JP2006049533A - Resin sealing light emitting diode device and sealing method - Google Patents

Resin sealing light emitting diode device and sealing method Download PDF

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JP2006049533A
JP2006049533A JP2004227410A JP2004227410A JP2006049533A JP 2006049533 A JP2006049533 A JP 2006049533A JP 2004227410 A JP2004227410 A JP 2004227410A JP 2004227410 A JP2004227410 A JP 2004227410A JP 2006049533 A JP2006049533 A JP 2006049533A
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emitting diode
light
composition
mpa
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Tetsuya Murakami
Gerhard Staiger
ゲルハルト・シユタイガー
哲也 村上
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Wacker Asahikasei Silicone Co Ltd
Wacker Chemie Gmbh
ワツカー−ケミー ゲゼルシヤフト ミツト ベシユレンクテル ハフツングWacker−Chemie GmbH
旭化成ワッカーシリコーン株式会社
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Priority to JP2004227410A priority Critical patent/JP2006049533A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/12Polysiloxanes containing silicon bound to hydrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/14Polysiloxanes containing silicon bound to oxygen-containing groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/14Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/20Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80Siloxanes having aromatic substituents, e.g. phenyl side groups
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52Encapsulations
    • H01L33/56Materials, e.g. epoxy or silicone resin

Abstract

Provided is a light-emitting diode encapsulated with a material in which obstacles due to distortion due to a rapid temperature change are remarkably improved while maintaining the transparency, light resistance, and heat resistance of a silicone material.
In a light-emitting diode device in which the surface of a light-emitting diode element is coated with a soft addition-curable silicone and further sealed with a resinous addition-curable silicone resin, the soft addition-curable silicone is (A) one. An organopolysiloxane having an alkenyl group bonded to at least 1.8 silicon atoms per molecule and having a viscosity of 10 to 10,000 mPa · s, (B) hydrogen bonded to at least 4 silicon atoms on average per molecule A cured product of a composition comprising an organohydrogenpolysiloxane having atoms and a viscosity of 10 to 10,000 mPa · s, and (C) a catalytic amount of a hydrosilylation catalyst that promotes curing of the composition. A light emitting diode device having a length of 5 or more and 75 or less in a type E durometer.
[Selection figure] None

Description

  The present invention relates to a light emitting diode device in which a light emitting diode element (hereinafter referred to as an LED element) composed of a light emitting diode chip, a lead frame, and a bonding wire connecting them is sealed with silicone, and a sealing method thereof, in particular, blue to ultraviolet light. The present invention relates to a light-emitting diode device including LED elements that emit light and a method for sealing the LED elements.

  An LED element is sealed with a transparent resin and used as a light emitting device, and an epoxy resin has generally been used as a transparent resin for sealing. The epoxy resin is excellent in transparency, and has sufficient strength and rigidity. However, in recent years, the demand for blue-ultraviolet light emitting LED elements, which are expected to increase in demand, or fluorescent light is expected. Silicone resins have attracted attention for white light emitting devices that seal LED elements emitting blue to ultraviolet light with a resin mixed with a body. This is because the epoxy resin does not have sufficient heat resistance and light resistance corresponding to the high brightness and short wavelength of the LED element. That is, when the epoxy resin encapsulant is irradiated with ultraviolet rays or the like from the chip, the joints of the organic polymer are cut, and various optical and chemical characteristics are deteriorated. This is because the epoxy resin is gradually yellowed to cause a coloring phenomenon and thus has a disadvantage that the lifetime of the light emitting device is limited. On the other hand, silicone resins are expected to be used for sealing LED elements that emit blue to ultraviolet light, in that they are excellent in transparency and are significantly less deteriorated by ultraviolet rays.

  For example, Patent Document 1 proposes to use a siloxane compound containing an alkoxy group capable of reacting with a hydroxyl group on a compound semiconductor and generating a silicone resin by an addition reaction as a sealing resin for an LED element. In some cases, a polymer compound having an organosiloxane skeleton is used. However, although the light resistance is improved when a hard silicone resin is used, the silicone resin generally has a large expansion coefficient, and when the LED element undergoes a rapid temperature change, the metal portion constituting the LED element and the silicone There is a problem that the strain generated by the difference in expansion increases. LED elements are high in energy and become hot when energized, and are subject to rapid temperature changes due to ON-OFF, and have the problem that cracks and the like are likely to occur due to distortion due to repeated temperature changes. .

  An example of using elastomer or gel silicone for sealing an LED element is also known. For example, in Patent Document 2, a liquid silicone in which a phosphor is dispersed is used for sealing. Silicone that becomes gel after heat-curing is compared with rubber-like silicone. It is preferable in terms of protection. When an elastic silicone elastomer is used for sealing an LED element, it is easily deformed by an external mechanical force. Depending on the deformation, there is a problem that the bonding wire of the LED element is cut. It is difficult to say that the mechanical strength of the elastomer itself is sufficient.

  On the other hand, instead of sealing with a single hard resin or a single soft material such as an elastomer as a sealing method of the LED element, the surface of the LED element is covered with a soft material and further sealed with a hard resin. A two-layer structure has also been proposed. For example, Patent Document 3 proposes using silicone having rubber elasticity, which can be called an elastomer, for the inner layer and using an epoxy resin for the outer layer. Patent Document 4 proposes that the surface of the LED element is first coated with gel-like or elastomer-like silicone and then sealed with a hard silicone resin.

  The light-emitting diode device obtained by this two-layer structure has improved defects when sealed with either one, but there is no problem that the expansion coefficient of the soft silicone of the inner layer used is significantly different from that of metal. I don't mean. Since the linear expansion of the soft silicone itself as the inner layer is large, the LED element metal part generated by the difference in expansion between the lead frame and the resin and the silicone part in contact with the LED element when there is a rapid temperature change in the LED element However, the problem of the peeling of the interface due to repeated rapid temperature changes still remained.

JP-A-6-314816 JP 2002-314142 A Japanese Patent Laid-Open No. 54-19660 JP 2004-140220 A

  In this way, the problem of sealing with a single silicone composition is solved by adopting a two-layer structure that uses soft silicone for the inner layer and hard silicone for the outer layer for sealing LED elements using silicone. However, it has not been sufficient yet, and there has been a demand for a silicone composition particularly suitable for use in the inner layer. Further, there has been a demand for a composition used for an outer hard silicone layer which is an optimal combination with an optimal soft silicone inner layer.

  The present invention relates to a two-layer LED element sealing in which soft silicone is used for the inner layer and hard silicone is used for the outer layer, in particular, sealing of LED elements emitting blue to ultraviolet light and sealing for making a white light emitting device. In view of the problems of conventional technology in Japan, cracks caused by strain accompanying rapid temperature changes have been remarkably improved while maintaining the transparency, light resistance and heat resistance of silicone materials. It is an object of the present invention to provide an excellent encapsulating material composition and a light emitting diode encapsulated thereby.

  As a result of intensive studies to solve the above problems, the present inventors sealed a LED by combining a soft addition-curable silicone having a specific composition and a specific addition-curable silicone resin. Cracking due to sudden temperature changes is extremely low, sealing without impairing characteristics such as light transmittance, refractive index, light resistance, heat resistance inherent to silicone sealing, hard and hard to crack, and little shrinkage during molding It has been found that a light emitting diode device can be provided, and the present invention has been made.

That is, the present invention
(1) In a light-emitting diode device in which the surface of a light-emitting diode element is coated with a soft addition-curable silicone and further sealed with a resin-like addition-curable silicone resin, the soft addition-curable silicone is (A) to ( A light-emitting diode device, which is a cured product of the composition comprising C) and has a hardness after curing of 5 to 75 with a Type E durometer.
(A) Organo having an alkenyl group bonded to at least 1.8 silicon atoms on average per molecule and having a viscosity at 25 ° C. and a shear rate of 0.9 s −1 of 10 mPa · s to 10,000 mPa · s Polysiloxane,
(B) an organohydrogenpolysiloxane having hydrogen atoms bonded to an average of 4 silicon atoms per molecule and having a viscosity at 25 ° C. and a shear rate of 0.9 s −1 of 10 mPa · s to 10,000 mPa · s Siloxane (provided that hydrogen atoms bonded to 0.9 to 2 silicon atoms with respect to one alkenyl group of component (A)),
(C) A catalytic amount of hydrosilylation catalyst that promotes curing of the composition

(2) The light-emitting diode device according to claim 1, wherein (A) is an organopolysiloxane having an average of about two alkenyl groups bonded to silicon atoms per molecule and located at the end of the molecule.
(3) Addition-curing silicone resin, (a) The average composition formula is (R 3 SiO 1/2 ) M · (R 2 SiO 2/2 ) D · (RSiO 3/2 ) T · (SiO 4/2 Q (provided that each R is selected from the same or different organic group, hydroxyl group or hydrogen atom, M, D, T, Q is a number from 0 to less than 1, and M + D + T + Q = 1, Q + T >, And R includes a hydrocarbon group having a multiple bond and a hydrogen atom, or R includes a hydrocarbon group and / or a hydrogen atom having a multiple bond. The light-emitting diode device according to (1) or (2), which is a cured product of a composition comprising an organopolysiloxane mixture and (b) an effective amount of a hydrosilylation catalyst.

(4) After immersing and applying the light emitting diode element in a liquid silicone composition which is cured and softened comprising (A) to (C), the softened composition is cured or uncured in a silicone state. (1)-(3) light emitting diode element sealing method cast-molded with a resin composition.

  The light emitting diode device according to the present invention is remarkably less likely to generate cracks due to rapid temperature changes, has a high light transmittance at the sealed portion, is excellent in light resistance and heat resistance, is hard and difficult to crack, and is molded. It is excellent in industrial usefulness because it has less shrinkage.

The present invention will be specifically described.
The component (A) of the present invention is a main component in the silicone of the inner layer that is cured to be soft and has an average of at least 1.8 alkenyl groups bonded to silicon atoms in one molecule and bonded to silicon atoms. The other organic group is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms and containing no carbon-carbon double bond or carbon-carbon triple bond, and has a shear rate of 0.9 s at 25 ° C. -1 is an alkenyl group-containing organopolysiloxane having a viscosity of 10 mPa · s to 10,000 mPa · s.

  (A) As an alkenyl group of a component, C2-C8 alkenyl groups, such as a vinyl group, an allyl group, 1-butenyl group, 1-hexenyl group, can be illustrated, Preferably a vinyl group, An allyl group, particularly preferably a vinyl group. These alkenyl groups react with the component (B) described later to form a network structure, and are required to be present in the molecule at least 1.8 or more, preferably 1.6 or more and 10 or less. . Such an alkenyl group may be bonded to a silicon atom at the end of the molecular chain, or may be bonded to a silicon atom in the middle of the molecular chain. From the viewpoint of curing reaction rate and characteristics, an alkenyl group organopolysiloxane having an average of two alkenyl groups in the molecule and bonded only to the silicon atom at the end of the molecular chain is preferred.

  The organic group other than the alkenyl group bonded to the silicon atom of the component (A) is preferably a substituted or unsubstituted monovalent group containing no carbon-carbon double bond or carbon-carbon triple bond having 1 to 12 carbon atoms. Specifically, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group Alkyl groups such as octyl group, nonyl group, decyl group and dodecyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; aryl groups such as phenyl group, tolyl group, xylyl group, biphenyl group and naphthyl group Aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl group; Chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, chlorophenyl group in which some or all of the hydrogen atoms in the hydrogen group are substituted by halogen atoms, cyano groups, etc. And substituted hydrocarbon groups such as a dibromophenyl group, a tetrachlorophenyl group, a difluorophenyl group, a β-cyanoethyl group, a γ-cyanopropyl group, and a β-cyanopropyl group. Particularly preferred organic groups are a methyl group and a phenyl group. In general, the refractive index of silicone varies depending on the type of organic group bonded to the siloxane skeleton, and the refractive index of silicone bonded with an aromatic group such as a phenyl group is higher than that of a methyl group. Accordingly, in the light-emitting diode device of the present invention, when the outer resin-like silicone layer that seals it contains a large amount of aromatic groups, the refractive index of the inner soft silicone layer is set to the same level accordingly. Therefore, it is more preferable to increase the ratio of the phenyl group.

The alkenyl group-containing organopolysiloxane (A) may be linear or branched, or a mixture thereof. The branch in the polysiloxane skeleton itself acts like a crosslink, and this branch is a trifunctional siloxane (T structure) as long as the silicone of the inner layer has a hardness within the scope of the present invention after curing. Or tetrafunctional siloxane (Q structure) may be sufficient. The composition to be cured and soft silicone of the present invention needs to have appropriate fluidity from the viewpoint of workability in the process of coating the LED element. From such a viewpoint, the viscosity of the component (A) is desirably in the range of 10 mPa · s to 10,000 mPa · s at 25 ° C. and a shear rate of 0.9 s −1 , more preferably 100 mPa · s or more. 5,000 mPa · s or less, particularly preferably in the range of 200 mPa · s to 3,000 mPa · s. This alkenyl group-containing organopolysiloxane is produced by methods known to those skilled in the art.

Component (B) of the present invention is an organohydrogenpolysiloxane that serves as a crosslinking agent for component (A) and has an average of at least 4, preferably 3 to 30, hydrogen atoms bonded to silicon atoms. The organic group other than hydrogen bonded to the silicon atom is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which does not contain a carbon-carbon double bond or carbon-carbon triple bond, The viscosity at 25 ° C. and a shear rate of 0.9 s −1 is 10 mPa · s or more and 10,000 mPa · s or less.

  The organic group other than the hydrogen atom in the component (B) is the same as that exemplified as the other organic group in the component (A), and is preferably a methyl group or a phenyl group. From the viewpoint of the refractive index of the sealing material, it is more preferable that the phenyl group is contained in the same manner as described above for the selection of the methyl group and the phenyl group of the component (A).

The crosslinking agent as component (B) may be linear or branched, or a mixture thereof. This organohydrogenpolysiloxane is prepared by methods known to those skilled in the art. Moreover, it is necessary that the component (A) has an appropriate fluidity as well as the viscosity of the component (A) is limited. The viscosity of the component (B) is 25 ° C. and a shear rate of 0.9 s −1 . Desirably, it is in the range of 10 mPa · s to 10,000 mPa · s, more preferably 50 mPa · s to 5,000 mPa · s, and particularly preferably in the range of 100 mPa · s to 2,000 mPa · s. .

  The blending amount of the component (B) of the present invention is 0.9 to 2 with respect to one alkenyl group of the component (A) in order to crosslink the component (A) and have the necessary hardness. It is used in such an amount that it becomes a hydrogen atom bonded to a silicon atom, and is usually 5 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of component (A).

The component (C) of the present invention is a hydrosilylation catalyst comprising a metal and a compound thereof for promoting an addition reaction between a carbon-carbon multiple bond and a hydrogen atom bonded to a silicon atom, and is usually used. is there. Examples of such metals include platinum, rhodium, palladium, ruthenium, and iridium, and platinum can be used advantageously. The metal is optionally fixed to a particulate support material (for example, activated carbon, aluminum oxide, silicon oxide). As the hydrosilylation catalyst, it is preferable to use platinum and a platinum compound. Platinum compounds include platinum halides (eg, PtCl 4 , H 2 PtCl 4 .6H 2 O, Na 2 PtCl 4 .4H 2 O), platinum-olefin complexes, platinum-alcohol complexes, platinum-alcolate complexes, platinum- Ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, platinum-vinylsiloxane complexes (eg, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes, bis- (γ-picoline)) -Platinum dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride), bis (alkynyl) bis (triphenylphosphine) platinum complex, bis (alkynyl) (Cyclooctadiene) platinum complex And the like. The hydrosilylation catalyst can also be used in a microencapsulated form. In this case, the particulate solid containing the catalyst and insoluble in the organopolysiloxane is, for example, a resin (for example, a polyester resin or a silicone resin). The hydrosilylation catalyst can also be used in the form of an inclusion compound, for example, in a cyclodextrin. The addition amount of the hydrosilylation catalyst is a catalytic amount, and when a platinum catalyst is used, the platinum metal in the composition comprising (A) and (B) is preferably 0.1 to 500 ppm, particularly preferably 1 to 200 ppm. .

  In the composition comprising (A) to (C) of the present invention, the hardness after curing is in accordance with the durometer hardness test method specified in JIS K6253, using a type E durometer, with a test piece thickness of about 10 mm. It needs to be 5 or more and 75 or less when measured, and preferably 5 or more and 60 or less. If it is 5 or less, it is too soft, and the deformation becomes large in the sealing process with a silicone resin. If it is 75 or more, a sufficient stress absorbing effect as a soft layer cannot be exhibited. This hardness is achieved by adjusting the degree of polymerization of the component (A) to be used, the alkenyl group and the branched structure serving as a crosslinking point, and the amount of hydrogen atoms and the degree of polymerization of the component (B).

The light-emitting diode device of the present invention is obtained by coating an LED element with a composition comprising (A) to (C), and further sealing with an addition-curable silicone resin that is cured into a resinous state, This addition-curable silicone resin has (a) an average composition formula of (R 3 SiO 1/2 ) M · (R 2 SiO 2/2 ) D · (RSiO 3/2 ) T · (SiO 4/2 ) Q (Wherein R is selected from the same or different organic groups, hydroxyl groups or hydrogen atoms, M, D, T and Q are a number from 0 to less than 1, and M + D + T + Q = 1, Q + T> 0 Or an organopolysiloxane mixture containing a hydrocarbon group and a hydrogen atom having multiple bonds as R, or an organopolysiloxane mixture containing a hydrocarbon group and / or a hydrogen atom having multiple bonds as R; A composition comprising an effective amount of an addition reaction catalyst. The component (a) has a branched structure of T unit (RSiO 3/2 ) and Q unit (SiO 4/2 ) as an average composition in the mixture, and has a more advanced three-dimensional network structure by a reaction such as crosslinking. It is a polymer that can be removed. Therefore, in all average composition formulas, Q + T> 0.

  Such a polyorganosiloxane is also called a silicone resin, and the composition before curing may be a solid or a liquid. It is more preferable because of the ease of molding. The polyorganosiloxane as component (a) may be produced by a method known to those skilled in the art, and is obtained, for example, by a reaction such as hydrolysis of organosilanes and / or organosiloxanes.

R in the component (a) may be the same or different each independently. Since the formula is an average composition formula, these selection methods are different in the same structural unit, for example, (R 2 SiO 2/2 ) D structural unit, as R at the same time, for example, methyl group, phenyl group and hydrogen atom. It does not preclude the simultaneous selection of these three types of groups. Moreover, the structure for connecting each unit may take the form different from each unit structure.

  Examples of R include a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms and a halogen-substituted product thereof, an acetylene group or a hydrocarbon group containing an acetylene group, and a cycloalkyl group having 5 to 25 carbon atoms. Group or cycloalkenyl group and its halogen substituent, aralkyl group having 6 to 25 carbon atoms or aryl group and its halogen substituent, and specific examples of these hydrocarbon groups include alkenyl group or What was illustrated as another organic group can be mention | raise | lifted. R having a multiple bond means a hydrocarbon group containing a carbon-carbon double bond and a carbon-carbon triple bond, and is an alkenyl group or an acetylene group, and is most preferably a hydrocarbon group having a multiple bond. It is a group.

R is further a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an alkenyloxy group, an acid anhydride group, a carbonyl group, a saccharide, a cyano group, an oxazoline group, an isocyanate group, and the like, and / or It can be selected from hydrocarbon substitutes. Specific examples thereof include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tertiary butoxy group, hexyloxy group, isohexyloxy group, 2-hexyloxy group, octyloxy group, isooctyloxy group, 2 -Octyloxy, acetoxy, dimethylketoxime, methylethylketoxime, glycidyl, ethyleneglycoxy, diethyleneglycoxy, polyethyleneglycoxy, propyleneglycoxy, dipropyleneglycoxy, polypropyleneglycoxy, methoxy Ethyleneglycoxy group, ethoxyethyleneglycoxy group, methoxydiethyleneglycoxy group, ethoxydiethyleneglycoxy group, methoxypropyleneglycoxy group, methoxydipropyleneglycoxy group, Toki Siji propylene glycoxy group, and the like. Of these, a methyl group, an ethyl group, a propyl group, a phenyl group, a vinyl group, and a hydrogen atom are particularly preferable.

  The component (a) can be combined in several combinations, for example, (a) a hydrocarbon group having multiple bonds and a hydrogen atom bonded to a silicon atom and a hydrogen atom bonded to a silicon atom are contained in one molecule. It may be an organopolysiloxane or a mixture thereof, and (b) an organopolysiloxane having multiple bonds in one molecule and containing a hydrocarbon group bonded to a silicon atom and not containing a hydrogen atom bonded to a silicon atom; A mixture with an organopolysiloxane containing a hydrogen atom bonded to a silicon atom but not containing a hydrocarbon group having multiple bonds, (c) and (a) an organopolysiloxane (having multiple bonds and bonding to a silicon atom) A hydrocarbon group and a hydrogen atom bonded to a silicon atom in one molecule) and a silicon atom containing a hydrocarbon group having multiple bonds in one molecule and bonded to a silicon atom. Including hydrogen atoms bonded to silicon atoms in the organopolysiloxane and or in one molecule containing no hydrogen atom bonded to be a mixture of an organopolysiloxane containing no hydrocarbon group with a multiple bond. That is, even when the component (a) is a mixture, both hydrocarbon groups having multiple bonds bonded to silicon atoms and hydrogen atoms are present in the mixture as a mixture, and the resin is cured as a mixture. It is only necessary to include a quantity of T units and / or Q units.

In the polysiloxane of component (a), it is preferable that the hydrocarbon group having a multiple bond bonded to a silicon atom and the hydrogen atom bonded to the silicon atom are present in the selected two or one unit. In the present invention, the position of the hydrocarbon group bonded to the silicon atom and the hydrogen atom bonded to the silicon atom are most preferably (R 2 SiO 2/2 ) structural unit.

The polyorganosiloxane which is the component (a) of the present invention preferably has an aromatic group as R in the average composition formula from the viewpoint of heat resistance, light resistance, and refractive index as a sealing material for LED elements. Examples of the aromatic group include an aralkyl group and an aryl group, and a phenyl group is most preferable. The amount of the aromatic group is preferably 5 to 90 mol%, more preferably 10 to 60 mol% with respect to R of all units. If the amount of the aromatic group is small, the effect of improving heat resistance, light resistance and refractive index cannot be obtained, and if the amount is too large, it is economically disadvantageous. The aromatic group can be introduced into any unit except the (SiO 4/2 ) structural unit, but is preferably introduced into the (R 2 SiO 2/2 ) structural unit and the (RSiO 3/2 ) structural unit, Most preferred is the introduction into the (RSiO 3/2 ) structural unit.

  In the component (a) of the present invention, the silicon atom directly bonded to the hydrogen atom is more preferably 1 to 40 mol%, further preferably 3 to 30 mol%, most preferably 5 to 20 mol% of all silicon atoms. It is. If this amount is large, the hardness tends to increase but it tends to be brittle. If this amount is small, the hardness does not increase, so it is more preferable that the amount falls within the above range. In addition, when the component (a) of the present invention contains both a hydrocarbon group having multiple bonds and a hydrogen atom bonded to a silicon atom and a hydrogen atom bonded to the silicon atom, a silicon atom directly bonded to the hydrogen atom Is more preferably 1 to 40 mol% of all silicon atoms, still more preferably 3 to 30 mol%, and most preferably 5 to 20 mol%. When the amount is 40 mol% or more, the hardness of the obtained cured product tends to increase but becomes brittle, and when the amount is 1 mol% or less, a cured product having sufficient hardness cannot be obtained.

  M, D, T, and Q are numbers indicating the ratio of each unit and are 0 or more and less than 1. Preferably, M is 0 to 0.6, D is 0.1 to 0.8, T is 0.1 to 0.7, Q is 0 to 0.3, and more preferably, M is 0.1. -0.4, D is 0.1-0.6, T is 0.3-0.6, and Q is 0. T + Q is preferably in the range of 0.9 to 0.3, more preferably 0.8 to 0.5.

  Further, the value of (2D + 3T + 4Q) / (D + T + Q) representing the degree of branching is preferably 3.0> (2D + 3T + 4Q) / (D + T + Q)> 2.0, more preferably 2.8> (2D + 3T + 4Q) / ( D + T + Q)> 2.2, and more preferably 2.8> (2D + 3T + 4Q) / (D + T + Q)> 2.5.

  As the hydrosilylation catalyst as the component (b) in the resinous addition-curable silicone resin of the present invention, the same catalyst as exemplified as the component (C) can be used, and a silicon atom bonded with a hydrogen atom and It is usually used as a catalyst for promoting an addition reaction with a hydrocarbon having multiple bonds. This catalyst for addition reaction is used in an effective amount (that is, so-called catalyst amount), and is usually 1 to 1000 ppm, preferably 2 to 500 ppm relative to component (a) in terms of metal.

  The sealing composition comprising (a) and (b) of the present invention needs to be resinous after cross-linking and curing by addition reaction. In the present invention, the resinous state is 30 to 90, more preferably 40 to 90, when measured at a thickness of 6 mm using a type D durometer in accordance with a durometer hardness test method defined in JIS K6253. Is to show the hardness. A cured product having such a hardness range is achieved by setting (2D + 3T + 4Q) / (D + T + Q) representing the degree of branching of the component (a) to be used in a specific range.

  Examples of LED elements in the present invention include conventional GaP, GaAs, and GaN-based red / green / yellow light emitting LED elements and high-luminance, short-wavelength LED elements that have been developed recently. The composition of the present invention can also be used for sealing conventional LED elements, but it is particularly high-brightness, short-wavelength, which has been developed in recent years. It is a high-luminance blue, white LED, blue to near-ultraviolet LED element having an emission peak wavelength of 490 to 350 nm. The sealing material used for these LED elements is particularly required to have light resistance to blue to ultraviolet wavelengths, and the LED element has a high emission luminance, so that it will be exposed to higher energy light, In particular, light resistance and heat resistance are required. Compared with the case where an epoxy-based encapsulant that is currently widely used is used, the encapsulant composition of the present invention is excellent in light resistance and heat resistance, thereby significantly improving the life of the light-emitting diode device. be able to. Examples of these high-luminance blue and white LED elements for blue to near-ultraviolet include AlGaInN yellow, InGaN blue, green, and a white light emitting diode device combining InGaN and a phosphor.

  Specific examples of the sealed light emitting diode device include a shell type, a large package type, and a surface mount type. These shapes are described, for example, in “Flat Panel Display Dictionary” issued on December 25, 2001, pages 897 to 906, published by Industrial Research Council, Inc.

  The method of coating the LED element with the composition that is cured and becomes soft silicone comprising (A) to (C) of the present invention is not particularly limited, and for example, the entire LED element is immersed in a liquid composition. For example, a method of dripping the liquid composition onto the LED element is used, and a method of dipping is preferably used to coat the surface of the element relatively uniformly. Although there is no particular limitation on the coating thickness, it is usually coated with a thickness of about 0.01 to 2 mm. After coating the liquid composition, the coated composition can be used as it is in the next sealing step without being cured or cured, but it is preferable to transfer the composition to the sealing step after curing. The composition can be easily cured by passing it through a furnace at a temperature suitable for curing. The curing temperature is usually 50 to 180 ° C., and the curing time is about 1 to 120 minutes.

  After being coated with the softened and soft silicone, the LED element is further sealed with a cured and resinous composition comprising (a) and (b). The sealing method is not particularly limited. For example, the sealing is made by a method of injecting the silicone composition of the present invention into a resin-made concave mold, dipping the element, raising the temperature and solidifying, a transfer molding method, or the like. It is also an advantage of sealing with the silicone resin of the present invention that not only a resin mold but also a metal mold that could not be used with a sealing agent using a conventional epoxy can be used.

  Moreover, in the composition of this invention, various additives can be added in the range which does not impair the effect. For example, for white light emission, such as a reaction control agent for addition reaction for imparting curability and pot life, and a reactive or non-reactive linear or cyclic low-molecular polyorganopolysiloxane for adjusting hardness and viscosity. Fluorescent light-emitting agents such as YAG, inorganic fillers such as particulate silica and titanium oxide, pigments, organic fillers, flame retardants, heat-resistant agents, antioxidants, and the like may be blended.

Although the detailed Example of this invention is shown below, this invention is not limited by this.
In the examples of the present invention, the following silicone compositions were used.
(A-1) Dimethylpolysiloxane having both ends blocked with dimethylvinylsilyl groups and having a viscosity of 900 mPa · s at 25 ° C.
(B-1) A methylhydrogen polysiloxane having both ends blocked with trimethylsilyl groups, having a viscosity of 300 mPa · s at 25 ° C., and containing 14 methylhydrogensiloxane units in the main chain.
(C, b) A vinyl group-containing siloxane platinum complex derived from chloroplatinic acid. (Hydrosilylation catalyst)
(A) The average composition is (Me 3 SiO 1/2 ) 0.17 · (MeHSiO 2/2 ) 0.20 · (MeViSiO 2/2 ) 0.25 (PhSiO 3/2 ) 0.38 , 25 Organopolysiloxane having a viscosity of 900 mPa · s at ° C. Here, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

  The hardness was measured with a sheet-like cured product having a thickness of 10 mm or 6 mm using a durometer. Moreover, the thermal shock test was implemented as a test of a cracking difficulty. The thermal shock test was carried out using a small thermal shock apparatus (TSE-11-A) manufactured by Espec Co., Ltd. under the conditions of holding at minus 40 ° C. and 110 ° C. for 30 minutes. Minus 40 ° C to 110 ° C and 110 ° C to minus 40 ° C are reached within 3 minutes.

[Example 1]
90 parts by weight of dimethylpolysiloxane (A-1), 10 parts by weight of methylhydrogenpolysiloxane (B-1), and 0.05 part of platinum complex (C) were weighed and mixed until uniform. This mixed solution was degassed under reduced pressure with an aspirator. The viscosity of this addition-curable silicone mixture was 700 mPa · s. Next, a silver-plated metal lead frame (for a 5 mm shell type) was immersed in the mixed solution for 2 minutes, and then the lead frame was taken out and held for 3 minutes to remove excess addition-curable silicone mixture, and then 100 Heat cured at 15 ° C. for 15 minutes. The obtained lead frame covered with the soft addition-curable silicone was observed with a microscope, and as a result, it was coated with a thickness of about 50 to 200 microns. Further, the hardness of a sheet having a thickness of 10 mm obtained by heating and curing the addition-cured mixture at 100 ° C. for 15 minutes was 50 with a type E durometer. Next, 100 parts by weight of the organopolysiloxane (a) and 0.02 part by weight of the platinum complex (b) were weighed and mixed until uniform. The viscosity of the addition-type silicone resin mixture obtained by degassing this mixed solution with an aspirator was 800 mPa · s. The obtained addition type silicone resin mixture was poured into a resin casting case (5 mm shell type), and the lead frame already coated with the soft addition type silicone previously obtained was inserted, and heated at 150 ° C. for 3 hours. Cured. The sheet of 6 mm thickness obtained by separately heat-curing this addition-type silicone resin mixture at 150 ° C. for 3 hours was transparent, and the hardness by a type D durometer was 60. When the obtained light-emitting diode device having a two-layered sealing portion was evaluated with a thermal shock tester for 300 cycles, no cracks were observed.

[Comparative Example 1]
In the same manner as in Example 1, 100 parts by weight of the organopolysiloxane (a) and 0.02 part by weight of the hydrosilylation catalyst (b) were weighed and mixed until uniform. The viscosity of the mixture after degassing under reduced pressure was 800 mPa · s. The obtained silicone resin mixture was poured into a resin casting case (5 mm shell type), and a silver-plated metal lead frame not covered with soft silicone was inserted and cured by heating at 150 ° C. for 3 hours. When the obtained light emitting diode device having a single-layer sealing portion was evaluated for 10 cycles with a thermal shock tester, cracks were found in all the samples.

  The light-emitting diode device according to the present invention, in particular, a light-emitting diode device composed of LED elements that emit blue to ultraviolet light is less likely to crack in the sealed portion even with a sudden temperature change. While maintaining transparency, light resistance, and heat resistance, it has an excellent balance between strength and hardness and is useful.

Claims (4)

  1. In the light-emitting diode device in which the surface of the light-emitting diode element is coated with a soft addition-curable silicone and further sealed with a resinous addition-curable silicone resin, the soft addition-curable silicone is changed from (A) to (C). A light-emitting diode device, which is a cured product of the composition having a hardness after curing of 5 to 75 in a type E durometer.
    (A) Organo having an alkenyl group bonded to at least 1.8 silicon atoms on average per molecule and having a viscosity at 25 ° C. and a shear rate of 0.9 s −1 of 10 mPa · s to 10,000 mPa · s Polysiloxane,
    (B) an organohydrogenpolysiloxane having hydrogen atoms bonded to an average of 4 silicon atoms per molecule and having a viscosity at 25 ° C. and a shear rate of 0.9 s −1 of 10 mPa · s to 10,000 mPa · s Siloxane (provided that hydrogen atoms bonded to 0.9 to 2 silicon atoms with respect to one alkenyl group of component (A)),
    (C) A catalytic amount of hydrosilylation catalyst that promotes curing of the composition
  2. 2. The light-emitting diode device according to claim 1, wherein (A) is an organopolysiloxane having an average of about 2 alkenyl groups bonded to silicon atoms per molecule and located at the end of the molecule.
  3. Addition-curing type silicone resin has (a) average composition formula (R 3 SiO 1/2 ) M · (R 2 SiO 2/2 ) D · (RSiO 3/2 ) T · (SiO 4/2 ) Q ( Provided that R is selected from the same or different organic group, hydroxyl group or hydrogen atom, M, D, T, Q is a number from 0 to less than 1, and M + D + T + Q = 1, Q + T> 0 And an organopolysiloxane containing a hydrocarbon group and a hydrogen atom having multiple bonds as R, or an organopolysiloxane containing a hydrocarbon group and / or a hydrogen atom having multiple bonds as R. The light-emitting diode device according to claim 1 or 2, which is a cured product of a composition comprising a mixture of siloxane and (b) an effective amount of a hydrosilylation catalyst.
  4. A silicone resin composition in which the softening composition is cured or uncured after the light-emitting diode element is dipped and applied in a cured and soft silicone liquid composition comprising (A) to (C). The method for sealing a light-emitting diode element according to claim 1, wherein the molding is performed by casting.
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