TW201247785A - Curable composition, cured article, optical semiconductor device and polysiloxane - Google Patents

Abstract

A curable composition, which is containing: polysiloxane (A) having alkenyl group and adhesive group, polysiloxane (B) having per molecule at least two hydrogen atom that is combined with silicon atom (but polysiloxane (A)), and catalyst (C) for the hydrosilylation reaction. It is characterized by the content ratio of polysiloxane (A) is 40 to 90 mass% when total content of all ingredients of the curable composition is 100 mass%. The curable composition of the present invention is capable of forming a hydrosilyl series polysiloxane composition which is having both high adhesiveness for substrates or metal lines, and high Initial luminance of LED etc. Therefore, an optical semiconductor device which is obtained by covering the semiconductor light-emitting element by the cured article obtained from the curable composition, the initial luminance is high, even in the case of undergoing heat cycle, the cured article is having high adhesiveness and could not separate of package and the like.

Description

201247785 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a curable composition, a cured product, an optical semiconductor device, and a polyoxyalkylene. [Prior Art] A polyoxane composition (hereinafter also referred to as a ydrosilyl polyoxane composition) used in a sealant for a semiconductor light-emitting device (LED) or the like is used. A technique for improving the adhesion to a package or the like. As a technique for improving the adhesion of a composition of a hydroxane-based polyoxane, a technique of adding an adhesion promoter such as an epoxy group-containing polyoxyalkylene to a hydroquinone-based polyoxane composition is known. Patent Document 1 describes a hydroquinane-based polyoxoxane composition containing 0.01 to 50 parts by weight of an alkenyl group as an adhesion promoter with respect to 1 part by weight of the organopolysiloxane as a main component. The epoxy-containing profit-seeking document 2 describes that it is contained in an organic two-part by weight of an alkenyl group and a phenyl group as a main component. .01~2. The weight fraction is promoted as adhesion: 3 per sulphate of the sulphate. Patent Document 3 describes a composition of a (4) polyoxygen-oxygen-fired composition, which contains 0.01 to 10 parts by mass of the organic polyfluorene-containing mass fraction containing an alkenyl group as a main component. The epoxy group-containing concentration. In the case of the one of the above-mentioned accelerators, the Japanese Patent Publication No. 200747785 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-3008 No. JP-A-2002-229402 DISCLOSURE OF THE INVENTION [Problem to be Solved by the Invention] In order to improve the adhesion between a substrate, a metal wiring and a sealant, it is necessary to add an epoxy group-containing polyoxane as an adhesion promoter. The epoxy group content. However, in the case where a large amount of such an adhesion promoter is used, there is a fear that the brightness is lowered. An object of the present invention is to provide a curable composition which is a composition of a hydrogen hydride-based polyoxan 6 composition and which can form a cured product which can achieve adhesion and brightness to a substrate or a metal wiring. [Means for Solving the Problem] The invention is a curable composition which is a poly(A) containing polyalkenyl group and an intimate group, and having at least two hydrogen atoms bonded to the atom: The curable composition of the oxime (B) (except for polyoxane (VIII)) and the catalyst for hydrogenation of hydrazine (C) is obtained by combining the contents of all the components contained in the curable composition; The content ratio of the polysulfate (A) is 40 to 90% by mass. Part 31=Sclerosing composition, when the content of the di-holoyl group contained in the Juxixi Hospital (8) is 3 〇 〇 莫 〇〇 〇〇 〇〇 ' ' ' ' ' ' ' ' ' ' ' ' ' ' Moer%. The content of the adhesion group is preferably 4. 〇1 to 1 〇 In the above curable composition, the above-mentioned adhesion group is preferably a group having an epoxy group of 201247785. In the curable composition, the polyoxyalkylene (a) is preferably represented by the following chemical formula:

^R^Vi〇l2V〇(R^a nl3Si〇1/2) b (RViRlsi〇^ c (RK o 1/2* S i〇2/2) d (R 2sl〇2/2) e (RlSi〇 3/2) f (Si〇4/2) h (x (wherein R represents a group having a weak group. REp represents a group having an epoxy group. R1 each independently represents a hydrocarbon group of Jia (but has X is a group of an alkenyl group. X represents a hydrogen atom or a group of carbon atoms. a represents an integer above 〇, b represents an integer of 0 or more, and represents an integer of 0 or more, and d represents an integer of 1 or ^. , e represents an integer of 0 or more, f represents (4) the upper (four) number, and the h table is not started with 0 or more. ΐ志々n·,,, the integer above the integer”, and the heart is working and the composition is changed. In the middle, the oxy-fired (4) has an aryl group, and the number of all the S1 atoms contained in the bismuth (4) is 1. The molar content of the aryl group contained in the polysulfide (4) is preferably _ = The other invention is a hardened material characterized by a chemical composition obtained. The hardened semiconductor has a body ==. The seeded semiconductor device is characterized by a cured product, and the aforementioned formula covering the semiconductor light-emitting element. Table ^ Bu 'other inventions are - a kind of Ju Shi Xi Xing The following chemical U i /2 e (R Sl〇3々)f (Si〇4/2) h (χ 201247785 (wherein Rvi represents a group having an alkenyl group. REp represents a group having an epoxy group) R1 each independently represents a monovalent hydrocarbon group (except for a group having an alkenyl group). X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. a represents an integer of 〇 or more, and b represents an integer of 0 or more. c represents an integer of 0 or more, d represents an integer of 1 or more, e represents an integer of 〇 or more, f represents an integer of 〇 or more, and h represents an integer of 0 or more. i represents an integer of 0 or more. And & + (: [Effect of the invention] The curable composition of the present invention is a hydroquinane-based polyoxane composition, which can form a cured product which can achieve adhesion to a substrate or a metal wiring or the like. Therefore, the optical semiconductor device obtained by covering the semiconductor light-emitting device with the cured product obtained from the curable composition is an optical semiconductor device having excellent reliability. [Embodiment] [Form of the invention] <Surability composition > The curable composition of the present invention which contains an olefin And a polyoxyalkylene (A) having an adhesion group, a polyoxyalkylene (B) having at least two hydrogen atoms bonded to a halogen atom per molecule (except for polyoxyalkylene (A)), and The curable composition of the catalyst for hydrogenation reaction (C), characterized in that the total content of all the components contained in the curable composition is i 〇〇 mass / 〇 守 ,, poly siloxane (A) The content ratio is 4 〇 to 9 〇 mass%. In the present invention, "polyoxane" means a shixi oxygen institute having a molecular skeleton in which two or more oxysomies (Si(D) are combined. . 201247785 [Polyoxane (A)] Polyoxyalkylene (A) is a polyoxyalkylene having an alkenyl group and an adhesion group. The polyoxyalkylene (A) is a main component of the composition, and is hardened by the hydrogenation reaction with polyhydrazine (B) to become a main body of the cured product. In addition, since the polyoxet (4) has an adhesive group, it also has a function of improving the adhesion of the cured product to the L E D package. Examples of the dilute group which the oxygen-containing oxygen (A) has include an ethylene group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentyl group, a heptenyl group, and a diene group. Cyclohexenyl and the like. Vinyl, allyl and hexyl. The content of the alkenyl group in the hydrous alkane (A) is preferably 3 to 5 moles per mole of the total number of si atoms contained in the polyoxyalkylene. a more preferably 5 to 4 〇 mole % ‘more preferably 1 〇 3 〇 耳 %. When the content of the baked base is within the above range, the polyoxetane (VIII) reacts with the Shixia hydrogen 2 of the polyoxin (8) to induce a hardened product having a high strength. The term "adhesive group" as used herein refers to a metal or an organic resin which is a material such as a semiconductor device or the like and has an adhesive group. Examples of the adhesion group which the polysulfide compound (4) has include a group having an epoxy group, a sulfinyl group, an isocyanate group, a triallyl group or an ester group. n, etc., it is difficult to prevent the nightmization reaction caused by the hardening of the curable composition, and it is preferable to take care of the adhesion and brightness of the substrate, metal, etc. The group having an epoxy group is a group having an epoxy group, and examples thereof include a glycidyl group such as propylene oxide 201247785 oxy group and 3-glycidoxypropyl group, and 3,4_epoxycyclopentyl, 3,4·epoxycyclohexyl, 2-(3,4-epoxycyclopentyl)ethyl, and 2-(3,4-epoxycyclohexyl)ethyl Oxycycloalkyl and the like. Specific examples of the group having an epoxy group include a group represented by the following structural formulae (丨) to (4). When the group having an epoxy group is such a group, a millimeter scale can be achieved. Forming hardened material.

[In the structural formula (1), R2 represents a methylene group or a divalent carbon group having 2 to 1 ring carbon atoms or a branched chain extending group having 3 to 10 carbon atoms. ] ~R3—CH—CH2

[In the formula (2), R3 represents a methylene group or a divalent linear alkyl group having 2 to 1 ring carbon atoms or a branched alkyl group having 3 to 1 ring carbon atoms. ] R4 ——Ο-CH2—· CH — CH, V (3)

[In the formula (3), R4 represents a methylene group or a divalent linear alkyl group having 2 to 1 ring carbon atoms or a branched alkyl group having 3 to 1 ring carbon atoms. [In the structural formula (4), R5 represents a methylene group or a divalent carbon group having 2 to 1 ring carbon atoms or a branched alkyl group having 3 to 1 ring carbon atoms. Specific examples of the group represented by the structural formula (1) include 2-(3,4-epoxycyclohexyl)ethyl and the like. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Wait. Specific examples of the group represented by the structural formula (4) include 2 phenylmethyl-3,4-epoxycyclohexyl)ethyl and the like. It is preferable that the content of the adhesion group in the polysulfide (4) is 1% by mole based on the number of all the Si atoms contained in the polysulfide oxide, and is preferably Η) mol%. More preferably 〇〇 5~5 mo. The heart is further better for 〇 ~ Moer%. When the content of the adhesion group is within the above range, a cured film having high adhesion between the cured product obtained from the composition and the coffee package and the like, and a high degree of twist can be obtained. The sclerosing property of the present invention, and the content of all the components contained in the composition of the polyoxyalkylene (A) contained in the raw material. When the total amount is 100% by mass, it is 40 to 90% by mass, preferably 5 to 85% by mass, and 65 to 85 by mass. /〇. In the conventional hydrogen consumption polyoxomorphous composition, in order to improve the viscosity: in addition to the polyoxalate as the main agent, the addition is relative to the composition of the whole 0.01~2〇Zeng Jinyu/〇/· 1 The epoxy group-containing dioxane as an adhesion promoter. On the other hand, in the curable composition of the present invention, the polyoxyl group of the oxy group is the main agent, and the content thereof is: = that is the content of the bucket 9 ft% m (4) is the aforementioned two The cured product obtained from the composition has high adhesion to the substrate or the metal, and maintains the high initial brightness of the LED or the like under the barrier of use as a sealing material such as (4). • 10-201247785 and another -1 main polyoxane (A) preferably has an aryl group. The polyoxyalkylene (A) two-day soil ' ’ exhibits a characteristic of 1 degree when used as an LED sealing material. The content of the aryl group contained in the polyoxyalkylene (A) of all the Si atoms contained in the polysulfide (4) is more than '·'·^20 moles/〇, more preferably 50~ 110% by mole, further better:::% by mole. The content of the aryl group is 3. ~12. In the range of % of moles, ... a cured film having a high degree of redundancy and a high refractive index. The description of the base group can be exemplified by a phenyl group, a tolyl group, a xylyl group, a decyl group or the like (4), which is determined by gel permeation chromatography. The average molecular weight of the heavy ruthenium is preferably 100~. The range of 50000 is better in the range of 500~5000. If the cumulative average molecular weight of the gas, +, Ρ 士 士 士 士 士 士 士 士 士 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ^ The material strength and characteristics of the sealing material. Examples of the polyoxyalkylene (A) include the following polyoxane: [Chemical Formula (1)] (RR^SiOj/a) 4 (R^SiO) fRv 1 R1 表: · d (Rl2Si〇2/) (rxV/o ^ S/〇2/2) ° (RA B (si〇4/2) h (x〇1/2) ( 2丄(R Sl〇3/2 a Si 〇 3 / 2) (wherein Rv · represents a group having a base group of an alkenyl group. (except for a divalent group independently represented by a valence). X represents a hydrogen atom or a carbon atom of ι to earth. The integer above 〇, the integer above 〇, and the c table. The number of a, ά represents the integer above * * _ The integer integer on ι is not an integer greater than G, and f is 〇 11-201247785 An integer, g represents an integer greater than 〇, h represents an integer greater than 。, i represents an integer greater than 。, and & + 〇 is an integer greater than i. An integer greater than i). With respect to the total of a, b, c, d, e, f, g, h, and yttrium, the ratio of a is preferably 〇% or more and 〇% or less, more preferably 5, when the total amount is 100%. /. Above 40%. The ratio of b is preferably 〇% or more and 5% or less, more preferably 0% or more and 20% or less. The ratio of c is preferably 〇% or more and 3% or less, more preferably 0% or more and 20% or less. The ratio of d is preferably 〇% or more and 1% or less, more preferably 0% or more and 5% or less. The ratio of e is preferably 〇% or more and 5% or less, more preferably 0% or more and 30% or less. The ratio of f is preferably 2% or more and 9% or less, more preferably 40% or more and 80% or less. The ratio of g is preferably 〇% or more and 10% or less, more preferably 〇% or more and 5% or less. The ratio of h is preferably 〇% or more and 50% or less, more preferably 〇% or more and 3 ()% or less. The ratio of i is preferably 〇% or more and 1% or less, more preferably 〇% or more and 5% or less. The ratio of greater than 0% ’ d +g is greater than 〇 〇/〇. In the polyoxanthene gas which is represented by the chemical formula (1), a cured material which can adhere to a high degree of adhesion to a substrate, a metal wiring or the like, and a cured product having a high degree of compatibility with a polysiloxane obtained by the following chemical formula (2) is formed. Preferably. [Chemical Formula (2)]

ρΒ^Ίΐ2ν〇Λ2) a (R, S i〇1/2) b (RViRlS i〇2/2) “RK

L〇2/2) d (R 2S 1〇2/2) e (R^si〇3/2) f (S i04/2) h (X i (wherein RVi represents a group having an alkenyl group). rEp represents a group having an epoxy group. R1 each independently represents "hydrocarbyl group of Jal (except for a group having an alkenyl group). X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. An integer, b represents an integer of 0 or more, c represents an integer greater than 〇, and d -12- 201247785 represents an integer of 1 or more. The raw _ * _ number table is not an integer greater than 0, and f represents 0. h represents a positive number on the 敕 above 〇. 丄 represents an integer of 0 or more. The above integers and a+c are 1 as a group having an alkenyl group, and the same group as the above group is exemplified. + ^ The group of the fluorenyl group is a group having an adhesion group, and is in close contact with the above, and a group having the same group as the octagenous group. For example, 盥μ, +. scoop has a group of the same group having an epoxy group as k-oxygen. As a monovalent hydrocarbon group, the "base group of propyl group, propyl group, butyl group, Pentyl "heptyl 4 alkyl; phenyl , tolyl, diphenyl, quinone and other aryl groups; benzyl, lean natrile aralkyl; gas methyl, 3-vapor propyl, ,, -difluoropropyl, nonafluorobutyl The alkyl group is substituted with an alkyl group. Examples of the method for producing the polyoxyalkylene (4) include exemplified by the Japanese Patent Publication No. 2, pp. (10) 008996, the Japanese Patent Publication No. 2〇〇71〇6798, and the Japanese Special Open 2GG7. No. 169427 and Japanese Patent Laid-Open No. 2(4)(4): A method known as a report, for example, a method of co-hydrolysis of each unit source, Tiger = Shi Xi, and calcined milk, and the co-hydrolyzate is balanced by the metal catalyst 4. Method for the reaction, etc. By using such poly 7 Oxygen, the hardened material obtained from the curable composition name of the present invention can be obtained.

Rt ^ also pays for strength, and exhibits the in-and-contact properties of the metal or organic tree tantalum film, and also the gauge too & τ ρ π _ . The clothing is now used as an LED sealing material to obtain high brightness characteristics.

[Polyoxane (B) J Baju Shixi Oxygen Institute (8) is for every! The molecule has at least two polydecane oximes which are hydrogen atoms at the junction of the Shixi atom, except for the oxime (A). That is, polyoxyl -13 - .201247785 alkane (B) has at least two SiH groups (hydroalkylene groups) per one knives. The polyoxyalkylene (B) is a crosslinker for the polyoxyalkylene (A) which is formed by a hydrogenation reaction with a polyoxane (A). As the polyoxyalkylene (B)', if the conventional hydrooxane-based polyoxane composition is used as a crosslinking agent, the oxy-anthracene having at least two hydrogen atoms bonded to the ruthenium atom per ruthenium molecule is used. The polyoxyalkylene (B) such as an organic hydrogenated polyoxo-oxygenate having a concentration of 5 or less may be used without particular limitation, for example, a phenyltrimethoxy group can be obtained by a known method. It is obtained by reacting an alkoxydecane such as a decane or a diphenyldimethoxy decane with a hydrogenated siloxane such as m3·tetramethylmonooxane. The content of the polyoxyalkylene (b) in the curable composition of the present invention is preferably 2 for the amount of the weak base in the oxygen-burning (eight), and (4) the molar amount of the atomic hydrogen atom in the oxygen (b). For the amount of 〇1~5, the better (8) of the Γ step is better than 〇.7~" the amount. If the geisha oxygen is burned in the other area? The hardening of the composition is fully carried out, The cured product of the member can obtain sufficient heat resistance. [矽 Catalyst for Hydrogenation Reaction (C)] The catalyst for the deuteration reaction (c) is a catalyst for the reaction of the polyoxygen (8). The atmosphere is said to be (4) and the dream As a catalyst for the hydrogenation reaction of the Shixi hydrogenation, the compound is used in the conventional hydroquinane, and the composition is used as a catalyst for the hydrogenation reaction, and can be used without particular limitation. Catalyst used for the ruthenium As a specific example of the catalyst (c) for the hydrogenation reaction, the catalyst of the ruthenium-14-201247785, the ruthenium-based catalyst, the palladium-based catalyst, and the Cuihua agent can be mentioned. From the viewpoint of promoting the hardening of the present composition, it is preferred that these are platinum-based catalysts. Examples of the platinum rhodium catalyst include a platinum-alkenyl oxygen tiger complex and the like. Examples of the dilute helioxane include 1,3-diethylene, 1 u-group-1,1,3,3-tetramethyldioxane, and 1,3,5,7-tetramethyl_1. , 3,5 7_ Ethyl group% four stone oxime and so on. In particular, from the viewpoint of the stability of the complex, it is preferably 1,1% divinyl-1,1,3,3-tetradecyl oxazepine. In the curable composition of the present invention, the catalyst for the deuteration reaction of the initial T (C) is used to hydrogenate the polyfluorene oxide (A) with polyfluorene chloride (H) and oxygen (B). The amount actually carried out. The curable composition of the present invention is not limited to the object of the present invention, and may contain, in addition to the above-mentioned components, particulate fine particles such as gas phase ceria or quartz powder, and inorganic materials such as titanium oxide and zinc oxide. a retarder; a retarder such as cyclo-tetradecyltetravinyltetraoxane; diphenyl bis(dimethylvinyl nonyloxy) decane, phenyl tris(dimethylvinyl decyloxy) decane Such as diluent; pigment; flame retardant; heat;; antioxidants. The curable composition of the present invention can be prepared by uniformly mixing the above components by a known method such as a mixer. The viscosity at 25 〇c of the curable composition of the present invention is preferably from 100 to 100 mPa s ' more preferably from 1 〇 to 1 〇〇〇〇 mpa s. When the viscosity is within this range, the operability of the composition is improved. The curable composition of the present invention can be prepared as a single agent or as a double agent, and can be used in combination with two agents. A hardening inhibitor such as acetylene alcohol may also be added in small amounts as needed. -15-201247785 <cured material> A cured product can be obtained by hardening the curable composition of the present invention. The semiconductor element is sealed and hardened by the curable composition of the present invention, and a cured product of the sealing material can be obtained. The method of curing the curable composition of the present invention may, for example, be a method in which the curable composition is applied to a substrate and then heated at 1 to 18 Torr for 1 to 13 hours. As described above, the hardened material obtained by curing the curable composition of the present invention has high adhesion to a substrate or a metal wiring, and the like, and high initial brightness of led or the like is achieved. <Optical semiconductor device> The optical semiconductor device of the present invention has a semiconductor light-emitting device and the cured product covering the semiconductor light-emitting device. The optical semiconductor device of the present invention is obtained by coating the curable composition on a semiconductor light-emitting device and curing the tantalum composition. The method of hardening the curable composition is as described above. LED (Liglu Emiuing) can be cited as an optical semiconductor device

Diode, light-emitting diode, LD (: Laser Diode), etc. Fig. 1 is a schematic view showing a specific example of the optical semiconductor device of the present invention. The optical semiconductor device 1 includes an electrode 6, a semiconductor light-emitting element 2 that is electrically connected to the electrode 6 and is electrically connected to the electrode 6 by a wire 7, and a reflector 3 that is disposed to house the semiconductor light-emitting device 2, and is filled in the reflector. 3 is a sealing material 4 that seals the semiconductor light emitting element 2. The sealing material 4 is obtained by hardening the curable composition of the present invention. Dispersion in the sealing material 4 -16- 201247785 There are particles 5 such as Shishi stone, phosphor or the like. As described above, the sealing material obtained by curing the curable composition of the present invention has a strong adhesion to the organic resin film of the material of the reflector or the metal of the electrode material, and is sealed even in the case of thermal cycling. The material will also not peel off from the LED package. Further, the sealing material maintains a high initial luminance of the LED or the like. That is, it can achieve both high adhesion and high initial brightness.

[Examples] (1) Synthesis of polyoxoxime (1-1) Synthesis of polyoxyalkylene [Synthesis Example 1] Synthesis of polyoxyalkylene (AR1) with a stirrer, reflux condenser, and inlet Into a four-necked flask of a thermometer, 82 g of 1,3-divinyl-m3-tetradecyldioxane, 525 g of phenyltrimethoxydecane, 143 g of water, 4 g of trifluorosulfonium sulfonate, and hydrazine were placed and mixed. Benzene 500 g, heated to reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer of the benzene solution was washed with water. To the toluene solution layer after washing with water, 0.4 g of potassium hydroxide was added, and the water was refluxed while removing water from the water separation tube. After the removal of water was completed, it was concentrated to a solid concentration of 75 mass%, and refluxed for another 5 hours. After cooling, the mixture was neutralized with 6 g of cerium acetate, and the benzene solution obtained by filtration was washed with water. Thereafter, concentration under reduced pressure was carried out to obtain polyoxyalkylene (AR1). The polystyrene-equivalent weight average molecular weight '(AR" was determined by gel permeation chromatography to be 2 〇〇〇. The chemical formula of polyoxyalkylene (AR1) was (ViMe2SiO丨/2) 25 (phSi〇3/2) 75 (Vi represents ethyl group, Me represents fluorenyl group, Ph represents phenyl group. The subscript number indicates mop/〇). [Synthesis Example 2] Synthesis of polyoxane (A1) -17-.201247785 , a reflux flask, an inlet, a thermometer, and a four-necked flask were charged and mixed with 1,3-divinyl_ι, ι, 3,3-tetramethyldioxane 82g, water I43g, stupid trimethoxy 521 g of decane, 〇.4 g of trifluorosulfonium sulfonate and 510 g of hydrazine were heated and refluxed for 1 hour. After cooling, the lower layer of 'the upper layer of the benzene solution was washed and washed. The layer of benzene solution after washing with water was added. 4 g of 3-glycidoxypropyl decyl decyloxydecane and 0.5 g of potassium hydroxide and heated to reflux for an hour. Then, the sterol was distilled off, and excess water was removed by azeotropic dehydration. After the reaction, the toluene/gluten solution is cooled, and neutralized with 〇. 6 g of acetic acid and washed with water. After removing the water, the benzene is distilled off under reduced pressure. The polyfluorene having an alkenyl group of 2 5 m 〇/〇 and an epoxy group 〇 5 mol % (the number of all the 丨 atoms contained in the polyoxoxime is 100 mol%) is obtained. Oxystane (A1). The polystyrene-equivalent weight average molecular weight of (A1) was determined by gel permeation chromatography, and the chemical formula of 2〇〇〇^ polyoxane (A1) was (ViMe2Si〇i/2). 25(phSi〇3/2)74 5 (EpMeSiOwV5 (Vi represents a vinyl group, ]^ represents a fluorenyl group, ph represents a phenyl group, and Ep represents a glycidoxypropyl group. The subscript number indicates a polyfluorene oxide ( When the number of atoms contained in A1) is ^(10) mol%, the content ratio of the alkenyl group is 25 m〇l%, and the content ratio of the epoxy group is 〇, 5 m〇1/°, and the content ratio of the aryl group 74.5 mol%. [Synthesis Example 3] Synthesis of polyoxane (A2) was carried out and mixed in a four-necked flask equipped with a stirrer, a home &# @ λ ^ μ machine condenser, an inlet, and a thermometer. 3,3-vinyl-1,1,3,3-tetradecyldioxane 82 g, phenyl trioxane 958 g of sulphonyl sulphate, 143 g of water, yttrium trifluorosulfonate. 4 g and hydrazine Benzene 500g, add the door, the gentleman..., back to 1 hour. Cold But then 'separate and remove the lower layer

' Washed the upper layer of A stupid + P 4 liquid layer. To the layer of the benzene solution after washing with water was added -18-'201247785 into 3 g of 3-glycidoxypropylmethyl decyloxy decane and 0.5 g of potassium hydroxide and heated under reflux for 1 hour. The methanol is then distilled off to dehydrate the excess water. It was then heated to reflux for 4 hours. After the reaction, the toluene solution was cooled, neutralized with acetic acid 0 _ 6 g, and washed with water. After removing water, the toluene was distilled off under reduced pressure to obtain a molar ratio of 25 mol% of an alkenyl group and 1 mol% of an epoxy group (in the case of poly; 100 mole % of polyoxyalkylene (A2). The weight average molecular weight of the polyethylidene of (A2) was measured by gel permeation chromatography to be 2 〇〇〇. The chemical formula of polyoxic (A2) is (ViMe2Si〇i/2h5 (phSi〇3/2h4 (EpMeSiOw), (Vi stands for vinyl, Me stands for sulfhydryl, ph stands for stupid, Ep stands for glycidoxy) Propyl. The subscript number indicates m〇丨..). When the number of all Si atoms contained in the polyoxan (A2) is 1% mol%, the content of the alkenyl group is 25 mol%. The content ratio of the epoxy group is lm 〇 1% 'the content ratio of the aryl group is 7 4 m ο 1 %. [Synthesis Example 4] Synthesis of polyoxy siloxane (A3) with a stirrer, a reflux condenser, and an input a four-necked flask of a mouth and a thermometer was charged and mixed with 1,3 -diethyl _ 1,1,3,3 -tetramethyl oxazepine 82 g, stupid dimethoxy decane 5 lig, water i 43 g, 4 g of trifluorosulfonium sulfonate and 500 g of toluene were heated under reflux for 1 hour. After cooling, the lower layer of the toluene solution of the upper layer was washed and removed. 3-glycidoxypropyl group was added to the layer of the benzene solution after washing. 16 g of decyloxydecane and 3 g of potassium hydroxide and 0.5 g of potassium hydroxide were heated under reflux for 1 hour. Then, the sterol was distilled off to remove the straight water by co-dehydration. Discharge for 4 hours. After the anti-corrosion toluene solution was cooled, it was neutralized with 〇6 g of acetic acid and washed with water. After removing the water, the carbendazole was removed under reduced pressure; the atrophy was obtained to obtain an alkenyl group of 2 5 m. -19- 201247785 /〇 and 裒oxy 2mol% (polyoxane (A3) in the number of all si atoms contained in the polyoxoxime). Gel permeation layer The polystyrene-equivalent weight average molecular weight of (A3) was determined by the analytical method, and the chemical formula of polyoxyalkylene (A3) was (ViMe2Si01/2)25(PhSi〇3/2)73 (EpMeSi02/2 2 (Vi represents vinyl, Me represents methyl, ph represents phenyl, EP represents glycidoxypropyl. The subscript number indicates mol%). All Si contained in polyoxyalkylene (A3) When the number of atoms is 1 〇〇 mol %, the content ratio of the alkenyl group is 25 mol 〇 /, and the content ratio of the epoxy group is 2 m 〇 1% 'the content ratio of the aryl group is 73 mol / 〇. [Synthesis Example 5 Synthesis of Polyoxane (A4) In a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, 1,3-divinyltetramethyldioxane 49g and phenyldiene were charged and mixed. 442 g of oxydecane, 85 g of dimethyldimethoxydecane, 143 g of water, 〇4 g of difluoromethane phthalate, and 5 g of fluorene benzene were heated under reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer was washed with water. Toluene solution layer. 3 g of glycidoxypropyl decyl dimethoxy decane and 5 g of potassium hydroxide were added to the toluene solution layer after washing with water and heated under reflux for 1 hour. Steaming removes 'to remove excess water by dehydration. It was then heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with cerium acetate & and washed with water. After removing the water, the toluene was distilled off under reduced pressure to concentrate to obtain an alkenyl group of 15 mol% and an epoxy group! Mole % (a total of i 00 mol% of the total amount of Si atoms contained in the polychalcoxime) is a polyoxymethane (A4). The polystyrene-equivalent weight average molecular weight ' of (A4) was determined by gel permeation chromatography to be 1800. The chemical formula of polyoxyalkylene (A4) is (ViMe2Si01/2)15(PhSi〇3/2)64(Me2Si02/2)2〇(EpMeSi〇2/2)] -20- 201247785 (Vi represents vinyl, Me Indicates a fluorenyl group, Ph represents a phenyl group, and Ep represents a glycidoxypropyl group. The subscript number indicates mol %). When the number of all Si atoms contained in the polyoxin (A4) is 100 mol%, the content of the dilute base is 15 mol%, and the content of the epoxy group is im〇l%, and the content of the aryl group The ratio is 64 mol%. [Synthesis Example 6] Synthesis of polyoxyalkylene (A5) In a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, 1,3-divinyl-l,l,3,3 was charged and mixed. - tetramethyl oxazepine 82 g, phenyl trimethoxy decane 525 g, water 143 g, trifluoroantimony ruthenium 4 g, and toluene 50,000 g were heated under reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer of the benzene solution was washed with water. To the layer of the benzene solution after washing with water, 3-1⁄4 of oxypropyloxypropylmethyl-methoxy-methoxy 314 g and 130 g of water and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Next, the sterol is distilled off to remove excess water by azeotropic dehydration. It was then heated to reflux for 4 hours. The reacted solution of the solution was neutralized with 0.6 g of acetic acid and washed with water after cooling. After removing water, 'the benzene was distilled off and concentrated under reduced pressure to obtain 25 mol% of a rare base and 40 mol% of an epoxy group (the number of all Si atoms contained in the polyoxyalkylene was 1〇〇) Mole %) of polyoxyalkylene (A5). The polystyrene-equivalent weight average molecular weight of (A5) was measured by gel permeation chromatography to be 1600. The chemical formula of polyoxyalkylene (A5) is (ViMe2Si〇i/2)25 (PhSiO3/2)75(EpMeSiO2/2)40 (Vi represents vinyl, Me represents fluorenyl, Ph represents phenyl, Ep represents epoxy Propoxypropyl. The subscript number indicates mol%). When the number of all Si atoms contained in the polyoxyalkylene (A5) is 1 〇〇 mol%, the content ratio of the 'alkenyl group is 25 πιο1%, and the content ratio of the epoxy group is 40 mol%'. It is 75rnol%. -21 - 201247785 [Synthesis Example 7] Synthesis of polyoxane (A6) In a four-necked flask equipped with a mixer, a reflux condenser, an inlet, and a thermometer, 丨, 3_divinyl--four 33 g of methyl dioxoxime, 442 g of phenyltrimethoxydecane, 85 g of dimethyldioxanoxane, 43 g of diphenyldimethoxydecane, 155 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene. Heat to reflux for 1 hour. After cooling, the lower layer was separated and washed, and the upper layer of the f-benzene solution was washed with water. To the layer of the benzene solution after washing with water, 8 g of 3-glycidoxypropylmethyldimethoxy decane and 5 g of potassium hydroxide hydrazine were added and heated under reflux for 1 hour. Next, the decyl alcohol was distilled off, and the excess water was removed by azeotropic dehydration. It was then heated to reflux for 4 hours. The toluene solution after the reaction was neutralized with 〇. 6 g of acetic acid and washed with water. After removing the water, the toluene was evaporated and concentrated under reduced pressure to obtain an alkenyl oxime % and an epoxy group 1 mol% (the number of all the Si atoms contained in the polyoxy siloxane was 1). 00 mol% of polyoxyalkylene (A6). The polystyrene-equivalent weight average molecular weight of (A6) was measured by gel permeation chromatography to be 18 Å. The chemical formula of polyanion (A6) is (viMe2Si01/2)1()(PhSi03/2)64(Ph2Si 〇2/2)5(Me2SiO2/2)20(EpMeSi〇"2)i (7) represents vinyl Me table: 曱 base, 卩 11 table is not stupid 'Ep represents glycidoxypropyl. The subscript number table is not mol/〇). When the total number of atoms contained in the polyoxane (A6) is 1% by mole, the content of the alkenyl group is i〇m〇i%, and the content ratio of the epoxy group is lm〇1. The % '彡 base content is 74m〇1%. [Synthesis Example 8] Synthesis of polyoxyalkylene (B1) was carried out in a four-necked vial equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, and the phenyltrimethoxyoxane 95 and the three were combined. 0.2 g of fluoromethanesulfonic acid - while stirring - 13 g of human water was dripped for 15 minutes, and after the completion of the dropping, -22-201247785 was heated to reflux for 1 hour. After cooling to room temperature, 119 g of M,3,3 tetramethyldioxane was added, and 88 g of acetic acid was added dropwise while stirring. After the completion of the dropwise addition, the mixture was stirred and heated to 5 (TC, reaction for 3 hours. After cooling to room temperature, toluene and water were added, and the mixture was thoroughly mixed and allowed to stand, and the aqueous layer was separated and removed: after washing the upper layer of the toluene solution, the mixture was reduced. Concentration by pressure to obtain nonylphenyl hydrogenated polyoxane (B1). The chemical formula of polyoxyalkylene (B1) is (ημ62 & 〇 1/2) 60 (PhSiO3/2) 40 (Me represents sulfhydryl, ph Phenyl. The subscript number indicates mol%). [Synthesis Example 9] Synthesis of polyoxyalkylene (B2) In a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, diphenyl was charged and mixed. 22 g of dimethoxydecane and 0.6 g of trifluorosulfonium sulfonate were added to 1,147 g of 1,1,3,3-tetramethyldiazepine, and 108 g of acetic acid was added dropwise over 30 minutes while mixing. After completion, the mixture was stirred and heated to 50 C and reacted for 3 hours. After cooling to room temperature, toluene and water were added, and the mixture was thoroughly mixed to allow 'separation and removal of the aqueous layer. The upper layer of the benzene solution was washed 3 times. Concentration under reduced pressure to obtain diphenyl hydrogenated polyoxane (B2). The chemical formula of polyoxyalkylene (B2) is (HMe2Si〇i /2) 5 〇 (ph2Si 〇 2/2) 5. (Me represents thiol ' Ph stands for phenyl. The subscript number indicates m 〇 1%). (1-2) Polyoxymethane obtained by weight average molecular weight The weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) under the following conditions and is obtained as a polystyrene equivalent. Device. HLC-8120C (manufactured by TOSOH CORPORATION) Columns · TSK- Gel MultiporeHXL-M (manufactured by TOSOH CORPORATION) -23- 201247785 Developer: THF, flow rate 55mL/min, loading amount 5.0%, ι〇〇μχ (1 -3) alkenyl group, epoxy group and aryl group The ratio, and the chemical formula of the polyoxyalkylene. The content ratio of the alkenyl group, the epoxy group, and the aryl group contained in the obtained polyoxyalkylene (the number of all Si atoms contained in the polyoxyalkylene is 1) 00 mol %), and the chemical formula of polyoxin, which was calculated by 29Si NMR and 13C NMR. (2) Preparation of hardenable composition [Examples 1 to 5 and Comparative Examples 1 and 2] At 95 atmospheric pressure Next, the components shown in the following Table 1 were mixed in the blending amounts shown in Table 1, and the curable compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were obtained. The numerical values represent parts by mass. Further, the details of the respective components in Table 1 are as follows. [Table "_Component Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 AR1 65 65 A1 68 A2 68 A3 68 3 A4 76 A5 3 A6 82 B1 3 3 3 3 3 3 3 B2 26 26 26 18 12 26 26 C1 0.01 0.01 0.01 0.01 0.01 0.01 D1 1 1 1 1 1 1 1 D2 1 1 1 1 1 1 1 D3 1 1 1 1 1 1 1 -24- 201247785 (:1:# complex with 1,3-divinyl-1,1,3,3_tetradecyldioxane (amount of platinum metal) 4 mass 〇/0) D1: cyclo-tetradecyltetravinyltetraoxane D2: diphenyl bis(dimethylvinyl decyloxy) decane D3: phenyl tris(didecylvinyl decyloxy) Evaluation of the curable composition of the decane (3) The curable compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated by the following methods (3-1) to (3-6). The evaluation results are shown in Table 2. (3-1) Viscosity The viscosity of the curable composition was measured at 25 ° C using an E-type viscometer. (3-2) Hardness A frame of 2 mm thick was placed on a flat plate of TEFLON (registered trademark), and the curable composition was applied to the height of the frame, and was produced by heating in a hot air circulating type of 5 hours of rc for 5 hours. 〇mm><50mmxlmm hardened material. The hardness of the cured product is measured by a d-type durometer specified in JIS K6253. (3 - 3) Refractive index is obtained by using a curable composition as a cured product for hardness measurement. Take

The refractive index at 25 ° C was measured by a Model 20 10 total reflection refractometer manufactured by Metricon Corporation. Further, the measurement wavelength was 408 nm. (3 - 4) Light transmittance change A circular (2 cm in diameter, thickness imm) frame was placed on a 1 mm quartz plate. The frame was filled with a hardenable composition, and the measurement was performed by a hot air circulating oven at 15 (rc). The light transmittance of the cured product (light path length 1.0 mm) which was cured by heating for 5 hours at a wavelength of 460 nm at 25 ° C. Next, in order to investigate the degree of coloration after the accelerated deterioration test, the same measurement was carried out at 15 〇 - 25-201247785 °C heat cycle oven to heat the above cured product after heating for 1 000 hours, the light transmittance at a wavelength of 460 nm at 25 ° C. The light transmittance after heat aging is relative to the light before heat aging The ratio of the ratio is evaluated by the following criteria: A: The ratio is 98% or more B: The ratio is 90% or more and 98% or less C: The ratio is less than 90% (3-5) A hardening composition was applied to the bottom surface of an aluminum cylinder having a diameter of 5 mm and a height of 5 mm and adhered to various test panels to be placed in a 15 〇 hot air circulating oven for 1 hour to obtain a height of 5 mm using a hardening composition. A 5 mm aluminum cylinder is attached to the test piece of the test panel. The age-ample series-4000PXY was used as a measuring device, and the aluminum cylinders which were intimately attached to various test panels were peeled off at a rate of 50 μm/sec. The load at this time was measured as the adhesion strength, and evaluated according to the following criteria. It is i〇kg or more B: the strength is 5kg or more and less than 1〇0 weight C. Then the strength is less than 5 kg (3-6) heat resistance, so that the curable composition becomes dry and thick, imm. Paint ^

After drying on Shihyang glass, dry and harden at i 00 °c for an hour, then at U

Dry and harden for 5 hours under C to make your stalks and stalks as hardened. This was stored at 1501; the appearance of the cured product after visual inspection of the ε 、 、 , , , , , , , , , f f f f f f f f f f f f f f f f f f f f f f f f f f f (color change) -26- 201247785 A : no color change B : slightly yellowish C : apparently yellow (3-7) total radiation beam measurement (brightness evaluation) The hardenable composition is mounted on the surface of the optical semiconductor The type (the topview type "the portion including the photo-semiconductor 2, the electrode 6' wire 7 and the reflector 3 of Fig. 3" was packaged and applied at 15 Å. The crucible was heated for 1 hour to prepare a sample for evaluation. The radiation beam measurement of the sample for evaluation described above was carried out using a total radiation beam measuring apparatus (ultraviolet, visible, near-infrared spectroscopic spectrometer MCPD-3700, φ 300 mm integrating sphere (hemispherical integrating sphere)). The ratio of the light beam ' of the sample for evaluation of the above evaluation to the initial radiation beam measured by light-emitting of the package before the application of the sealing material was measured in %, and was evaluated on the basis of the following criteria. A: The aforementioned ratio is 1 1 〇 % or more B : The aforementioned ratio is less than 1 丨〇❹ /. , 1 0 〇 % or more C : The aforementioned ratio is less than 1 〇 〇 〇/0 [Table 2]

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Viscosity (mPa.s) 2000 2000 2000 4000 15000 2000 2000 Hardness (D) 55 55 55 45 45 55 55 Refractive index 1.57 1.57 1.57 1.56 1.57 1.57 1.57 light transmittance AAAAAAA followed by intensity AAAAAAC and then thermal AAAAAAA total radiation beam AAAAABA -27- 201247785 From the results of Table 2, it is known that the epoxy group-containing polyoxyalkylene oxide (A) In Comparative Examples 1 and 2 used as an adhesion promoter, Comparative Example 1 in which a polylactic acid group having a bad emulsification group was obtained, and the total radiation beam was bright, and a polyoxyalkylene having a small amount of oxygen was used. In Comparative Example 2 of A3), only 2' was achieved with both high brightness and high adhesion. On the other hand, the polyoxyxane of the poly(oxyloxy) having 3 methoxy groups was used as the main component f. In the first to fifth embodiments, the total radiation beam and the subsequent strength were high, and the brightness and the high adhesion were achieved. [Industrial Applicability] The hardenable composition of this month's month is transparent because it is cured! It is also placed in a high-temperature gas environment, and its light transmittance is also lowered. It has a high point-and-shoot, and is used for optical semiconductor components and optical components, such as sealants, dots, and potting agents. Potting agent), two cloth = bottom ° 卩 filler. The cured product of the present invention has a small decrease in light transmittance even in the case of a dish, and has a small decrease in light transmittance in a manufacturing step of high temperature: long-term reliability is excellent: In the case of a semiconductor device for high-intensity optical use, since the total radiation beam is high, it is used as an optical member used in the vicinity of a high-luminance light source. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing the main components of a mode I of a specific example of an optical semiconductor device. 1 Optical semiconductor device 2 Semiconductor light-emitting device - 3 The degree of concentration of the reflector is low, and High, and small, semi-conducting protection is a violent condition with a light element and a circle 0 -28- 201247785 4 sealing material 5 particles 6 electrode 7 wire -29

Claims (1)

201247785 VII. Patent application scope: 1. A kind of hardening composition' contains: a polyoxyalkylene (A) having a dilute group and an adhesion group, and at least two of each molecule are combined with a deuterium atom. The polyoxyalkylene (B) of the hydrogen atom (except for the polyoxyalkylene (A)) and the curable composition of the catalyst for the deuteration reaction (C) are characterized by being contained in the curable composition. When the total content of all the components is 1% by mass, the content of the polyoxyalkylene (A) is 4 〇 to 9 〇% by mass. 2. The sclerosing composition according to the scope of the patent application, wherein When the number of all Si atoms contained in the polyoxyalkylene (A) is 100 mol%, the content of the polydecane (A) dedecenyl group is 3 to 5 mol%, and the content of the adhesion group is It is 0.01 to 10 mol%. Here, the close contact 3. The hardenable constituent physical group as in the second aspect of the patent application is a group having an epoxy group. Among them, the polyfluorene (RE 4 · the sclerosing composition of the third item of the patent application scope (A) is represented by the following chemical formula: S i 〇 1/2) b (RViRi si 02/2) Ο (R 1 R12 S i 01/2) a (rs · RJSi〇2/2) d (R^Sio^^ u (R^si〇3/2) (}si〇Z2) h (X 1/2' (where 'RV1 represents a group having an alkenyl group' rEp represents a group having an epoxy group, and R each independently represents a monovalent hydrocarbon group (except for a group having an alkenyl group) 'X represents a hydrogen atom or a number of carbon atoms (1) In the case of a base, a is not an integer of 0 or more, b is an integer of 〇 or more, c is an integer of 〇 or more, an integer of 1 or more, e is an integer of 〇 or more, f is an integer of 〇 or more, and h is 〇 or more. The integer, 丨 represents an integer above 〇, and a+c is an integer of 1 or more.) -30- 201247785 5. The sclerosing composition of claim 4, wherein 'polyoxane (4) has a fang The base 'and all contained in the polyoxane (4). When the number of atoms is 100 mol%, the content of the aromatic content contained in the polyoxyalkylene (4) is 30 to 12 mol%. Hardened The invention is obtained by the curable composition as claimed in any one of the above claims. The light-emitting semiconductor device is characterized in that it has a semiconductor light-emitting element and a patent application covering the +-conductor light-emitting element. The hardened material of the sixth item. 8. The oxane, which is represented by the following chemical formula: (RR 2S 1 01/2) a (RJ3S i 01/2) b (RViRi si 〇 2/2) c (RE PR1 S i 2/2) d (R^S i 02/2) e (riS i 〇3/2) f (S i 〇4/2) h (x 〇l/2>> R represents a group having an alkenyl group, and REp represents a group having an epoxy group, 'R1 each independently represents a hydrocarbon group of a valence (except for a group having an alkenyl group), and X represents a hydrogen atom or a carbon number of 1 to The alkyl group of 3 is an integer above a, the b represents an integer of 〇 or more, c represents an integer of 〇 or more, d represents an integer of 1 or more, e represents an integer of 〇 or more, and f represents an integer of 〇 or more, h. Indicates an integer above 〇, 丨 denotes an integer above 〇, true a + c is an integer of 1 or more) ° '31-