JP2007224193A - Curable resin composition and optical device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition and an optical device, which have excellent transparency, high refractive index, weatherability, heat resistance, and appropriate hardness and strength and enables production of well-balanced cured products. <P>SOLUTION: The curable resin composition comprises (A) a polyorganosiloxane having an average of two or more ethylenically unsaturated group in one molecule, (B) a fluorene compound represented by formula [1], wherein X and Y denote ethylenically unsaturated groups and may be the same or different, R<SP>1</SP>denotes a 1 to 20C divalent hydrocarbon group, R<SP>2</SP>denotes a 1 to 10C alkyl group or aryl group, "a" is an integer between 0 and 4, (2+2n) "a"s may be the same or different, and "n" is an integer between 0 and 10, (C) a polyorganohydrogenpolysiloxane having two or more hydrogen atoms binding to a silicon atom in one molecule, and (D) a catalyst for hydrosilylation reaction. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a cured product having a high refractive index, heat resistance, and weather resistance suitable for sealing optical devices such as LEDs (hereinafter sometimes referred to as light emitting elements), photosensors, lasers, and general optical materials. The present invention relates to a curable resin composition containing a fluorene compound and a polyorganosiloxane, and further relates to an optical device sealed with the curable resin composition.

In recent years, the field of opto-devices has made remarkable progress. In particular, LEDs have excellent features such as long life, high brightness, and low power consumption, and their applications are expanding year by year. In particular, blue and ultraviolet light emitting LEDs have been developed in recent years, and are rapidly spreading in applications such as illumination light sources, display devices, and liquid crystal display backlights.
Conventionally, the epoxy resin excellent in intensity | strength and light transmittance has been mainly used for the material used for sealing of LED (for example, patent document 1, 2, 3).
However, an LED that emits light having a wavelength of about 350 nm to 500 nm, such as a blue LED or an ultraviolet LED, generates a large amount of heat from the semiconductor chip, and the light has a short wavelength. Coloring due to deterioration of the light is promoted, and thus light emitted from the semiconductor chip is absorbed, so that transmitted light is reduced, resulting in a decrease in luminance of the LED in a short time.
Silicone resins are known as other LED sealing materials. Sealing materials using silicone resins are excellent in transparency, weather resistance, and heat resistance, and thus are increasingly used in blue LED and ultraviolet LED applications that are degraded by epoxy resins.
However, many of the conventional silicone-based sealing materials are gel-like or rubber-like elastic bodies (for example, Patent Documents 4 and 5), which are easy to absorb impacts but are easily deformed. The problem of wire breakage is likely to occur. Furthermore, since the refractive index is lower than that of the epoxy resin, there is a problem that the light extraction efficiency is low, and there is a problem that tack is likely to remain on the cured product, and dust adheres to the surface or is easily damaged. As a means for solving these problems, a composition (for example, Patent Document 6) of an unsaturated group-containing organic compound and hydrogen polysiloxane has been proposed, but an alicyclic compound has a refractive index. A silicone-based sealing material having a good balance of physical properties has been strongly desired because it cannot be increased, and an ether structure such as allyl ether or a compound containing a nitrogen atom is not sufficient in that it tends to be colored at high temperatures.

JP 2003-277473 A JP 2003-176334 A JP 2003-26763 A JP-A-3-166262 JP-A-3-22553 JP 2002-80733 A

  In view of the above-mentioned problems of the prior art, the object of the present invention is to provide a cured product excellent in balance, having excellent transparency, high refractive index, weather resistance, heat resistance, and having an appropriate hardness and strength. An object of the present invention is to provide a silicone-based curable resin composition suitable for optical device use, particularly for blue LED and ultraviolet LED sealing, and an opto-device sealed with the same curable resin composition.

As a result of intensive studies to solve the above problems, the present inventors have made polyorganosiloxanes having ethylenically unsaturated groups, fluorene compounds having ethylenically unsaturated groups, polyorganohydrogenpolysiloxanes and hydrosilyls. By using a composition containing a fluorination reaction catalyst, a curable resin that provides a cured product with excellent balance, excellent transparency, high refractive index, weather resistance, heat resistance, moderate hardness and strength It has been found that a composition and an optical device can be provided, and the present invention has been completed.
That is, the present invention includes the following (1) to (9),
(1) (A) Polyorganosiloxane having two or more ethylenically unsaturated groups on average in one molecule, (B) fluorene compound represented by the formula [1]

[Wherein, X and Y represent ethylenically unsaturated groups, which may be the same or different. R ¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, R ² represents an alkyl group or aryl group having 1 to 10 carbon atoms, a is an integer of 0 to 4, and (2 + 2n) a are It can be the same or different. n is an integer from 0 to 10],
(C) a curable resin composition comprising a polyorganohydrogenpolysiloxane having two or more hydrogen atoms bonded to a silicon atom in one molecule, and (D) a hydrosilylation reaction catalyst,
(2) The curable resin composition according to the above (1), wherein X and Y in the formula [1] are at least one selected from an allyl group, a methallyl group, and a vinylbenzyl group,
(3) The curable resin composition according to the above (1) or (2), wherein both n and a in formula [1] are 0,
(4) A compound obtained by subjecting the fluorene compound of component (B) and the polyorganohydrogenpolysiloxane of component (C) to a hydrosilylation reaction in advance is blended into a mixture of component (A) and component (D). The curable resin composition according to the above (1),
(5) Said (1)-(4) mix | blended so that the ratio of (B) component with respect to the total amount of (A) component and (B) component may become the range used as 0.1 mass%-80 mass% The curable resin composition according to any one of
(6) Component (C) is added to the silicon atom in component (C) with respect to the total molar amount of ethylenically unsaturated groups in component (A) and ethylenically unsaturated groups in component (B). The curable resin composition according to any one of the above (1) to (5), wherein the molar ratio of directly connected hydrogen atoms is 0.5 to 2.0.
(7) The curable resin composition according to any one of the above (1) to (6), wherein the hydrosilylation reaction catalyst of (D) is a platinum group metal catalyst,
(8) The curable resin composition according to any one of the above (1) to (7), which is used for optical device sealing, and
(9) An optical device sealed with the curable resin composition according to any one of (1) to (7) above is provided.

  According to the present invention, as a sealing material for opto device applications, particularly blue LEDs and ultraviolet LEDs, it has excellent transparency, a high refractive index, weather resistance, heat resistance, and a balance having appropriate hardness and strength. A silicone-based curable resin composition that provides an excellent cured product and an excellent optical device are provided.

The present invention will be specifically described below.
The polyorganosiloxane as component (A) in the curable resin composition of the present invention is not particularly limited as long as it has at least two ethylenically unsaturated groups on average in one molecule, and the following average composition formula [2]
(R ⁵ ) _b (R ⁶ ) _C SiO _{(4-bc) / 2} [2]
The well-known compound represented by these, or mixtures thereof can be used. In this average composition formula [2], R ⁵ is an ethylenically unsaturated group, preferably an ethylenically unsaturated group having 2 to 10 carbon atoms, for example, vinyl group, allyl group, methallyl group, propenyl group, butenyl. Group, hexenyl group, cyclopentenyl group, cyclohexenyl group, octenyl group, vinylbenzyl group and the like. R ⁶ is a substituted or unsubstituted monovalent hydrocarbon group, or two R ⁶ may be combined to form a lower alkylene group. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an octyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclobutyl group; a phenyl group Aryl groups such as tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; or part or all of hydrogen atoms bonded to these hydrocarbon groups are chlorine, Groups substituted by halogen atoms such as fluorine and bromine, such as halogenated hydrocarbon groups such as chloromethyl, trifluoropropyl, chlorophenyl, dibromophenyl, tetrachlorophenyl, and difluorophenyl as the lower alkylene group can be also formed of two R ⁶ , Ethylene group, trimethylene group, methyl methylene group, tetramethylene group, hexamethylene group or the like. Also, b is a number 0 <b <3, and c is a number 0 <c <3, where 0 <b + c <4. The organopolysiloxane represented by the average composition formula [2] may be linear or branched, or may be a mixture thereof. Such organopolysiloxanes are used singly or in combination of two or more, but those having a molecular weight of about 500 to 100,000 are preferably used from the viewpoint of solubility with other components.

Examples of the branched polyorganosiloxane as the component (A) include the following general formulas (R ⁷ ₂ SiO _2/2 ) d, (CH ₂ = CHR ⁷ ₂ SiO _1/2 ) e, (R ⁷ A mixture having a structural unit represented by SiO _3/2 ) f and an average composition can be used.
In each structural unit, d, e, and f represent the mole fraction of each structural body in the mixture, and preferably satisfy the relationship of 0 <d, e, f ≦ 0.5, and d + e + f = 1.
In the above general formulas, R ⁷ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aromatic group, and may be the same or different. Examples of R ⁷ are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, Linear or branched alkyl group such as heptyl group, isoheptyl group, octyl group, isooctyl group, nonyl group, decyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptyl group, cyclooctyl group, dicyclopentyl And a cycloalkyl group such as a decahydronaphthyl group, a phenyl group, a naphthyl group, a tetrahydronaphthyl group, a tolyl group, and an ethylphenyl group, an aryl group, and the like. Among these, a methyl group, an ethyl group, a propyl group, and a phenyl group are particularly preferable from the viewpoint of availability.

  The organosilanes and / or organosiloxanes corresponding to the structural units of the above formulas can be used as raw materials, and can be obtained by cohydrolysis or copolymerization of a cohydrolyzed condensate. Examples of raw materials include trimethylchlorosilane, triethylchlorosilane, triphenylchlorosilane, tripropylchlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, trimethylmethoxysilane, diphenyldimethoxysilane, vinyltri Examples include methoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, and ethyltrimethoxysilane.

  As the linear polyorganosiloxane which is the component (A) in the curable resin composition of the present invention, for example, an ethylenically unsaturated group-containing siloxy-terminated diorganosiloxane represented by the following formula [3] is used. You can also

In the above formula [3], each R ³ is a monovalent hydrocarbon group which may have a substituent having 1 to 20 carbon atoms, and may be the same or different. Each R ⁴ is the same as R ³ or an ethylenically unsaturated group, m and l are ≧ 0, and they are not simultaneously 0, and the component (A) has an average of at least 2 per molecule. It is a numerical value including one ethylenically unsaturated group.
The upper limit of m is about 20, and in the embodiment described later, about 8 and l are 0. The ethylenically unsaturated group has about 2 to 10 carbon atoms, specifically, vinyl group, propenyl group, butenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group, octenyl group, allyl group, methallyl group. Vinyl benzyl group and the like, and vinyl group is preferable.
Preferably, R ³ is a monovalent hydrocarbon group having no substituent having less than 7 carbon atoms or a halogenated alkyl group having less than 7 carbon atoms, more preferably an alkyl group such as a methyl group or an ethyl group. A cycloalkyl group such as a cyclohexyl group, and an aryl group such as a phenyl group. Usually a methyl group.
Specific examples of the polyorganosiloxane represented by the above formula include dimethylvinylsiloxy-terminated polydimethylsiloxane and dimethylhexenylsiloxy-terminated dimethylsiloxane.

The ethylenically unsaturated group-containing fluorene compound represented by the formula [1], which is the component (B) in the curable resin composition of the present invention, has a high refractive index and excellent rigidity and heat resistance. In addition, it has the characteristics that it is hard to be colored by not containing an ether structure, ester structure or hetero atom in the molecule, and by adding this, it has excellent heat resistance inherent to the silicone resin The strength and refractive index of the cured product can be improved without degrading the physical properties such as.
In the formula [1], X and Y represent an ethylenically unsaturated group, which may be the same or different. As the ethylenically unsaturated group, those having about 2 to 10 carbon atoms, specifically vinyl group, propenyl group, butenyl group, hexenyl group, octenyl group, cyclopentenyl group, cyclohexenyl group, allyl group, There are a methallyl group, a vinylbenzyl group, and the like, and any one selected from an allyl group, a methallyl group, and a vinylbenzyl group is preferable.
R ¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, R ² represents an alkyl group or aryl group having 1 to 10 carbon atoms, a is an integer of 0 to 4, and (2 + 2n) a are It can be the same or different. n is an integer of 0 to 10, preferably 0 or 1.

  The ethylenically unsaturated group-containing fluorene compound of the formula [1] can be obtained by reacting a fluorene compound with a corresponding halogen compound having an ethylenically unsaturated group in the presence of an alkali metal. As the fluorene compound as one raw material, a compound having at least one active hydrogen at the 9,9′-position of the fluorene skeleton can be used, for example, fluorene, 2,7-dimethylfluorene, 2,7-diphenylfluorene. 1,2-bis (9-fluorenyl) ethane obtained by dehydration reaction of fluorene derivatives such as fluorene or the corresponding diol compound, or dehydrohalogenation reaction with a dihalomethyl compound, 1,3 Fluorene dimers such as -bis (9-fluorenyl) propane, 1,4-bis (9-fluorenyl) butane, 1,5-bis (9-fluorenyl) pentane, 1,6-bis (9-fluorenyl) hexane, Fluorene oligomers and the like can be mentioned. From the viewpoint of easy availability, fluorene, 2,7-dimethylfluorene, 1,6-bis (9 -Fluorenyl) hexane is preferred. These may be used alone or in admixture of two or more.

  Examples of the halogen compound as the other raw material include allyl chloride, allyl bromide, methallyl chloride, methallyl bromide, vinyl benzyl chloride, and vinyl benzyl bromide. These may be used alone or in combination of two or more. Also good.

Specific compounds of the component (B) include diallyl fluorene, dimethallyl fluorene, 9,9′-bis (vinylbenzyl) -2,7-dimethylfluorene, fluorene part of 1,6-bis (9-fluorenyl) hexane. A compound in which two vinylbenzyl groups are substituted at the 9′-position, ie, bis (vinylbenzyl) in which R ^{1 in} formula [1] is — (CH ₂ ) ₆ —, R ² is H, and n = 1 Fluorene compound, a compound in which two vinylbenzyl groups are substituted at the 9′-position of the fluorene moiety of an oligomer obtained by reacting fluorene with xylylene dichloride, that is, R ^{1 in the} formula [1] is —CH ₂ PhCH ₂ —, R ² Are bis (vinylbenzyl) fluorene oligomer compounds in which n is H and n = 1 to 3 (Ph is a phenyl group).

The blending amount of the component (B) is not particularly limited, and may be determined according to the strength and refractive index required for the optical device that is the target cured product, preferably the component (A) and the component (B). It is good to mix | blend in the range from which the ratio of (B) component with respect to the total amount of a component will be 0.1 mass%-80 mass%, More preferably, it will be 5 mass%-50 mass%.
By maintaining the blending ratio of the component (A) and the component (B) in the above range, the transparency is excellent, the refractive index is high, the weather resistance and the heat resistance are excellent, and the balance having appropriate hardness and strength is excellent. Cured product is obtained.

The polyorganohydrogenpolysiloxane which is the component (C) in the curable resin composition of the present invention is used as a crosslinking agent when the composition is cured by hydrosilylation reaction with the components (A) and (B). What is necessary is just at least one polyorganohydrogenpolysiloxane that works and has an average of two or more hydrogen atoms bonded to silicon atoms in one molecule.
Examples of the organohydrogenpolysiloxane include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,3-tetraphenyldisiloxane, 3,5,7-tetraphenylcyclotetrasiloxane, both ends trimethylsiloxy group-capped methylhydrogen polysiloxane, both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-capped dimethyl Polysiloxane, both ends dimethylhydrogensiloxy-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethyl Siloxy groups at methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymers, copolymers consisting of (CH _{3) 2} HSiO _1/2 units and SiO _4/2 units, (CH _{3) 2} HSiO _1/2 units And a copolymer composed of (C ₆ H ₅ ) SiO _3/2 units.

  The blending amount of the polyorganohydropolysiloxane as the component (C) is (C) based on the total molar amount of the ethylenically unsaturated group in the component (A) and the ethylenically unsaturated group in the component (B). By setting the molar ratio of hydrogen atoms directly bonded to silicon atoms in the component to 0.5 to 2.0 times, preferably 0.8 to 1.5 times, a good cured product can be obtained. .

  In the present invention, from the viewpoint of improving the compatibility of each component in the composition, a part or all of the component (B) and the component (C) to be used are subjected to a hydrosilylation reaction in advance, and the resulting product ( It can also be used as a curable resin composition mixed with the component (A) and the component (D).

The hydrosilylation reaction catalyst which is the component (D) in the curable resin composition of the present invention is a catalyst usually used for promoting the hydrosilylation reaction between a silicon atom bonded with a hydrogen atom and a hydrocarbon having multiple bonds. In the present invention, it is used to accelerate the hydrosilylation reaction between the ethylenically unsaturated group in component (A) and component (B) and the SiH group in component (C). Examples of the hydrosilylation reaction catalyst as component (D) include metals and metal compounds such as platinum, rhodium, palladium, ruthenium, and iridium, and it is particularly preferable to use platinum and platinum compounds. The platinum _{compounds, PtCl 4, H 2 PtCl 4} · 6H 2 O, platinum halides, such as _{Na 2 PtCl 4 · 4H 2 O} , H2PtCl 4 · 6H 2 O and the reaction products of cyclohexane, platinum-1,3 -Divinyl-1,1,3,3-tetramethyldisiloxane complex, bis- (γ-picoline) -platinum dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, And various platinum complexes such as cyclopentadiene-platinum dichloride), bis (alkynyl) bis (triphenylphosphine) platinum complex, and bis (alkynyl) (cyclooctadiene) platinum complex.

  In addition, the compounding quantity of this hydrosilylation reaction catalyst which is (D) component is 1-500 ppm with respect to the total mass of (A), (B) and (C) component as a platinum group metal normally, Especially 2-100 ppm. It is preferable to mix about. When a part or all of the components (B) and (C) are subjected to a hydrosilylation reaction in advance, the hydrosilylation reaction catalyst as the component (D) is added to the total mass of the components (B) and (C). It is preferable to add about 500 ppm, particularly about 2-100 ppm.

Moreover, in the curable resin composition of this invention, various additives can be added in the range which does not impair the effect. For example, a reaction control agent for hydrosilylation reaction to give curability and pot life, a phosphor such as YAG for white light emission, and inorganic fillers and pigments such as fine-particle silica and titanium oxide as necessary, organic filling You may mix | blend an agent, a metal filler, a flame retardant, a heat-resistant agent, an oxidation degradation agent, etc.
Curing conditions are 30 ° C. to 200 ° C., preferably 80 ° C. to 150 ° C., and cured at a temperature suitable for the type of catalyst used for 10 minutes to 300 minutes to obtain a good molded product. be able to.

When the curable resin composition of the present invention is used as an encapsulant for an opto device, the refractive index is high in order to increase the light extraction efficiency from the light emitting element as well as being transparent because of the necessity of transmitting light. It is desirable. In addition, in order to reduce deformation and distortion so that stress is not applied to the light emitting element as much as possible, it is required to have a certain degree of hardness and be resistant to impact because it needs to withstand impact. Further, as described above, weather resistance is necessary, and the light emitting portion is heated, so heat resistance is necessary. It is important that the weather resistance and heat resistance not only keep the mechanical strength but also prevent the coloring and the like from occurring because the light transmittance of the sealing material should not be inhibited. The curable resin composition of the present invention sufficiently satisfies these required characteristics, and is particularly effective as an encapsulant composition for optical devices, particularly LEDs.
The sealed optical device of the present invention is obtained by coating a light emitting element having a main light emission peak of 550 nm or less using the curable resin composition of the present invention and heat curing at a predetermined temperature.

  In this case, the light-emitting element is not particularly limited as long as the main light emission peak is 550 nm or less, and conventionally known LEDs are exemplified, and nitride LEDs such as GaN and InGaN are particularly preferable. Such LED is produced by laminating a semiconductor material on a substrate provided with a buffer layer of GaN, AlN or the like, if necessary, by various methods such as MOCVD, HDVPE, and liquid phase growth. Things. Various materials can be used as the substrate in this case, and examples thereof include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Of these, sapphire is preferably used from the viewpoint that GaN having good crystallinity can be easily formed and has high industrial utility value.

  An electrode can be formed on the LED by a conventionally known method, and the electrode on the LED is electrically connected to a lead terminal or the like by various methods. As the electrical connection member, those having good ohmic mechanical connectivity with the electrode of the light emitting element are preferable, and examples thereof include bonding wires using gold, silver, copper, platinum, aluminum, alloys thereof, and the like. Alternatively, a conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can be used. Of these, it is preferable to use an aluminum wire or a gold wire from the viewpoint of good workability.

  The lead terminal used in the present invention preferably has good adhesion to an electrical connection member such as a bonding wire, electrical conductivity, etc., and the electrical resistance of the lead terminal is preferably 300 μΩ · cm or less, more preferably Is 3 μΩ · cm or less. Examples of these lead terminal materials include iron, copper, iron-containing copper, tin-containing copper, and those plated with silver, nickel, or the like. The glossiness of these lead terminals may be adjusted as appropriate in order to obtain a good light spread.

  The sealed opto-device of the present invention, particularly the LED package, can be produced by coating the LED connected with electrodes, lead terminals, etc. with the curable resin composition of the present invention, followed by heat curing. In this case, the covering is not limited to directly sealing the LED, but includes a case where the LED is indirectly covered. Specifically, the LED may be encapsulated by various methods conventionally used directly with the curable resin composition of the present invention, and conventionally used epoxy resin, acrylic resin, urea resin, imide resin, etc. After sealing LED with resin or glass, you may coat | cover the top or circumference | surroundings with the curable resin composition of this invention. Further, after the LED is sealed with the curable resin composition of the present invention, it may be molded with a conventionally used epoxy resin, acrylic resin, urea resin, imide resin or the like. Various effects such as a lens effect can be provided by the difference in refractive index and specific gravity by the above method.

  Various methods can be applied as a sealing method. For example, the liquid curable resin composition of the present invention may be injected into a cup, cavity, package recess, or the like in which an LED is disposed on the bottom by a dispenser or other methods and cured under the above heating conditions, or in a solid state Alternatively, the curable resin composition of the present invention in a high-viscosity liquid may be flowed by heating or the like and similarly injected into a package recess or the like and further heated to be cured. The package in this case can be manufactured using various materials, and examples thereof include polycarbonate resin, polyphenylene sulfide resin, epoxy resin, acrylic resin, silicone resin, and ABS resin. In addition, a method of injecting a curable resin composition of the present invention into a mold frame in advance and immersing a lead frame or the like on which the LED is fixed and then curing the mold can be applied. A sealing layer made of the curable resin composition of the present invention may be formed and cured in the frame by injection with a dispenser, transfer molding, injection molding, or the like.

  Further, the curable resin composition of the present invention simply in a liquid or fluid state may be dropped or coated on the LED and cured. Alternatively, a sealing layer made of the curable resin composition of the present invention can be formed and cured on the LED by stencil printing, screen printing, or application through a mask. In addition, a method of fixing the curable resin composition of the present invention, which has been partially cured or cured in a plate shape or a lens shape, on the LED in advance may be used. Furthermore, it can also be used as a die bond agent for fixing the LED to a lead terminal or a package, or can be used as a passivation film on the LED.

  The shape of the covering portion is not particularly limited and can take various shapes. For example, a lens shape, a plate shape, a thin film shape, or a shape described in JP-A-6-244458, such as “the side surface of the light emitting element is cut at an acute angle from the vertical direction of the upper surface of the translucent substrate”, etc. Can be mentioned. These shapes may be formed by molding and curing the curable resin composition of the present invention, or may be formed by post-processing after curing the curable resin composition of the present invention.

  The sealed opto-device of the present invention, particularly the LED package, can be of various types, for example, any type such as a lamp type, an SMD type, and a chip type. Various types of SMD type and chip type package substrates are used, and examples thereof include epoxy resin, BT resin, and ceramic.

  The sealed opto-device of the present invention, particularly the LED package, can be used for various known applications. Specifically, for example, a backlight, illumination, sensor light source, vehicle instrument light source, signal lamp, indicator lamp, display device, planar light source, display, decoration, various lights, and the like can be given.

  The present invention will be described in more detail with reference to examples and comparative examples below, but the present invention is not limited to the following examples. In addition, the measuring method of each characteristic performed by the Example and the comparative example is shown below.

(1) Light transmittance Each curable resin composition is poured into a glass plate with a spacer having a thickness of 2 mm, and is cured by heating at 150 ° C. for 180 minutes, and then a spectrophotometer manufactured by Shimadzu Corporation The transmittance at 400 nm was measured using UV-1650PC.
(2) Illuminance retention after high-temperature energization test An initial illumination integrated value of the LED package sealed with each curable resin composition and a lighting test for 1000 hours were conducted by passing a current of 20 mA in an oven at 100 ° C. The subsequent integrated illuminance value was measured using a spectroradiometer USR-30 manufactured by USHIO INC., And the illuminance retention rate was calculated according to the following equation.
Illuminance retention rate (%) = [(integrated illuminance value after test) / (initial integrated illuminance value)] × 100
(3) Hardness The same resin plate as that for light transmittance measurement was prepared, and the hardness (Shore D) was measured with a durometer according to JIS K6253.
(4) Refractive index The same resin plate as that for light transmittance measurement was produced and measured according to JIS K7105.
(5) Weather resistance After preparing the same resin plate as that for light transmittance measurement and irradiating 365 nm (600 mW / cm ² ) of ultraviolet light for 10 hours using an Exfo ultraviolet irradiation machine Acticure 4000, at 400 nm The transmittance (%) was measured and used as an indicator of weather resistance.
(6) Heat resistance After preparing the same resin plate as that for light transmittance measurement and leaving it in an oven at 150 ° C. for 72 hours, the transmittance (%) at 400 nm was measured and used as an index of heat resistance. .

[Synthesis Example 1]
19.8 g (0.1 mol) of phenyltrimethoxysilane, 48.6 g (0.2 mol) of diphenyldimethoxysilane, 24.0 g (0.2 mol) of dimethyldimethoxysilane, 39.6 g (0.3 mol) of dimethylvinylethoxysilane and After charging 500 g of acetic acid and polymerizing at 110 ° C. for 10 hours, 500 g of toluene was added and washed 5 times with 500 ml of water to obtain a toluene solution of a polyorganosiloxane mixture.
Toluene was removed from this solution by vacuum distillation to obtain a polyorganosiloxane mixture having an average composition of the following formula corresponding to component (A). This is designated as “A-1”. The numbers on the right side of each structural unit indicate the molar ratio [Ph indicates a phenyl group].
(PhSiO _3/2 ) _0.1 , (Ph ₂ SiO _2/2 ) _0.2 , ((CH ₃ ) ₂ SiO _2/2 ) _0.2 , (CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) _0.3

[Synthesis Example 2]
49.8 g (0.3 mol) of fluorene, 200 g of methyl isobutyl ketone, 2.91 g of tetra-n-butylammonium bromide in a 1 liter four-necked flask equipped with a temperature controller, a stirring device, a cooling condenser, and a dropping funnel (9 × 10 ⁻³ mol), 0.73 g of hydroquinone, and 96 g of 50% by weight NaOH aqueous solution (NaOH purity 95% by weight, 1.14 mol) were heated to 60 ° C. with stirring to obtain a uniform solution. . To this solution, 53.5 g (0.7 mol) of allyl chloride was added dropwise over 20 minutes, and then reacted at 60 ° C. for 7 hours.
After adding 200 ml of toluene to the obtained reaction product, the solution was neutralized with 2N hydrochloric acid, washed with distilled water three times, toluene was removed under reduced pressure, and the resulting yellow liquid was used with silica gel. Purification by column chromatography gave 59 g of a colorless liquid of 9,9′-diallylfluorene. This is referred to as “B-1”.

[Synthesis Example 3]
49.8 g (0.3 mol) of fluorene, 200 g of methyl isobutyl ketone, 2.91 g of tetra-n-butylammonium bromide in a 1 liter four-necked flask equipped with a temperature controller, a stirring device, a cooling condenser, and a dropping funnel (9 × 10 ⁻³ mol), 0.73 g of hydroquinone, and 96 g of 50 wt% NaOH aqueous solution (NaOH purity mass 95%, 1.14 mol) were heated to 60 ° C. with stirring to obtain a uniform solution. . To this solution, 63.3 g (0.7 mol) of methallyl chloride was added dropwise over 20 minutes, and then reacted at 60 ° C. for 7 hours.
After adding 200 ml of toluene to the obtained reaction product, the solution was neutralized with 2N hydrochloric acid, washed with distilled water three times, toluene was removed under reduced pressure, and the resulting yellow liquid was used with silica gel. Purification by column chromatography gave 67 g of a colorless liquid of 9,9'-dimethallylfluorene. This is referred to as “B-2”.

[Synthesis Example 4]
In a 1 liter four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser, and a dropping funnel, 58.2 g (0.3 mol) of 2,7-dimethylfluorene, 200 g of methyl isobutyl ketone, tetra-n-butyl 2.91 g (9 × 10 ⁻³ mol) of ammonium bromide, 0.73 g of hydroquinone, 96 g of 50% by weight NaOH aqueous solution (NaOH purity 95% by weight, 1.14 mol) were charged and the temperature was raised to 60 ° C. while stirring. A homogeneous solution was obtained.
To this solution, 117 g (purity 91% by mass, 0.7 mol) of vinylbenzyl chloride (m- / p-isomer: 50/50% by mass mixture) was added dropwise over 20 minutes, and then reacted at 60 ° C. for 7 hours. It was. After adding 200 ml of toluene to the obtained reaction product, the solution was neutralized with 2N hydrochloric acid, washed with distilled water three times, and the toluene was removed under reduced pressure. By recrystallizing from pure toluene, 73.4 g of 9,9′-bis (vinylbenzyl) -2,7-dimethylfluorene was obtained as a white solid. This is designated as “B-3”.

[Synthesis Example 5]
In a 1 liter four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser, and a dropping funnel, 207 g (0.5 mol) of 1,6-bis (9-fluorenyl) hexane, 400 g of toluene, tetra-n-butyl 14 g of ammonium bromide and 152.5 g of vinylbenzyl chloride (m / p isomer 50/50 mass ratio mixture) (purity 91 mass%, 1.0 mol) were charged, and the temperature was raised to 40 ° C. with stirring to be uniform. Into solution. To this was added 80 g of 50% by weight NaOH aqueous solution (NaOH, 2 mol) and then reacted at 70 ° C. for 8 hours.
Next, the flask contents were neutralized with 2N hydrochloric acid, washed twice with distilled water, toluene was distilled off under reduced pressure, and the resulting orange viscous liquid was purified by column chromatography using silica gel. , 6-Bis (9-fluorenyl) hexane is substituted with two vinylbenzyl groups at the 9′-position of the fluorene moiety [bis (vinyl) in which R ^{1 in} formula [1] is — (CH ₂ ) ₆ —, n = 1 Benzyl) compound] was obtained. This is designated as “B-4”.

Example 1
60 parts by mass of “B-1” and 100 parts by mass of polyphenyl (dimethylsiloxy) siloxane (number average molecular weight 1000) represented by the following formula [4] are added to 100 parts by mass of “A-1”, and this mixture is added. Then, 100 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added as a catalyst, and the mixture was thoroughly stirred and defoamed.
Next, when this resin composition is potted on a stem mounted with an LED chip having a peak wavelength of 465 nm and cured by heating at 150 ° C. for 180 minutes, a transparent LED package free from tacks and cracks is obtained in the sealed portion. It was. The illuminance when a current of 20 mA was passed through the LED package was measured. Moreover, the said composition was poured between the glass plates which pinched | interposed the spacer of thickness 2mm, and it hardened | cured on the same conditions and obtained the resin plate. The transmittance of this resin plate at 400 nm was measured. The measurement results are shown in Table 1.

(Example 2)
100 parts by mass of a commercially available vinyldimethylsiloxy-terminated polydimethylsiloxane (number average molecular weight 770) represented by the following formula [5]: 140 parts by mass of “B-2”, commercially available 1,3,5,7-tetramethylcyclotetra 90 parts by mass of siloxane was added, 100 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added as a catalyst to this mixture, and the mixture was thoroughly stirred and defoamed.
About this composition, the LED package and hardened | cured material were produced by the method similar to Example 1, and the measurement was performed.

(Example 3)
Commercially available vinyldimethylsiloxy-terminated polydimethylsiloxane diphenylsiloxane copolymer represented by the following formula [6] (number average molecular weight 9500, n: m (molar ratio) = 6: 1) is 80 parts by mass and “B-2” is 140 parts by mass. , 80 parts by mass of commercially available 1,3,5,7-tetramethylcyclotetrasiloxane was added, and 100 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added to the mixture as a catalyst. In addition, the mixture was thoroughly stirred and degassed.
About this composition, the LED package and hardened | cured material were produced by the method similar to Example 1, and the measurement was performed.

Example 4
200 parts by mass of toluene, 15 parts by mass of “B-3”, 40 parts by mass of commercially available 1,3,5,7-tetramethylcyclotetrasiloxane, platinum-1,3-divinyl-1,1,3,3-tetra After dissolving 30 ppm of methyldisiloxane complex and stirring at 60 ° C. for 3 hours, 100 parts by mass of “A-1” was obtained as a total amount of the liquid compound obtained by carrying out a hydrosilylation reaction beforehand obtained by removing toluene under reduced pressure. In addition, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added to a concentration of 50 ppm, and the mixture was thoroughly stirred and defoamed.
About this composition, the LED package and hardened | cured material were produced by the method similar to Example 1, and the measurement was performed.

(Example 5)
200 parts by mass of toluene, 50 parts by mass of “B-4”, 100 parts by mass of commercially available polyphenyl (dimethylsiloxy) siloxane (number average molecular weight 1000) represented by the above formula [4], platinum-1,3-divinyl- The total amount of the liquid compound subjected to the hydrosilylation reaction previously obtained by dissolving 30 ppm of 1,1,3,3-tetramethyldisiloxane complex and stirring at 60 ° C. for 3 hours and then removing toluene under reduced pressure In addition to 100 parts by mass of the terminal vinyl polydimethylsiloxane (number average molecular weight 770) represented by [5], 50 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex may be added. The mixture was stirred and degassed. About this composition, the LED package and hardened | cured material were produced by the method similar to Example 1, and the measurement was performed.

(Comparative Example 1)
50 parts by mass of a commercially available polyphenyl (dimethylsiloxy) siloxane (number average molecular weight 1000) represented by the above formula [4] is added to 100 parts by mass of “A-1”, and platinum-1,3- 100 ppm of divinyl-1,1,3,3-tetramethyldisiloxane complex was added, and the mixture was thoroughly stirred and defoamed.
About this composition, the LED package and hardened | cured material were produced by the method similar to Example 1, and the measurement was performed.

(Comparative Example 2)
40 parts by mass of triallyl isocyanurate and 140 parts by mass of polyphenyl (dimethylsiloxy) siloxane (number average molecular weight 1000) represented by the above formula [4] are added to 100 parts by mass of “A-1”. 100 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added as a catalyst, and the mixture was thoroughly stirred and defoamed.
About this composition, the LED package and hardened | cured material were produced by the method similar to Example 1, and the measurement was performed.

(Comparative Example 3)
50 parts by mass of polyphenyl (dimethylsiloxy) siloxane represented by the formula [4], which is commercially available as an organohydrogenpolysiloxane, is added to 100 parts by mass of the terminal vinyl polydimethylsiloxane (number average molecular weight 770) represented by the above formula [5]. In addition, 100 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added to the mixture as a catalyst, and the mixture was thoroughly stirred and defoamed.
About this composition, the LED package and hardened | cured material were produced by the method similar to Example 1, and the measurement was performed. The LED package had a soft sealing part, had a slight tack, and was easily scratched.

(Comparative Example 4)
Add 100 parts by mass of hydrogenated bisphenol A diglycidyl ether as an epoxy resin, 80 parts by mass of 4-methylhexahydrophthalic anhydride as an acid anhydride curing agent, and 1 part by mass of methyltributylphosphonium dimethyl phosphate as a curing accelerator and stir well. Mix and degas. About this composition, the hardened | cured material was produced by the method similar to Example 1, and it measured.

  According to Table 1 and Table 2, the cured product and LED package obtained from the curable resin composition of the present invention have improved refractive index and hardness while maintaining excellent light transmittance, weather resistance, and heat resistance. I understand that.

Claims (9)

(A) A polyorganosiloxane having two or more ethylenically unsaturated groups on average in one molecule, (B) a fluorene compound represented by the formula [1]

[Wherein, X and Y represent ethylenically unsaturated groups, which may be the same or different. R ¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, R ² represents an alkyl group or aryl group having 1 to 10 carbon atoms, a is an integer of 0 to 4, and (2 + 2n) a are It can be the same or different. n is an integer from 0 to 10],
(C) A curable resin composition comprising a polyorganohydrogenpolysiloxane having two or more hydrogen atoms bonded to a silicon atom in one molecule and (D) a hydrosilylation reaction catalyst.   2. The curable resin composition according to claim 1, wherein X and Y in the formula [1] are each at least one selected from an allyl group, a methallyl group, and a vinylbenzyl group.   The curable resin composition according to claim 1 or 2, wherein both n and a in the formula [1] are 0.   A compound obtained by subjecting a fluorene compound of component (B) and a polyorganohydrogenpolysiloxane of component (C) to a hydrosilylation reaction in advance in a mixture of component (A) and component (D). The curable resin composition according to 1.   The ratio of the (B) component with respect to the total amount of (A) component and (B) component was mix | blended so that it might become the range used as 0.1 mass%-80 mass%. Curable resin composition.   Hydrogen in which the blending amount of component (C) is directly connected to silicon atoms in component (C) with respect to the total molar amount of ethylenically unsaturated groups in component (A) and ethylenically unsaturated groups in component (B). The curable resin composition according to any one of claims 1 to 5, wherein the molar ratio of the atoms is 0.5 to 2.0.   The curable resin composition according to any one of claims 1 to 6, wherein the hydrosilylation reaction catalyst (D) is a platinum group metal catalyst.   Curable resin composition in any one of Claims 1-7 used for opto device sealing.   An opto-device sealed with the curable resin composition according to claim 1.