JP2015209491A - Sealant for optical semiconductor device and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealant for an optical semiconductor device which can significantly improve the adhesive force of the cured product of a sealant.SOLUTION: A sealant for an optical semiconductor device according to the present invention is cured by hydrosilylation reaction for use, and comprises a silicone resin capable of hydrosilylation reaction, a hydrosilylation reaction catalyst, and a compound represented by the following formula (1), where R1 and R2 represent a hydrocarbon group having 1-3 carbon atoms, and R3 represents a hydrocarbon group having 1-8 carbon atoms or an alkoxy group having 1-3 carbon atoms.

Description

  The present invention relates to an encapsulant for an optical semiconductor device used for encapsulating an optical semiconductor element in an optical semiconductor device. The present invention also relates to an optical semiconductor device using the optical semiconductor device sealing agent.

  Optical semiconductor elements such as light emitting diode (LED) elements are widely used as light sources for display devices. An optical semiconductor device using an optical semiconductor element has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.

  When an optical semiconductor element (for example, an LED), which is a light emitting element used in an optical semiconductor device, is in direct contact with the atmosphere, the light emission characteristics of the optical semiconductor element rapidly deteriorate due to moisture in the atmosphere or floating dust. For this reason, the said optical semiconductor element is normally sealed with the sealing compound for optical semiconductor devices.

  The following Patent Document 1 discloses an invention relating to a self-adhesive polyorganosiloxane composition, and this composition can be widely used for general purpose applications in semiconductor packages such as LEDs, photodiodes, CCDs, and CMOSs. It describes what you can do. The following Patent Document 2 discloses an invention related to a silicone composition, and it is described that this composition can be widely used as a semiconductor package material such as LED, photodiode, CCD, and CMOS.

  Patent Documents 1 and 2 disclose a compound represented by the following formula (101) and a compound represented by the following formula (102) as an adhesion-imparting agent.

  In said formula (101), R represents a methyl group or an ethyl group.

  The following Patent Document 3 discloses an invention relating to a self-adhesive organopolysiloxane composition, and the composition is a resin fiber used as, for example, an air bag as a sealing material, a potting material, and a coating material. It is described that it can be used as a coating material for a textile fabric, a general resin film, and a sealing material.

  The following Patent Document 4 discloses an invention relating to a curable composition, and it is described that the composition can be used as a sealant for semiconductor elements such as IC, LSI and LED.

  Patent Documents 3 and 4 disclose a compound represented by the following formula (103), a compound represented by the following formula (104), and a compound represented by the following formula (105) as an adhesion-imparting agent. ing.

  Patent Document 5 below discloses a composition containing an organopolysiloxane having (3,5-diglycidyl isocyanuryl) alkyl groups at both ends of the main chain. This composition is suitable for a case-type light emitting semiconductor device, that is, a light emitting element is disposed in a ceramic and / or plastic casing, and the composition disposed in the casing is covered with the composition. It is described that it is suitable to be used after being filled with a resin.

  Patent Document 6 below discloses a composition containing an organopolysiloxane having an isocyanuric ring and having at least one terminal vinylsiloxy group in the molecule. The cured product of this composition has transparency. It is described that it is an optimal material for optical materials such as LED lenses and LED sealing materials required, and particularly for semiconductor sealing materials.

JP 2010-0665161 A JP 2011-057755 A JP 2006-137797 A JP 2005-343984 A JP 2009-275206 A JP 2011-099008 A

  In an optical semiconductor device using a conventional sealing agent, the adhesive force between a cured product of the sealing agent and a member in contact with the cured product may not be sufficiently high. Examples of the member in contact with the hardened material of the sealant include a package and a metal member.

  The objective of this invention is providing the sealing compound for optical semiconductor devices which can raise considerably the adhesive force of the hardened | cured material of sealing compound. Another object of the present invention is to provide an optical semiconductor device in which the above-mentioned encapsulant for optical semiconductor devices is used, and the adhesive force between the sealing portion and a member in contact with the sealing portion is sufficiently increased. It is.

  According to a wide aspect of the present invention, there is provided an encapsulant for an optical semiconductor device that is used after being cured by a hydrosilylation reaction, a silicone resin capable of hydrosilylation reaction, a catalyst for hydrosilylation reaction, the following formula (1) An encapsulant for optical semiconductor devices comprising a compound represented by the formula:

  In said Formula (1), R1 and R2 represent a C1-C3 hydrocarbon group, respectively, R3 represents a C1-C8 hydrocarbon group or a C1-C3 alkoxy group.

  In a specific aspect of the encapsulant for optical semiconductor devices according to the present invention, the compound contains an alkoxy compound having an alkoxy group, which is different from the compound represented by the formula (1), and the alkoxy compound has a period of IUPAC. An alkoxy compound having a tetravalent group 4 atom having an atomic number of up to 40 in the table, an alkoxy compound having a divalent group 12 atom having an atomic number of up to 40 in the IUPAC periodic table, or an atomic number in the periodic table of IUPAC It is an alkoxy compound having up to 40 trivalent group 13 atoms.

  On the specific situation with the sealing compound for optical semiconductor devices which concerns on this invention, the said alkoxy compound is an alkoxy compound which has titanium.

  In a specific aspect of the encapsulant for optical semiconductor devices according to the present invention, the alkoxy compound having a titanium atom is tetrakis (2-ethylhexyloxy) titanium, titanium-isopropoxyoctylene glycolate, or titanium di-2. -Ethylhexoxybis (2-ethyl-3-hydroxyhexoxide).

  In a specific aspect of the encapsulant for optical semiconductor devices according to the present invention, the silicone resin capable of hydrosilylation reaction includes at least one first silicone resin having two or more alkenyl groups bonded to silicon atoms. And at least one second silicone resin having two or more hydrogen atoms bonded to silicon atoms.

  In a specific aspect of the sealant for optical semiconductor devices according to the present invention, the first silicone resin is represented by the following first formula (11A) and the following first formula (11B): The second silicone resin contains a second silicone resin represented by the following formula (12A).

  In the formula (11A), a, b, and c satisfy 0.05 ≦ a ≦ 0.20, 0.50 ≦ b ≦ 0.95, and 0 ≦ c ≦ 0.30, respectively. -15 mol% represents an alkenyl group, 20-50 mol% of R1 to R6 represents an aryl group, and R1 to R6 other than the aryl group and alkenyl group represent a hydrocarbon group having 1 to 6 carbon atoms.

  In the formula (11B), e, f, and g satisfy 0.15 ≦ e ≦ 0.30, 0 ≦ f ≦ 0.20, 0.60 ≦ g ≦ 0.85, and 10 of R11 to R16 -20 mol% represents an alkenyl group, 20-50 mol% of R11 to R16 represents an aryl group, and R11 to R16 other than the aryl group and the alkenyl group represent a hydrocarbon group having 1 to 6 carbon atoms.

  In the formula (12A), h, i, and j satisfy 0.50 ≦ h ≦ 0.75, 0.25 ≦ i ≦ 0.50, and 0 ≦ j ≦ 0.25, and R21 to R26 of 20 ˜30 mol% represents a hydrogen atom directly bonded to a silicon atom, 10 to 25 mol% of R 21 to R 26 represents an aryl group, and R 21 to R 26 other than the hydrogen atom directly bonded to the aryl group and the silicon atom have a carbon number of 1 Represents a hydrocarbon group of ˜6.

  In a specific aspect of the encapsulant for optical semiconductor devices according to the present invention, the number of alkenyl groups in the entire first silicone resin is relative to the number of hydrogen atoms bonded to silicon atoms in the entire second silicone resin. The ratio is 0.9 or more and 1.1 or less.

  According to a wide aspect of the present invention, an optical semiconductor element and a sealing portion obtained by curing the above-described sealing agent for an optical semiconductor device are provided, and the sealing portion seals the optical semiconductor element. An optical semiconductor device is provided that is arranged to stop.

  The encapsulant for optical semiconductor devices according to the present invention contains a silicone resin capable of hydrosilylation reaction, a catalyst for hydrosilylation reaction, and a compound represented by formula (1). Adhesion can be increased considerably.

1A and 1B are a cross-sectional view and a perspective view schematically showing an optical semiconductor device using an optical semiconductor device sealing agent according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a modification of the optical semiconductor device shown in FIG. FIG. 3 is a cross-sectional view schematically showing a modification of the optical semiconductor device shown in FIG.

  Details of the present invention will be described below.

  The encapsulant for optical semiconductor devices according to the present invention (hereinafter sometimes abbreviated as encapsulant) is used by being cured by a hydrosilylation reaction. The sealant according to the present invention includes a silicone resin capable of hydrosilylation reaction, a hydrosilylation reaction catalyst, and a compound represented by the following formula (1).

  In said formula (1), R1 and R2 represent a C1-C3 hydrocarbon group, respectively, R3 represents a C1-C8 hydrocarbon group or a C1-C3 alkoxy group.

  Since the composition mentioned above is employ | adopted in the sealing compound which concerns on this invention, the adhesive force of the hardened | cured material of a sealing compound can be raised considerably. When the sealant according to the present invention is cured by a hydrosilylation reaction, high adhesive strength is exhibited.

  Since the compound represented by the above formula (1) is used in the sealant according to the present invention, the compounds represented by the above formula (101) and the formula (102) (Japanese Patent Laid-Open No. 2010-066511 and JP, 2011-057755, A) The above-mentioned formula (103), the above-mentioned formula (104), and the compound denoted by the above-mentioned formula (105) (JP-A 2006-137797 and JP-A-2005-343984) , Organopolysiloxanes having (3,5-diglycidyl isocyanuryl) alkyl groups described in JP 2009-275206 A at least at both ends of the main chain, and JP 2011-0909008 A Compared to the case where an organopolysiloxane having an isocyanuric ring and having at least one terminal vinylsiloxy group in the molecule is used, Force application can be enhanced considerably.

  Moreover, as a member which contacts the hardened | cured material of sealing agent, PPA (polyphthalamide), PCT (polycyclohexylene dimethylene terephthalate), EMC (epoxy molding compound), Cu (Cu) which carried out Ag plating, etc. are mentioned. . The sealant is used so as to come into contact with such various members. Since the composition mentioned above is employ | adopted in the sealing agent which concerns on this invention, the adhesive force of the hardened | cured material of a sealing agent can be improved considerably with respect to various members. The sealant according to the present invention can be effectively used particularly by bonding PPA and PCT.

  Moreover, in order to reflect the light which reached the back surface side of the light emitting element, an electrode plated with silver may be formed on the back surface of the light emitting element. If a hardened product of the sealant is cracked or the sealant is peeled off from the housing material, the silver-plated electrode is exposed to the atmosphere. In this case, the silver plating may be discolored by a corrosive gas such as hydrogen sulfide gas or sulfurous acid gas present in the atmosphere. When the color of the electrode changes, the reflectance decreases, which causes a problem that the brightness of the light emitted from the light emitting element decreases.

  On the other hand, since the composition mentioned above is employ | adopted in the sealing agent which concerns on this invention, the heat-resistant cycle characteristic of the hardened | cured material of sealing agent can be improved. Even if the cured product of the sealant according to the present invention is used in a harsh environment that repeatedly undergoes heating and cooling, the cured product of the sealant is hardly cracked, and the cured product of the sealant is removed from the housing material or the like. It can be made difficult to peel.

  Furthermore, since the composition mentioned above is employ | adopted in the sealing agent which concerns on this invention, the moisture resistance of the hardened | cured material of sealing agent can also be improved. Even if the optical semiconductor device using the sealing agent according to the present invention is exposed to high humidity, the light intensity emitted from the optical semiconductor device can be made difficult to decrease.

  Furthermore, in the sealing agent which concerns on this invention, since the composition mentioned above is employ | adopted, the heat resistance of the hardened | cured material of sealing agent can be improved. Even if the optical semiconductor device using the sealing agent according to the present invention is exposed to a high temperature, the light intensity emitted from the optical semiconductor device can be made difficult to decrease.

  In the sealing agent according to the present invention, it is possible to improve any of adhesiveness, cold cycle resistance, moisture resistance, and heat resistance.

  Hereinafter, the detail of each component contained in the sealing compound for optical semiconductor devices which concerns on this invention is demonstrated.

(Silicone resin capable of hydrosilylation reaction)
The said silicone resin contained in the said sealing agent will not be specifically limited if hydrosilylation reaction is possible as a whole. Only 1 type may be used for the said silicone resin which can be hydrosilylated, and 2 or more types may be used together.

  The silicone resin is preferably an organopolysiloxane. The silicone resin capable of hydrosilylation includes at least one first silicone resin having two or more alkenyl groups bonded to silicon atoms and a second silicone resin having two or more hydrogen atoms bonded to silicon atoms. It is preferable to contain at least one of these. By using the first and second silicone resins in combination, the hydrosilylation reaction proceeds efficiently. The first silicone resin preferably does not have a hydrogen atom bonded to a silicon atom.

  From the viewpoint of further suppressing the generation of cracks in the cured product of the sealant (hereinafter sometimes referred to as sealant) and the peeling of the sealant, the silicone resin preferably has an aryl group. From the viewpoint of further suppressing generation of cracks in the sealant and peeling of the sealant, the first silicone resin preferably has an aryl group. In the first silicone resin, the aryl group is preferably directly bonded to a silicon atom. From the viewpoint of further suppressing the generation of cracks in the sealant and the peeling of the sealant, the second silicone resin preferably has an aryl group. In the second silicone resin, the aryl group is preferably directly bonded to the silicon atom. As said aryl group, an unsubstituted phenyl group and a substituted phenyl group are mentioned.

  Each number average molecular weight (Mn) of the silicone resin capable of hydrosilylation reaction and the first and second silicone resins is preferably 500 or more, more preferably 800 or more, still more preferably 1000 or more, preferably 50000 or less. More preferably, it is 15000 or less. When the number average molecular weight is not less than the above lower limit, volatile components are reduced during thermosetting, and the thickness of the sealant is difficult to decrease under a high temperature environment. When the number average molecular weight is not more than the above upper limit, viscosity adjustment is easy.

  The number average molecular weight (Mn) is a value obtained by using polystyrene as a standard substance using gel permeation chromatography (GPC). The number average molecular weight (Mn) was measured using two measuring devices manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: Tetrahydrofuran, standard substance: polystyrene) means a value measured.

  The method for synthesizing the silicone resin capable of hydrosilylation and the first and second silicone resins is not particularly limited, and a method of hydrolyzing and condensing an alkoxysilane compound, hydrolyzing and condensing a chlorosilane compound. A method is mentioned. A method of hydrolyzing the alkoxysilane compound is preferable because the reaction can be easily controlled.

  Examples of the method for hydrolyzing and condensing the alkoxysilane compound include a method of reacting the alkoxysilane compound in the presence of water and an acidic catalyst or a basic catalyst. Further, the disiloxane compound may be hydrolyzed and used.

  Examples of the organosilicon compound for introducing an aryl group into the silicone resin capable of hydrosilylation reaction and the organosilicon compound for introducing an aryl group into the first and second silicone resins include triphenylmethoxysilane, Examples include phenylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyl (phenyl) dimethoxysilane, and phenyltrimethoxysilane.

  Examples of the organosilicon compound for introducing an alkenyl group into the silicone resin capable of hydrosilylation reaction and the organosilicon compound for introducing an alkenyl group into the first silicone resin include vinyltrimethoxysilane and vinyltriethoxysilane. Vinylmethyldimethoxysilane, methoxydimethylvinylsilane, vinyldimethylethoxysilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and the like.

  As the organosilicon compound for introducing hydrogen atoms bonded to silicon atoms into the silicone resin capable of hydrosilylation reaction, and the organosilicon compound for introducing hydrogen atoms bonded to silicon atoms into the second silicone resin, , Trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, 1,1,3,3-tetramethyldisiloxane, and the like.

  Examples of the silicone resin capable of hydrosilylation reaction and other organosilicon compounds that can be used to obtain the first and second silicone resins include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, and dimethyl. Diethoxysilane, isopropyl (methyl) dimethoxysilane, cyclohexyl (methyl) dimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane and octyltrimethoxysilane It is done.

  Examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides of inorganic acids and derivatives thereof, and acid anhydrides of organic acids and derivatives thereof. Examples of the basic catalyst include alkali metal hydroxides, alkali metal alkoxides, and alkali metal silanol compounds.

  From the viewpoint of effectively improving the adhesiveness, thermal cycle resistance, moisture resistance and heat resistance of the sealant, the first silicone resin is a first silicone resin represented by the following formula (11A), and The first silicone resin represented by the following formula (11B) is preferably included. Even when the first silicone resin represented by the following formula (11A) and the following formula (11B) is not used, the compound represented by the above formula (1) can be obtained by using a silicone resin capable of hydrosilylation. There is a difference in the effect of the present invention when the silicone resin capable of hydrosilylation reaction is the same type between the case where the compound represented by the above formula (1) is not used and the case where is used.

  In the above formula (11A), a, b, and c satisfy 0.05 ≦ a ≦ 0.20, 0.50 ≦ b ≦ 0.95, and 0 ≦ c ≦ 0.30, respectively. -15 mol% represents an alkenyl group, 20-50 mol% of R1 to R6 represents an aryl group, and R1 to R6 other than the aryl group and alkenyl group represent a hydrocarbon group having 1 to 6 carbon atoms.

  In the above formula (11B), e, f, and g satisfy 0.15 ≦ e ≦ 0.30, 0 ≦ f ≦ 0.20, 0.60 ≦ g ≦ 0.85, and 10 of R11 to R16 -20 mol% represents an alkenyl group, 20-50 mol% of R11 to R16 represents an aryl group, and R11 to R16 other than the aryl group and the alkenyl group represent a hydrocarbon group having 1 to 6 carbon atoms.

  From the standpoint of effectively enhancing the adhesiveness, thermal cycle resistance, moisture resistance and heat resistance of the sealant, the second silicone resin includes the second silicone resin represented by the following formula (12A). It is preferable. Even when the second silicone resin represented by the following formula (12A) is not used, if a silicone resin capable of hydrosilylation reaction is used, the case where the compound represented by the above formula (1) is used and the above The effect of the present invention is different when the silicone resin capable of hydrosilylation reaction is the same type when the compound represented by the formula (1) is not used.

  In the above formula (12A), h, i, and j satisfy 0.50 ≦ h ≦ 0.75, 0.25 ≦ i ≦ 0.50, 0 ≦ j ≦ 0.25, and R21 to R26 of 20 ˜30 mol% represents a hydrogen atom directly bonded to a silicon atom, 10 to 25 mol% of R 21 to R 26 represents an aryl group, and R 21 to R 26 other than the hydrogen atom directly bonded to the aryl group and the silicon atom have a carbon number of 1 Represents a hydrocarbon group of ˜6.

  The total content of the silicone resin capable of hydrosilylation reaction in 100% by weight of the sealing agent is preferably 70% by weight or more, more preferably 80% by weight or more, still more preferably 85% by weight or more, preferably 98% by weight. % Or less, more preferably 97% by weight or less, and still more preferably 96% by weight or less. When the content of the silicone resin capable of hydrosilylation reaction is not less than the above lower limit and not more than the above upper limit, the light intensity emitted from the optical semiconductor device is further increased.

  The content of the second silicone resin is preferably 10 parts by weight or more, more preferably 30 parts by weight or more, still more preferably 50 parts by weight or more, preferably 400 parts by weight with respect to 100 parts by weight of the first silicone resin. Part or less, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less. When the content of the second silicone resin with respect to 100 parts by weight of the first silicone resin is not less than the lower limit and not more than the upper limit, the curability and storage stability of the sealant are further enhanced, and further sealing is performed. The heat resistance of the agent is further increased.

  The ratio of the number of alkenyl groups in the entire first silicone resin to the number of hydrogen atoms bonded to silicon atoms in the entire second silicone resin (number of alkenyl groups / number of hydrogen atoms bonded to silicon atoms) is Preferably it is 0.8 or more, More preferably, it is 0.9 or more, Preferably it is 1.2 or less, More preferably, it is 1.1 or less. When the above ratio (number of alkenyl groups / number of hydrogen atoms bonded to silicon atoms) is not less than the above lower limit and not more than the above upper limit, the adhesion, the heat cycle resistance, the moisture resistance and the heat resistance of the sealant are effective. To be high.

(Catalyst for hydrosilylation reaction)
The sealing agent contains a hydrosilylation reaction catalyst. The catalyst for hydrosilylation reaction is a catalyst for hydrosilylation reaction of the silicone resin capable of hydrosilylation reaction. The hydrosilylation catalyst is a catalyst that causes a hydrosilylation reaction between an alkenyl group in the first organopolysiloxane and a hydrogen atom bonded to a silicon atom in the second silicone resin.

  As the hydrosilylation reaction catalyst, various catalysts that cause the hydrosilylation reaction to proceed can be used. Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Since the transparency of the sealant can be increased, a platinum-based catalyst is preferable. As for the said catalyst for hydrosilylation reaction, only 1 type may be used and 2 or more types may be used together.

  Examples of the platinum-based catalyst include platinum powder, chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex or a platinum-olefin complex is preferable.

  Examples of the alkenylsiloxane in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethyl-1,3,5. , 7-tetravinylcyclotetrasiloxane and the like. Examples of the olefin in the platinum-olefin complex include allyl ether and 1,6-heptadiene.

  Since the stability of the platinum-alkenylsiloxane complex and platinum-olefin complex can be improved, alkenylsiloxane, organosiloxane oligomer, allyl ether or olefin is added to the platinum-alkenylsiloxane complex or platinum-olefin complex. Is preferred. The alkenylsiloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. The organosiloxane oligomer is preferably a dimethylsiloxane oligomer. The olefin is preferably 1,6-heptadiene.

  From the viewpoint of further suppressing the decrease in luminous intensity when used in a state of being energized in a harsh environment under high temperature or high humidity, and further suppressing discoloration of the sealant, the hydrosilylation reaction The catalyst is preferably an alkenyl complex of platinum. From the viewpoint of further suppressing the decrease in luminous intensity when used in a state of being energized in a harsh environment at high temperature or high humidity, and further suppressing discoloration of the sealant, the above platinum alkenyl complex Is preferably a platinum alkenyl complex obtained by reacting chloroplatinic acid hexahydrate with 6 equivalents or more of a bifunctional or higher alkenyl compound. In this case, the platinum alkenyl complex is a reaction product of chloroplatinic acid hexahydrate and 6 equivalents or more of a bifunctional or higher alkenyl compound. Moreover, the transparency of the sealant can be increased by using the platinum alkenyl complex. As for the said platinum alkenyl complex, only 1 type may be used and 2 or more types may be used together.

It is preferable to use the chloroplatinic acid hexahydrate (H ₂ PtCl ₆ .6H ₂ O) as a platinum raw material for obtaining the platinum alkenyl complex.

  Examples of the bifunctional or higher alkenyl compound of 6 equivalents or more for obtaining the platinum alkenyl include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-dimethyl- Examples include 1,3-diphenyl-1,3-divinyldisiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

  Regarding the “equivalent” in the bifunctional or higher alkenyl compound of 6 equivalents or more, the equivalent weight of 1 mol of the bifunctional or higher alkenyl compound is 1 equivalent to 1 mol of the chloroplatinic acid hexahydrate. . It is preferable that the bifunctional or higher alkenyl compound having 6 equivalents or more is 50 equivalents or less.

  Examples of the solvent used to obtain the platinum alkenyl complex include alcohol solvents such as methanol, ethanol, 2-propanol, and 1-butanol. Aromatic solvents such as toluene and xylene may be used. As for the said solvent, only 1 type may be used and 2 or more types may be used together.

  In order to obtain the platinum alkenyl complex, a monofunctional vinyl compound may be used in addition to the above components. Examples of the monofunctional vinyl compound include trimethoxyvinylsilane, triethoxyvinylsilane, and vinylmethyldimethoxysilane.

  Regarding the reaction product of chloroplatinic acid hexahydrate and 6 equivalents or more of bifunctional or higher alkenyl compound, platinum element and 6 equivalents or more of bifunctional or higher alkenyl compound are covalently bonded or distributed. Or are covalently bonded and coordinated.

  The content of the hydrosilylation catalyst is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, preferably 0 parts by weight based on 100 parts by weight of the total silicone resin capable of hydrosilylation reaction. 0.5 parts by weight or less, more preferably 0.3 parts by weight or less. When the content of the hydrosilylation catalyst is equal to or higher than the lower limit, it is easy to sufficiently cure the sealant. If the content of the hydrosilylation reaction catalyst is not more than the above upper limit, the problem of coloring of the sealant hardly occurs.

(Compound represented by Formula (1))
The compound represented by the above formula (1) greatly contributes to effectively increasing the adhesiveness, cold heat cycle characteristics, moisture resistance and heat resistance of the sealant.

  In said formula (1), R1 and R2 represent a C1-C3 hydrocarbon group, respectively, R3 represents a C1-C8 hydrocarbon group or a C1-C3 alkoxy group. R1 and R2 are each preferably a saturated hydrocarbon group, and the hydrocarbon group may be linear or branched. R3 is preferably a saturated hydrocarbon group, an aromatic hydrocarbon group or a saturated alkoxy group, and may be linear, branched or cyclic.

  R1 and R2 each preferably represent a hydrocarbon group having 1 or 2 carbon atoms.

  R3 preferably represents a hydrocarbon group having 1 to 3 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. R3 preferably represents a hydrocarbon group having 1 or 2 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an alkoxy group having 1 or 2 carbon atoms. The aryl group having 6 to 8 carbon atoms is preferably a phenyl group.

  Examples of the hydrocarbon group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples thereof include aliphatic hydrocarbon groups such as n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl, and aromatic hydrocarbon groups such as phenyl group. Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.

  The content of the compound represented by the formula (1) is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the total silicone resin capable of hydrosilylation reaction. More preferably, it is 0.5 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less. When the content of the compound represented by the above formula (1) is not less than the above lower limit and not more than the above upper limit, the adhesiveness, cold heat cycle characteristics, moisture resistance and heat resistance of the sealant are further effectively increased. .

(Alkoxy compound)
Unlike the compound represented by the formula (1), it is preferable to include an alkoxy compound having an alkoxy group. By using the alkoxy compound, the adhesive force of the sealant is further increased.

  The alkoxy compound includes an alkoxy compound having a tetravalent group 4 atom having an atomic number of up to 40 in the periodic table of IUPAC, an alkoxy compound having a divalent group 12 atom having an atomic number of up to 40 in the periodic table of IUPAC, or It is an alkoxy compound having a trivalent group 13 atom having an atomic number of up to 40 in the periodic table of IUPAC. Examples of the tetravalent group 4 atom having an atomic number up to 40 in the periodic table of IUPAC include titanium and zirconium. Examples of the divalent group 12 atom having an atomic number of up to 40 in the IUPAC periodic table include zinc. Examples of the trivalent group 13 atom having an atomic number of up to 40 in the periodic table of IUPAC include boron, aluminum, and gallium. The alkoxy compound is an organic compound having an alkoxy group.

  As said alkoxy group, a C1-C10 alkoxy group is preferable. The carbon chain of the alkoxy group may be linear or branched. The alkoxy group is not particularly limited, and for example, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and 2-ethylhexyloxy group. Etc.

  From the viewpoint of further increasing the adhesive strength of the sealant, the alkoxy compound is preferably an alkoxy compound having titanium, zirconium or aluminum, more preferably an alkoxy compound having titanium or zirconium, and titanium. It is particularly preferable that it is an alkoxy compound. In particular, the use of an alkoxy compound having titanium (titanium atoms) significantly increases the adhesive strength of the sealant.

  Specific examples of the alkoxy compound having titanium include tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium, tetra (n-butoxy) titanium, tetrakis (2-ethylhexyloxy) titanium, titanium- Examples thereof include isopropoxyoctylene glycolate and titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide). Among these, from the viewpoint of further increasing the adhesive strength of the sealant, the alkoxy compound having a titanium atom includes tetra (n-butoxy) titanium, tetrakis (2-ethylhexyloxy) titanium, titanium-isopropoxyoctyleneglycol. Preferred is a rate or titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), tetrakis (2-ethylhexyloxy) titanium, titanium-isopropoxyoctylene glycolate or titanium di- 2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide) is preferred.

  Examples of the alkoxy compound having zirconium include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraisopropoxide and zirconium tetra n-butoxide. Of these, zirconium tetramethoxide is preferable.

  Examples of the alkoxy compound having aluminum include trimethoxy aluminum, triethoxy aluminum, tri n-propoxy aluminum, triisopropoxy aluminum, tri n-butoxy aluminum, and acetoalkoxy aluminum diisopropylate. Of these, triisopropoxyaluminum is preferable.

  The content of the alkoxy compound is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and still more preferably 0.5 parts by weight based on 100 parts by weight of the total silicone resin capable of hydrosilylation reaction. Part by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less. When the content of the alkoxy compound is not less than the above lower limit and not more than the above upper limit, the adhesive force of the sealant is further increased.

(Silicon oxide particles)
The sealant preferably contains silicon oxide particles. By using the silicon oxide particles, the viscosity of the sealant before curing can be adjusted to an appropriate range without impairing the heat resistance and light resistance of the cured product of the sealant. Therefore, the handleability of the sealing agent can be improved. The silicon oxide particles are preferably surface-treated with an organosilicon compound. By this surface treatment, the dispersibility of the silicon oxide particles becomes very high, and the decrease in the viscosity due to the increase in the temperature of the sealant before curing can be further suppressed.

  The content of the silicon oxide particles is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, preferably 40 parts by weight or less based on 100 parts by weight of the silicone resin capable of hydrosilylation reaction. More preferably, it is 35 parts by weight or less, and still more preferably 20 parts by weight or less. When the content of the silicon oxide particles is equal to or higher than the lower limit, it is possible to suppress a decrease in viscosity at the time of curing. When the content of the silicon oxide particles is not more than the above upper limit, the viscosity of the sealant can be controlled to a more appropriate range, and the transparency of the sealant can be further enhanced.

(Phosphor)
The sealing agent may further contain a phosphor. The above phosphor acts to absorb light emitted from a light emitting element that is sealed using a sealant for an optical semiconductor device and generate fluorescence to finally obtain light of a desired color. To do. The phosphor is excited by light emitted from the light emitting element to emit fluorescence, and light of a desired color can be obtained by a combination of light emitted from the light emitting element and fluorescence emitted from the phosphor.

  For example, when it is intended to finally obtain white light using an ultraviolet LED chip as a light emitting element, it is preferable to use a combination of a blue phosphor, a red phosphor and a green phosphor. When it is intended to finally obtain white light using a blue LED chip as a light emitting element, it is preferable to use a combination of a green phosphor and a red phosphor, or a yellow phosphor. As for the said fluorescent substance, only 1 type may be used and 2 or more types may be used together.

The blue phosphor is not particularly limited. For example, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu and the like.

It is not particularly restricted but includes the red phosphor, for _{example, (Sr, Ca) S:} Eu, (Ca, Sr) 2 Si 5 N 8: Eu, CaSiN 2: Eu, CaAlSiN 3: Eu, Y 2 O 2 S : Eu, La ₂ O ₂ S: Eu, LiW ₂ O ₈ : (Eu, Sm), (Sr, Ca, Bs, Mg) ₁₀ (PO ₄ ) ₈ Cl ₂ : (Eu, Mn), Ba ₃ MgSi ₂ And O ₈ : (Eu, Mn).

The green phosphor is not particularly limited, and for example, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, SrGa ₂ S ₄ : Eu, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, SrSiON: Eu, ZnS: (Cu, Al), BaMgAl ₁₀ O ₁₇ (Eu, Mn), SrAl ₂ O ₄ : Eu, and the like.

Is not particularly restricted but includes the yellow phosphor, for _{example, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 Al 5 O 12: Ce, Tb 3 Al 5 O 12: Ce, CaGa 2 S 4: Eu , Sr ₂ SiO ₄ : Eu, and the like.

  The phosphor content can be adjusted as appropriate so as to obtain light of a desired color, and is not particularly limited. The content of the phosphor is preferably 0.1 parts by weight or more and preferably 40 parts by weight or less with respect to 100 parts by weight of the sealant. The content of the phosphor is preferably 0.1 parts by weight or more and preferably 40 parts by weight or less with respect to 100 parts by weight of all components excluding the phosphor of the sealant.

(Other ingredients)
The sealing agent may further contain additives such as a dispersant, an antioxidant, an antifoaming agent, a colorant, a modifier, a leveling agent, a light diffusing agent, or a flame retardant, as necessary.

(Details and applications of sealants for optical semiconductor devices)
When the sealing agent has thermosetting properties, the curing temperature of the sealing agent is not particularly limited. The curing temperature of the sealing agent is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. When the curing temperature is equal to or higher than the above lower limit, the sealant is sufficiently cured. When the curing temperature is not more than the above upper limit, the package is unlikely to be thermally deteriorated.

  The curing method is not particularly limited, but it is preferable to use a step cure method. The step cure method is a method in which the resin is temporarily cured at a low temperature and then cured at a high temperature. By using the step cure method, curing shrinkage of the sealant can be suppressed.

  The method for producing the sealant is not particularly limited, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a three roll or a bead mill, at room temperature or under heating, Examples include a method of mixing the silicone compound, a filler excluding the phosphor, and other components blended as necessary.

  The light-emitting element is not particularly limited as long as it is a light-emitting element using a semiconductor. For example, when the light-emitting element is a light-emitting diode, for example, a structure in which a semiconductor material for forming an LED is stacked on a substrate can be given. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

  Examples of the material for the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Further, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the material of the buffer layer include GaN and AlN.

  Specific examples of the optical semiconductor device according to the present invention include a light emitting diode device, a semiconductor laser device, and a photocoupler. Such optical semiconductor devices include, for example, backlights such as liquid crystal displays, illumination, various sensors, light sources such as printers and copiers, vehicle measuring instrument light sources, signal lights, indicator lights, display devices, and light sources for planar light emitters. , Displays, decorations, various lights, switching elements and the like.

  In the optical semiconductor device according to the present invention, the light emitting element formed by the optical semiconductor is sealed by the sealing portion (cured product) obtained by curing the sealing agent for optical semiconductor device according to the present invention. . In the optical semiconductor device according to the present invention, a sealing portion (cured product) obtained by curing an encapsulant for optical semiconductor devices is disposed so as to seal a light emitting element formed of an optical semiconductor such as an LED. Has been. For this reason, the luminous intensity emitted from the optical semiconductor device can be increased. Cracks are unlikely to occur in the sealant that seals the light emitting element, and peeling from the package can be prevented. Moreover, the luminous intensity emitted from the optical semiconductor device can be increased, and heat resistance, weather resistance, and gas barrier properties can also be improved.

(Embodiment of optical semiconductor device)
1A and 1B schematically show an optical semiconductor device using an optical semiconductor device sealing agent according to an embodiment of the present invention in a cross-sectional view and a perspective view.

  The optical semiconductor device 1 according to this embodiment includes a lead frame 2, an optical semiconductor element 3, a first molded body 4, and a second molded body 5. The optical semiconductor element 3 is preferably a light emitting diode (LED). The first molded body 4 and the second molded body 5 are not formed integrally, but are two other members. The first molded body 4 and the second molded body 5 may be integrally formed. The first molded body 4 is a frame portion. The 2nd molded object 5 is a bottom part. In the optical semiconductor device 1, the molded body has a frame portion (first molded body 4) and a bottom portion (second molded body 5). The frame part which is the 1st molded object 4 is an outer wall part. The frame part which is the 1st molded object 4 is cyclic | annular.

  An optical semiconductor element 3 is mounted and arranged on the lead frame 2. A first molded body 4 (frame portion) is disposed on the lead frame 2. A second molded body 5 (bottom part) is disposed between the plurality of lead frames 2 and below the lead frames 2. Note that the molded body or the bottom member may not be disposed below the lead frame, and the lead frame may be exposed. The optical semiconductor element 3 is disposed inside the first molded body 4. A first molded body 4 is disposed on the side of the optical semiconductor element 3, and the first molded body 4 is disposed so as to surround the optical semiconductor element 3. The 1st molded object 4 has light reflectivity, and has a light reflection part in the inner surface 4a. That is, the inner surface 4a of the first molded body 4 is a light reflecting portion. Therefore, the periphery of the optical semiconductor element 3 is surrounded by the inner surface 4 a having the light reflectivity of the first molded body 4.

  The first molded body 4 (frame part) has an opening through which light emitted from the optical semiconductor element 3 is extracted. The first and second molded bodies 4 and 5 are white. The inner surface 4a of the first molded body 4 is formed such that the diameter of the inner surface 4a increases as it goes toward the opening end. Therefore, of the light emitted from the optical semiconductor element 3, the light indicated by the arrow B reaching the inner surface 4 a is reflected by the inner surface 4 a and travels forward of the optical semiconductor element 3.

  The optical semiconductor element 3 is connected to the lead frame 2 using a die bond material 6. The die bond material 6 has conductivity. A bonding pad (not shown) provided on the optical semiconductor element 3 and the lead frame 2 are electrically connected by a bonding wire 7. In a region surrounded by the inner surface 4a of the first molded body 4 so as to seal the optical semiconductor element 3 and the bonding wire 7, a sealing portion 8 (cured product of sealing agent) is disposed. . As the sealing part 8, the hardened | cured material obtained by hardening the sealing compound for optical semiconductor devices which concerns on one Embodiment of this invention is used.

  In the optical semiconductor device 1, when the optical semiconductor element 3 is driven, light is emitted as indicated by a broken line A. In the optical semiconductor device 1, the light reaching the inner surface 4 a of the first molded body 4 as indicated by the arrow B as well as the light irradiated from the optical semiconductor element 3 to the side opposite to the upper surface of the lead frame 2, that is, the upper side. There is also light that is reflected by the light. Therefore, the light extracted from the optical semiconductor device 1 is bright.

  FIG. 2 shows a modification of the optical semiconductor device 1 shown in FIG. The optical semiconductor device 1 shown in FIG. 1 differs from the optical semiconductor device 21 shown in FIG. 2 only in the electrical connection structure using the die bonding materials 6 and 22 and the bonding wires 7 and 23. The die bond material 6 in the optical semiconductor device 1 has conductivity. On the other hand, the optical semiconductor device 21 has a die bond material 22, and the die bond material 22 does not have conductivity. In the optical semiconductor device 1, a bonding pad (not shown) provided on the optical semiconductor element 3 and a lead frame 2 (lead frame located on the right side in FIG. 1A) are electrically connected by a bonding wire 7. Has been. The optical semiconductor device 21 has a bonding wire 23 in addition to the bonding wire 7. In the optical semiconductor device 21, a bonding pad (not shown) provided on the optical semiconductor element 3 and a lead frame 2 (a lead frame located on the right side in FIG. 2) are electrically connected by a bonding wire 7. Further, a bonding pad (not shown) provided on the optical semiconductor element 3 and the lead frame 2 (lead frame located on the left side in FIG. 2) are electrically connected by a bonding wire 23.

  FIG. 3 shows a modification of the optical semiconductor device 21 shown in FIG. The optical semiconductor device 31 shown in FIG. 3 is also a modification of the optical semiconductor device 1 shown in FIG. The optical semiconductor device 21 shown in FIG. 2 and the optical semiconductor device 31 shown in FIG. 3 differ only in the structures of the first and second molded bodies 4 and 5 and the molded body 32. In the optical semiconductor device 21, the first and second molded bodies 4 and 5 are used. The first molded body 4 is disposed on the lead frame 2, and the second molded body 5 includes a plurality of second molded bodies 5. Between the lead frames 2 and below the lead frame 2. On the other hand, in the optical semiconductor device 31, one molded body 32 is used. The molded body 32 has a frame portion 32 a disposed on the lead frame 2 and a filling portion 32 b disposed between the plurality of lead frames 2. The frame part 32a and the filling part 32b are integrally formed. As described above, the optical semiconductor device only needs to have a frame portion disposed on the side of the optical semiconductor element in the optical semiconductor device. The molded body may not be disposed below the lead frame. The molded body may not have a bottom portion disposed below the lead frame. The back surface of the lead frame may be exposed.

  The structures shown in FIGS. 1 to 3 are merely examples of the optical semiconductor device according to the present invention, and can be appropriately modified to a structure of a molded body, a mounting structure of an optical semiconductor element, and the like.

  Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.

(Silicone resin capable of hydrosilylation reaction)
In the synthesis of each of the following polymers, the following organosilicon compounds were used to introduce the following structural units (Ph is a phenyl group, Vi is a vinyl group, and Me is a methyl group).

Structural unit of Me ₂ ViSiO _1/2 : 1,3-divinyl-1,1,3,3-tetramethyldisiloxane Structural unit of Me ₂ HSiO _1/2 : 1,1,3,3-tetramethyldisiloxane structural units MePhSiO _2/2: structural units of methyl phenyl dimethoxy silane Ph ₂ SiO _2/2: structural units of diphenyldimethoxysilane Me ₂ SiO _2/2: structural units of dimethyldimethoxysilane MeViSiO _2/2: methyl vinyl dimethoxy silane MeSiO _3/2 structural unit: methyltrimethoxysilane PhSiO _3/2 structural unit: phenyltrimethoxysilane

[Synthesis of Polymer A] Synthesis of First Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 164.1 g of methylphenyldimethoxysilane, 6.6 g of methylvinyldimethoxysilane, and 1,3 -4.7 g of divinyl-1,1,3,3-tetramethyldisiloxane was added and stirred at 50 ° C. A solution obtained by dissolving 2.2 g of potassium hydroxide in 35.1 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, volatile components were removed under reduced pressure, 2.4 g of acetic acid was added to the reaction solution, and the mixture was heated under reduced pressure. Thereafter, potassium acetate was removed by filtration to obtain a polymer (A).

The number average molecular weight of the obtained polymer (A) was 3,500. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (A) had the following average composition formula.

(MePhSiO _2/2 ) _0.90 (MeViSiO _2/2 ) _0.05 (Me ₂ ViSiO _1/2 ) _0.05 Formula

  In the above formula, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group. The obtained polymer (A) had a phenyl group content of 43.9 mol% and a vinyl group content of 4.88 mol%.

  The molecular weight of each polymer was measured by GPC measurement by adding 1 mL of tetrahydrofuran to 10 mg, stirring until dissolved. In GPC measurement, a measuring device manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) x 2 manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: Polystyrene) was used.

[Synthesis of Polymers B to H] Synthesis of First Silicone Resin Synthesis of Polymer A except that the type and blending amount of the organosilicon compound used in the synthesis were changed, and that the blending amounts of catalyst, acetic acid and water were changed. In the same manner as above, polymers B to H were obtained.

[Synthesis of Polymer I] Synthesis of Second Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 80.6 g of diphenyldimethoxysilane and 1,1,3,3-tetramethyldisiloxane 45 g was added and stirred at 50 ° C. Into this, a solution of 100 g of acetic acid and 23.9 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (I) was obtained.

The number average molecular weight of the obtained polymer (I) was 850. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (I) had the following average composition formula.

(Ph ₂ SiO _2/2 ) _0.67 (Me ₂ HSiO _1/2 ) _0.33 Formula

  In the above formula, Me represents a methyl group, and Ph represents a phenyl group. The content ratio of the phenyl group of the obtained polymer I was 24.7 mol%, and the content ratio of hydrogen atoms bonded to silicon atoms was 25.09%.

[Synthesis of Polymers J to L] Synthesis of Second Silicone Resin Synthesis of Polymer I except that the kind and blending amount of the organosilicon compound used for the synthesis were changed, and that the blending amounts of catalyst, acetic acid and water were changed. In the same manner as above, Polymers J to L were obtained.

  Details of the polymers A to L are shown in Table 1 below.

(Catalyst for hydrosilylation reaction)
Catalyst for hydrosilylation reaction (1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum)

(Compound represented by Formula (1))
Compound 1A represented by the following formula (1A)

  Compound 1B represented by the following formula (1B)

  Compound 1C represented by the following formula (1C)

  Compound 1D represented by the following formula (1D)

(Compound similar to the compound represented by Formula (1))
Compound 102 represented by the following formula (102)

  Compound 101A represented by the following formula (101A)

  Triallyl isocyanurate represented by the following formula (106)

  Diallyl monoglycidyl isocyanurate (104) represented by the following formula (104)

  Monoallyl diglycidyl isocyanurate (103) represented by the following formula (103)

  Triglycidyl isocyanurate (105) represented by the following formula (105)

(Alkoxy compound)
Zirconium tetramethoxide (manufactured by Yamanaka Hutech)
Triisopropoxy aluminum (manufactured by Yamanaka Hutech)
Tetra (n-butoxy) titanium (manufactured by Yamanaka Hutech)
Tetrakis (2-ethylhexyloxy) titanium (Nippon Soda Co., Ltd.)
Titanium-isopropoxyoctylene glycolate (Nippon Soda Co., Ltd.)
Titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide) (Matsumoto Fine Chemical Co., Ltd.)

Example 1
Polymer A: 23.7 parts by weight, Polymer E: 64.5 parts by weight, Polymer I: 11.8 parts by weight, hydrosilylation catalyst (1,3-divinyl-1,1,3, platinum) 3-tetramethyldisiloxane complex): 0.02 part by weight and compound 1A represented by the above formula (1A): 1 part by weight were mixed and degassed to obtain a sealant.

(Examples 2-14 and Comparative Examples 1-11)
A sealant was obtained in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Table 2 below.

(Evaluation)
(1) Measurement of viscosity at 25 ° C. Using an E-type viscometer (TV-22 type, manufactured by Toki Sangyo Co., Ltd.), the viscosity (mPa · s) of the obtained sealant at 25 ° C. at 10 rpm is measured. did.

(2) Adhesive strength (die shear strength)
A sealant was applied on a PPA (polyphthalamide) plate (5 cm × 5 cm × 1 mm) so that the adhesion area was 3 mm × 3 mm, and a 3 mm square Si chip was placed thereon to obtain a test sample.

  The obtained test sample was heated at 150 ° C. for 2 hours to cure the sealant. Next, the die shear strength at 80 ° C. was evaluated at a speed of 300 μ / second using a die shear tester (“DAGE 4000” manufactured by Arctech).

  In addition, PPA (polyphthalamide) plate of the same size, PCT (polycyclohexylene dimethylene terephthalate) plate, EMC (epoxy molding compound) plate, and Ag plated Cu (copper) plate (Ag in the table) A modified board was prepared. Die shear strength was similarly evaluated for these plates. The die shear strength was determined according to the following criteria.

[Die shear strength criteria]
◯: Die shear strength is 30N or more ○: Die shear strength is 25N or more and less than 30N △: Die shear strength is 20N or more and less than 25N ×: Die shear strength is less than 20N

(3) Cooling and heat cycle characteristics A light-emitting element (emission peak 460 nm) is mounted on a silver-plated housing material with a lead electrode (PPA (polyphthalamide)) by a die-bonding material. In the structure connected by the gold wire, the obtained sealant was injected, and heated and cured at 150 ° C. for 2 hours to produce an optical semiconductor device.

  The obtained optical semiconductor device was held at −50 ° C. for 30 minutes using a liquid tank thermal shock tester (“TSB-51” manufactured by ESPEC), then heated to 135 ° C., and 30 at 135 ° C. A cold cycle test was conducted in which the temperature was lowered to -50 ° C after being held for 1 minute, and the cycle was one cycle. Twenty samples were taken out after 500 cycles, 750 cycles, 1000 cycles, and 2000 cycles, respectively.

  The sample was observed with a stereomicroscope ("SMZ-10" manufactured by Nikon Corporation). It is observed whether there are cracks in the cured material of the sealant of 20 samples, or whether the cured product is peeled off from the package or electrode, and whether there is a sample with cracks or peeling. I confirmed. The cold / heat resistance cycle characteristics were determined according to the following criteria.

[Criteria for cold cycle resistance characteristics]
◯: No cracks and exfoliation occurred until 2000 cycles. ○: No cracks and exfoliation occurred until 1000 cycles, but cracks and exfoliation occurred during 2000 cycles. Δ: No cracks and exfoliation occurred until 750 cycles. , Cracks and peeling occurred at 1000 cycles. X: cracks and peeling occurred at 750 cycles.

(4) Moisture resistance An optical semiconductor device obtained by the evaluation of the above (3) cold-heat cycle characteristics was prepared. The light semiconductor device was measured for light intensity (initial light intensity) when a current of 60 mA was passed through the light emitting element using a light intensity measurement device (“OL770” manufactured by Optronic Laboratories) at a temperature of 23 ° C.

  Next, in a state where a current of 60 mA was passed through the light emitting element, the optical semiconductor device was placed in a chamber under an atmosphere of 60 ° C. and a relative humidity of 90 RH% and left for 1000 hours. Measure the light intensity (light intensity after leaving) of the light-semiconductor device using a light intensity measuring device ("OL770" manufactured by Optronic Laboratories) at a temperature of 23 ° C. did. The decrease rate of the luminous intensity after being left from the initial luminous intensity was determined. The moisture resistance was determined according to the following criteria.

[Criteria for moisture resistance]
◯: Decrease rate of luminosity is less than 5% ◯: Decrease rate of luminosity is 5% or more and less than 10% Δ: Decrease rate of luminosity is 10% or more and less than 20% ×: Decrease rate of luminosity is 20% or more

(5) Heat resistance The optical semiconductor device obtained by the evaluation of the above (3) cold resistance cycle characteristics was prepared. The light semiconductor device was measured for light intensity (initial light intensity) when a current of 60 mA was passed through the light emitting element using a light intensity measurement device (“OL770” manufactured by Optronic Laboratories) at a temperature of 23 ° C.

  Next, in a state where a current of 60 mA was passed through the light emitting element, the optical semiconductor device was placed in a chamber under an atmosphere of 85 ° C. and left for 1000 hours. Measure the light intensity (light intensity after leaving) of the light-semiconductor device using a light intensity measuring device ("OL770" manufactured by Optronic Laboratories) at a temperature of 23 ° C. did. The decrease rate of the luminous intensity after being left from the initial luminous intensity was determined. The heat resistance was determined according to the following criteria.

[Criteria for heat resistance]
◯: Decrease rate of luminosity is less than 5% ◯: Decrease rate of luminosity is 5% or more and less than 10% Δ: Decrease rate of luminosity is 10% or more and less than 20% ×: Decrease rate of luminosity is 20% or more

  The composition and results are shown in Table 2 below.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Lead frame 3 ... Optical semiconductor element 4 ... 1st molded object 4a ... Inner surface 5 ... 2nd molded object 6 ... Die-bonding material 7 ... Bonding wire 8 ... Sealing part (curing of sealing agent) object)
DESCRIPTION OF SYMBOLS 21 ... Optical semiconductor device 22 ... Die bond material 23 ... Bonding wire 31 ... Optical semiconductor device 32 ... Molded object 32a ... Frame part 32b ... Filling part

Claims (8)

An encapsulant for an optical semiconductor device used by being cured by a hydrosilylation reaction,
A silicone resin capable of hydrosilylation reaction;
A catalyst for hydrosilylation reaction;
The sealing compound for optical semiconductor devices containing the compound represented by following formula (1).

In said Formula (1), R1 and R2 represent a C1-C3 hydrocarbon group, respectively, R3 represents a C1-C8 hydrocarbon group or a C1-C3 alkoxy group. Unlike the compound represented by the formula (1), an alkoxy compound having an alkoxy group is included,
The alkoxy compound has a tetravalent group 4 atom with an atomic number of up to 40 in the periodic table of IUPAC, an alkoxy compound with a divalent group 12 atom with an atomic number of up to 40 in the periodic table of IUPAC, or The encapsulant for optical semiconductor devices according to claim 1, which is an alkoxy compound having a trivalent group 13 atom having an atomic number of up to 40 in the periodic table of IUPAC.   The encapsulant for optical semiconductor devices according to claim 1, wherein the alkoxy compound is an alkoxy compound having titanium.   The alkoxy compound having a titanium atom is tetrakis (2-ethylhexyloxy) titanium, titanium-isopropoxyoctylene glycolate, or titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide). The encapsulant for optical semiconductor devices according to claim 3.   The silicone resin capable of hydrosilylation is at least one first silicone resin having two or more alkenyl groups bonded to silicon atoms, and a second silicone resin having two or more hydrogen atoms bonded to silicon atoms. The sealing agent for optical semiconductor devices of any one of Claims 1-4 containing at least 1 sort (s) of these. The first silicone resin includes a first silicone resin represented by the following formula (11A) and a first silicone resin represented by the following formula (11B):
The encapsulant for optical semiconductor devices according to claim 5, wherein the second silicone resin contains a second silicone resin represented by the following formula (12A).

In the formula (11A), a, b, and c satisfy 0.05 ≦ a ≦ 0.20, 0.50 ≦ b ≦ 0.95, and 0 ≦ c ≦ 0.30, respectively. -15 mol% represents an alkenyl group, 20-50 mol% of R1 to R6 represents an aryl group, and R1 to R6 other than the aryl group and alkenyl group represent a hydrocarbon group having 1 to 6 carbon atoms.

In the formula (11B), e, f, and g satisfy 0.15 ≦ e ≦ 0.30, 0 ≦ f ≦ 0.20, 0.60 ≦ g ≦ 0.85, and 10 of R11 to R16 -20 mol% represents an alkenyl group, 20-50 mol% of R11 to R16 represents an aryl group, and R11 to R16 other than the aryl group and the alkenyl group represent a hydrocarbon group having 1 to 6 carbon atoms.

In the formula (12A), h, i, and j satisfy 0.50 ≦ h ≦ 0.75, 0.25 ≦ i ≦ 0.50, and 0 ≦ j ≦ 0.25, and R21 to R26 of 20 ˜30 mol% represents a hydrogen atom directly bonded to a silicon atom, 10 to 25 mol% of R 21 to R 26 represents an aryl group, and R 21 to R 26 other than the hydrogen atom directly bonded to the aryl group and the silicon atom have a carbon number of 1 Represents a hydrocarbon group of ˜6.   The ratio of the number of alkenyl groups in the entire first silicone resin to the number of hydrogen atoms bonded to silicon atoms in the entire second silicone resin is 0.9 or more and 1.1 or less. 6. Sealant for optical semiconductor devices according to 6. An optical semiconductor element;
A sealing part obtained by curing the sealing agent for optical semiconductor device according to any one of claims 1 to 7,
An optical semiconductor device, wherein the sealing portion is disposed so as to seal the optical semiconductor element.

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