enhance its practicality. Various compounding agents such as an adhesion promoter can be added as necessary. The amount of these additives is arbitrary as long as the properties of the LED are not impaired and the physical properties of the cured product obtained from the composition are not impaired.

（式中、ｆは１以上の整数、ｈは２又は３であり、かつ前記一般式（１）におけるｍ＋ｎ（平均）及びｒの和よりも小さい。）］ As a plasticizer, a viscosity modifier, and a flexibility imparting agent, a polyfluoromonoalkenyl compound represented by the following general formula (6) and / or a linear poly represented by the following general formulas (7) and (8) A fluoro compound can be used in combination.
Rf ³ − (X ′) _p CH═CH ₂ (6)
[Wherein, X ′ and p are the same as those described in the above formula (1), and Rf ³ is a group represented by the following general formula (9).

(In the formula, f is an integer of 1 or more, h is 2 or 3, and is smaller than the sum of m + n (average) and r in the general formula (1).)]

_{D-O- (CF 2 CF 2} CF 2 O) c -D (7)
(In the formula, D is a group represented by the formula: C _s F _{2s + 1} — (s is 1 to 3), c is an integer of 1 to 200, and m + n in the general formula (1) (Less than the sum of (average) and r.)
_{D-O- (CF 2 O)} d (CF 2 CF 2 O) e -D (8)
(Wherein D is the same as above, d and e are each an integer of 1 to 200, and the sum of d and e is equal to or less than the sum of m + n (average) and r in the general formula (1)) .)

  Specific examples of the polyfluoromonoalkenyl compound represented by the general formula (6) include, for example, the following (note that m2 below corresponds to f in the general formula (9)). .

Specific examples of the linear polyfluoro compound represented by the general formulas (7) and (8) include the following (for example, the following n3 and the sum of n3 and m3 are the above general formulas). (7) and (8) respectively corresponding to the sum of c and d + e).
_{CF 3 O- (CF 2 CF 2} CF 2 O) n3 -CF 2 CF 3
_{CF 3 - [(OCF 2 CF} 2) n3 (OCF 2) m3] -O-CF 3
(M3 + n3 = 2 to 201, m3 = 1 to 200, n3 = 1 to 200)

  Examples of the inorganic filler include fumed silica, precipitated silica, silica aerogel, and the like. The surface of the filler may be treated with various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes and the like.

  Moreover, adhesion promoters, such as a carboxylic acid anhydride and a titanic acid ester, can be added as an adhesion promoter.

  In addition, as a control agent for hydrosilylation reaction catalyst, 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl Acetylenic alcohols such as -1-penten-3-ol and phenylbutynol, and a reaction product of chlorosilane having the above monovalent fluorine-containing substituent and acetylenic alcohol, 3-methyl-3-penten-1-yne 3,5-dimethyl-3-hexen-1-in, triallyl isocyanurate, or the like, or polyvinylsiloxane, an organic phosphorus compound, or the like can be added.

  The production method of the curable perfluoropolyether rubber composition is not particularly limited, and the above components (A) to (E) and other optional components are mixed with a mixing device such as a planetary mixer, a loss mixer, a Hobart mixer, a kneader. It can be produced by mixing using a kneading apparatus such as a three roll. Moreover, it can also heat-process as needed.

  Regarding the configuration of the curable perfluoropolyether rubber composition, it is configured as a so-called one-component type in which the above components (A) to (E) and all other optional components are handled as one composition depending on the use. Alternatively, a two-component type may be used, and both may be mixed at the time of use.

  When the curable perfluoropolyether rubber composition is cured, it is preferably heated from the viewpoint of workability.

  Although various settings can be made as the heating temperature, for example, a temperature of 20 to 200 ° C. can be applied, and 50 to 180 ° C. is more preferable. If the reaction temperature is low, the reaction time for sufficient reaction will be long, and if the reaction temperature is high, various members constituting the light emitting device of the present invention may be deteriorated. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

  The curing time may be appropriately selected as long as the curing reaction is completed, but in general, curing is preferably performed in a time of about 10 minutes to 10 hours, and more preferably about 30 minutes to 8 hours.

  The refractive index at 25 ° C. and 589 nm (sodium D-line) of the cured product of the fluororesin composition that is the second transparent resin portion 6 is the first light-transmitting property for the purpose of the present invention. It needs to be smaller than the refractive index of the resin part 5, and specifically needs to be less than 1.40.

  Moreover, it is preferable that the total light transmittance in 6 mm thickness of the hardened | cured material of the said fluorine-containing resin composition is 80% or more, and 85% or more is more preferable. When the total light transmittance is less than 80%, the light extraction efficiency may be insufficient. The total light transmittance is measured according to JIS K7361-1.

  Furthermore, the various additives demonstrated about the said epoxy resin composition and the silicone resin composition can be added to the said fluorine-containing resin composition.

[Method for Manufacturing Light-Emitting Device of the Present Invention]
The light-emitting device of the present invention can be manufactured by first coating a semiconductor light-emitting element (LED chip) with the first light-transmitting resin portion, and further covering it with the second light-transmitting resin portion. it can.

  The method of coating is not particularly limited as long as the semiconductor light-emitting element is covered with the first light-transmitting resin portion as described above, and further covered with the second light-transmitting resin portion. First, the semiconductor light-emitting element is coated with a curable composition that provides the first translucent resin portion, and cured under the above-described curing conditions. Next, when the first light-transmitting resin part is coated with the second light-transmitting resin part, when the copolymer is used for the second light-transmitting resin part, workability is improved. From this point, it is desirable to coat the first light-transmitting resin part by dissolving the copolymer in a suitable solvent at a desired concentration to form a solution. Then, what is necessary is just to heat at the temperature of the range which does not degrade the various members which comprise the light-emitting device of this invention, and just to remove a solvent. Or you may soften the said copolymer until it has fluidity | liquidity by heating, and may coat | cover this 1st translucent resin part. Even when a Cytop is used for the second translucent resin portion, the solvent in the Cytop may be removed by heating in the same manner after the first translucent resin portion is coated. On the other hand, when the curable perfluoropolyether rubber composition is used as the second translucent resin portion, the first translucent resin portion is used as it is because the composition has fluidity. And then cured under the above curing conditions.

  As another coating method, when the density of the first light-transmitting resin portion is larger than the density of the second light-transmitting resin portion, the semiconductor light-emitting element is connected to the first light-transmitting resin portion. After coating with the curable composition that gives the second translucent resin part, the composition giving the first translucent resin part as described above is coated with the composition that gives the second translucent resin part, You may harden simultaneously on the conditions which satisfy | fill a hardening condition.

  When manufacturing the light emitting device of the present invention, the semiconductor light emitting element and the package substrate and the first translucent resin portion, or the first translucent resin portion and the package substrate and the second translucent resin portion. Various primers can be used in order to improve the adhesion and the like.

  The light emitting device of the present invention can be used for various known applications. Specifically, for example, backlights, general lighting, sensor light sources, vehicle instrument light sources, signal lights, indicator lights, display devices, planar light source light sources, displays, decorations, vehicle interior lighting, headlamps, stop lamps, etc. Examples include vehicle exterior lamps.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part and Me shows a methyl group.

[Preparation Example 1]
The fluorine-containing acetylene alcohol 0.9 represented by the following formula (11) is added to 100 parts of a polymer represented by the following formula (10) (vinyl group amount: 0.031 mol / 100 g, kinematic viscosity: 2,200 mm ² / s). Part, a toluene solution of a platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass) 0.3 part, 9.7 parts of a fluorine-containing organohydrogensiloxane represented by the following formula (12), the following formula (13) Then, 2.0 parts of an organosilicon compound represented by the formula (1) was sequentially added and mixed to be uniform. Then, the composition 1 was prepared by performing defoaming operation.

[Preparation Example 2]
A composition 2 was prepared in the same manner as in Preparation Example 1 except that 2.0 parts of an organosiloxane represented by the following formula (14) was used instead of the organosilicon compound represented by the above formula (13) in Preparation Example 1. Prepared.

[Example 1]
Example 1 is an example of a light emitting device having a configuration similar to that of the embodiment of FIG. That is, in FIG. 2, the two-component curable epoxy resin EL438 (manufactured by Sanyu Rec Co., Ltd.) is formed in the concave portion so as to immerse the LED chip 1 capable of emitting blue (450 nm) in order to form the first translucent resin portion 5. The LED chip 1 was sealed with the first translucent resin portion 5 by being injected into 9 ′ and heated at 120 ° C. for 4 hours. Next, on the first translucent resin portion 5, the above composition 1 is injected so as to fill the concave portion 9 ′ in order to form the second translucent resin portion 6, and at 90 ° C. The light emitting device shown in FIG. 2 was manufactured by heating at 150 ° C. for 2 hours and further for 5 hours.

[Example 2]
In Example 1, instead of the epoxy resin, a two-component curable silicone resin KER-2500A / B (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the first translucent resin portion 5 at 100 ° C. for 1 hour, Further, a light emitting device was produced in the same manner as in Example 1 except that heating was performed at 150 ° C. for 3 hours.

[Example 3]
In Example 1, a light emitting device was produced in the same manner as in Example 1 except that the above composition 2 was used instead of the above composition 1.

[Example 4]
In Example 1, a solution obtained by dissolving fluororesin Cytop CTL107M (manufactured by Asahi Glass Co., Ltd.) in the solvent Cytop CT-Solv100 instead of the composition 1 was used at 90 ° C. for 4 hours, and further at 120 ° C. for 4 hours. A light emitting device was manufactured in the same manner as in Example 1 except that the heating was performed for a time.

[Comparative Example 1]
In FIG. 3, the epoxy resin as the first translucent resin portion 5 is injected so as to fill the concave portion 9 ′, and heated at 120 ° C. for 4 hours, thereby producing the light emitting device shown in FIG. 3.

[Comparative Example 2]
In FIG. 3, the silicone resin as the first translucent resin portion 5 is injected so as to fill the concave portion 9 ′, and heated at 120 ° C. for 4 hours, thereby producing the light emitting device shown in FIG. 3.

  About each resin used for the 1st translucent resin part 5 or the 2nd translucent resin part 6 in the said Examples 1-4, it poured into the type | mold of 85 mm x 105 mm x thickness 3mm, and each said Example 1 A cured sample having a thickness of 3 mm was obtained by curing under the curing conditions described in -4. And the refractive index in 25 degreeC and 589 nm (sodium D line | wire) was measured with the multiwavelength Abbe refractometer DR-M2 / 1550 (made by Atago Co., Ltd.) using this hardening sample. The results are shown in Table 1.

  About each resin used for the 1st translucent resin part 5 or the 2nd translucent resin part 6 in the said Examples 1-4, it poured into the type | mold of 50 mm x 70 mmx thickness 6mm, and each said Example 1 A cured sample having a thickness of 6 mm was obtained by curing under the curing conditions described in -4. And the total light transmittance was measured with the haze meter HGM-2 (made by Suga Test Instruments Co., Ltd.) using this hardening sample. The results are shown in Table 1.

  The light emitting devices of Examples 1 to 4 and Comparative Examples 1 and 2 were turned on with ratings, and the light intensity was measured. The results are shown in Table 2 as relative values with the luminous intensity of Example 1 as 1.00.

It is a schematic sectional drawing which shows an example of embodiment which concerns on this invention. It is a schematic sectional drawing which shows another example of embodiment which concerns on this invention. It is a schematic sectional drawing which shows an example of the form of the comparative example which concerns on this invention.

Explanation of symbols

1 LED chip 2 First lead frame 2a First lead frame tip 2b First lead frame terminal 2 'Recess 3 Second lead frame 3a Second lead frame tip 3b Second lead Frame terminal portion 4 Bonding wire 5 First light-transmitting resin portion 6 Second light-transmitting resin portion 7 Convex lens portion 8 Light-transmitting resin portion 9 Package substrate 9 ′ Recess 10 Electrode

Claims (15)

  A semiconductor light-emitting element, a first light-transmitting resin portion made of a cured product of a silicone resin composition and / or an epoxy resin composition, which is provided so as to cover the semiconductor light-emitting element; A light emitting device comprising: a second translucent resin portion made of a cured product of a fluororesin composition.   The refractive index of the first translucent resin part at 25 ° C. and 589 nm (sodium D line) is 1.40 or more, and the second translucent resin part has a refractive index of 25 ° C. and 589 nm (sodium The light-emitting device according to claim 1, wherein the refractive index at D-line is less than 1.40.   3. The light emitting device according to claim 1, wherein the total light transmittance at 6 mm thickness of the first translucent resin portion is 80% or more.   The light-emitting device according to any one of claims 1 to 3, wherein the total light transmittance at 6 mm thickness of the second translucent resin portion is 80% or more. The fluorine-containing resin composition forming the second translucent resin is
(A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain: 100 parts by mass;
(B) Fluorine-containing organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule: 0.5 to 3.0 moles of SiH group per mole of alkenyl group of component (A) amount,
(C) Platinum group metal catalyst: 0.1 to 500 ppm in terms of platinum group metal atom
The light-emitting device according to claim 1, wherein the light-emitting device is a curable perfluoropolyether rubber composition containing The curable perfluoropolyether rubber composition further has, as component (D), an organosilicon compound having at least one epoxy group and / or alkoxy group directly bonded to a silicon atom in one molecule: (A) component 100 mass The light-emitting device according to claim 5, wherein the light-emitting device contains 0.01 to 10.0 parts by mass with respect to parts.   The organosilicon compound of component (D) is one or more monovalent perfluoroalkyl groups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylene groups, or divalent perfluorooxy groups in one molecule. The light emitting device according to claim 6, wherein the light emitting device has an alkylene group.   The light-emitting device according to claim 6 or 7, wherein the organosilicon compound as component (D) has a hydrogen atom directly bonded to one or more silicon atoms in one molecule. The curable perfluoropolyether rubber composition further includes, as component (E), 1 epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom in one molecule. 9. The light-emitting device according to claim 5, wherein 0.01 to 10.0 parts by mass is contained per 100 parts by mass of the organosiloxane: component (A).   The (E) component organosiloxane has at least one monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom. The light-emitting device according to claim 9.   The light-emitting device according to claim 9 or 10, wherein the organosiloxane of component (E) has hydrogen atoms directly bonded to one or more silicon atoms in one molecule.   The light-emitting device according to any one of claims 5 to 11, wherein the linear polyfluoro compound (A) has an alkenyl group content of 0.002 to 0.3 mol / 100 g. (A) component is the following general formula (1)

[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ² -CO- (Y is -CH ₂ - or the following structural formula (2)

(Wherein R ¹ is an alkenyl group, R ³ is a substituted or unsubstituted monovalent saturated hydrocarbon group, a is 0, 1 or 2), o, m or p-silylphenylene group) Group, R ² is a hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group, X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y ′ — ( Y ′ represents —CH ₂ — or the following structural formula (3)

A group (R ¹ and R ³ are .b is the same group as the above 0,1 or 2) represented by o represented by, m or p- dimethylsilylphenylene group), R ² is the Is the same group. p is independently 0 or 1, r is an integer of 2 to 6, m and n are each an integer of 1 to 90, and the sum of m and n is 2 to 180. ]
The light-emitting device according to claim 5, wherein the light-emitting device is a linear polyfluoro compound represented by the formula:   The fluorine-containing organohydrogensiloxane of component (B) is one or more monovalent perfluoroalkyl groups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylene groups, or divalent perfluoro groups in one molecule. The light-emitting device according to claim 5, wherein the light-emitting device has a fluorooxyalkylene group.   The semiconductor light emitting element is covered with the first light transmitting resin portion, and the first light transmitting resin portion is further covered with the second light transmitting resin portion. The manufacturing method of the light-emitting device of any one of these.

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