TW201041975A - Resin composition for encapsulating optical semiconductor element - Google Patents

Abstract

A composition for encapsulating an optical semiconductor element is provided. It includes (A) a first silicone resin having a unit with an epoxy group-containing non-aromatic group and a unit formed of a linear diorganopolysiloxane segment, (B) a second silicone resin having a unit with an epoxy group-containing non-aromatic group and a unit with diorganosiloxy units, (C) a curing agent, and (D) a curing catalyst. The composition has a good curability and resistance to heat discoloration.

Description

201041975 VI. INSTRUCTION DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a composition for encapsulating an optical semiconductor element, and more particularly to a composition of a seed capsule-packaged optical semiconductor element, wherein The matrix resin is temporarily only τ fine, and is composed of a polyoxymethylene resin and exhibits excellent heat discoloration resistance and superior curability. [Prior Art] Epoxy resin compositions have been widely used for encapsulating optical semiconductor elements. These epoxy resin compositions typically comprise an alicyclic epoxy resin acting as a matrix resin, a curing agent and a curing catalyst. The optical semiconductor element is typically encapsulated by a transfer molding method or the like by using a caster composition to be poured into a mold in which an optical semiconductor element has been placed, and then curing the resin composition. However, as the brightness and power output of the coffee increase, 'discoloration of the epoxy resin and 'solution problems' have begun to appear. In particular, the alicyclic epoxy resin tends to yellow when exposed to blue light or ultraviolet light, resulting in a shortened life of the LED element. In this case, polysulfide resin which exhibits excellent heat resistance and light resistance is currently used. However, the strength of the cured resin is weaker than that of the epoxy resin. & To overcome this problem, it has been proposed to use a high-hardness rubber-like polysulfide resin for capsule encapsulation. I::: See the patent document υ. However, 'this high hardness poly-stone resin: see weak adhesion, and in the embedded light-emitting semiconductor package 1 (also f and / or inside the plastic casing ' and then filled with poly-gel: the inside of the peripheral In the device), in,. ...the thermal shock test that is caught. It is easy to make the Tao Shi Xi oxygen tree moon shell or the ceramic shell is the plastic win. 201041975 A polyoxynium tree containing an epoxy group has been proposed for good adhesion and thermal shock resistance (see Patent Document 2). However, these polyoxyxylene resins are synthesized by condensing a nucleus-containing decane with a decyl alcohol, and the cured products of these polyoxyxides are easily broken and have a low modulus of elasticity. Therefore, the LED stomach encapsulated with this type of resin knee capsule exhibits cracks in the resin during temperature cycle testing. Known materials for solving this cracking problem include a composition comprising an epoxy resin and sesquioxane containing at least two epoxy rings (see Patent Document 3), and an epoxy resin as a stress reducing agent and containing A composition of a polyanthracene resin of an isocyanuric acid-derived group (see Patent Document 4). However, even with these two types of compositions, cracking was observed during the temperature cycle test of the cured product, and it was asserted that neither of the two types of compositions could provide a completely satisfactory thermal shock resistance. [Previous Technical Literature]

[Patent Document 1] JP 2002-314143 A [Patent Document 2] JP 7-97433 A [Patent Document 3] JP 2005-263869 A

[Patent Document 4] JP 2004-99751 A SUMMARY OF THE INVENTION An object of the present invention is to solve the problems outlined above, and to provide a resin composition for encapsulating an optical semiconductor element. , the monthly b is enough to form not only the hardness of the crucible, the good earning property and the excellent thermal shock resistance' but also has a significantly improved thermochromic capsule seal curing product 201041975, and has a good curing rate and the like nature. Means for Solving the Problems As a result of various studies, the inventors of the present invention have found that by epoxidizing an epoxy group-modified resin having a specific linear polyoxyalkylene structure and by condensing two organic gases Further, the above-mentioned (4)' and the inventors' invention can be obtained by obtaining a combination of the epoxy group-modified epoxy group and the second epoxy group of the epoxy group. In other words, the present invention provides a composition for encapsulating an optical semiconductor element comprising the components (a), (b), (c)^d = (A) first polyfluorene described below. An oxy-resin having a non-aromatic beauty containing an epoxy group represented by the average composition formula (1) shown below, in an amount of up to 9 〇 parts by mass,

Wherein R1 represents a non-aromatic group containing an epoxy group, and each R2 independently represents a group selected from the group consisting of a mercapto group, a CjC2G monovalent hydrocarbon group, and a CjC6 alkoxy group, each R3 represents a C丨 to Cm monovalent hydrocarbon group, x and y each independently represents an integer of 〇, 1 or 2, a represents a value in the range of 0.25 to 0.75, b represents a value in the range of 0.25 to 0.75, and c represents a value in the range of 0 to 0.3, with a constraint of a +b + c 201041975 and η represents an integer of 2 to 20, (Β) a second polyfluorene oxide resin having an epoxy group-containing non-aromatic group represented by the average composition formula (2) shown below, The amount is from 1 part by mass to 50 parts by mass, R1·

fZ -SiC^jQ

(2) wherein R1, R2 and R3 are as defined above, each z independently represents an integer of 〇, 1 or 2, d represents a value not in the range of 0.5 to 0.8, and e represents a value in the range of 0.2 to 0.5, The limiting condition is d+e = i, (C) a curing agent having a functional group reactive with an epoxy group in an amount of 0.4 mole per 1 mole of all epoxy groups in the component and component (8) An ear to 1.5 mol of a functional group reactive with an epoxy group, and (D) a curing catalyst in an amount of 0.01 part by mass to 3 parts by mass per 100 parts by mass of the combination of the component (A) and the component (B) Within the scope. EFFECTS OF THE INVENTION The resin composition of the present invention contains the above-mentioned second polysulfide tree t to form a cured product having high hardness. In addition, the Tian or Zhe M horse second polyoxon resin exhibits a high degree of reactivity, so that an optical semiconductor package having excellent heat discoloration resistance can be produced in a relatively short period of time. [Embodiment] 201041975 <Component (A) > In the composition of the present invention, the first poly-stone resin (A) having an epoxy group-containing non-aromatic group is represented by the average shown below The composition formula (1) is represented.

In the formula (1), η represents an integer of 2 to 2 Å, preferably a positive number of 3 to 3, and more preferably an integer of 3 to 1 Å. And 丫 each independently represents an integer of 〇, 1 or 2. As the first part of the polyoxyl resin, the subscript "a" is attached.

- each of the structural unit and the third structural unit to which the subscript %" is attached, X or y is: a methoxyalkane unit (T unit), x or y is 1 oxane monoterpene (D early兀) and a oxane unit (M unit) in which x*y is 2 usually coexist in a resin molecule. The ratio of such diarrhea to early enthalpy in each of the first and third structural units depends on the type of r2 in the monomer used in the manufacturing method described below and the degree of hydrolysis and condensation of the zeoliton And set. τ unit: D unit: μ single Κ Moer is better in coffee (10) 1 98: 1:1 40:30:30 to (10) called, 1 ^ king%.1:1, and more preferably 60:2 〇: 2 〇 to 96:2:2, and more preferably 80:10:10 to 95:3:2. For example, when η is 3, the formula (1) is represented by (R32Si〇)n and has the structure shown below. , 201041975

When the polyoxyxene resin has a linear structure, the (R32Si〇)n unit may be present in the main chain, or when the polyoxyxene resin has a branched structure, this (R32Si0)n

The unit can be keyed to the branch chain. The inclusion of this (κν〇)η unit makes it possible to obtain a cured product having excellent thermal shock resistance. In the formula (1), R1 represents a non-aromatic group containing an epoxy group, and examples thereof include a linear or branched aliphatic group containing an epoxy group such as a glycidoxyalkyl group (e.g., γ-glycidyloxy) Ethylethyl); an epoxy group-containing alicyclic group 诸如 such as a (3,4-epoxycyclohexyl)ethyl group; and an epoxy group-containing heterocyclic group such as a monoglycidyl isocyanurate group Or: glycidyl isocyanuramide. Among such groups, an epoxy group-containing alicyclic group is preferred, and a heart 0, an atrial epoxy group hexyl) ethyl group is particularly desirable. At the same time, it is assumed that a non-aromatic group containing an oxetane group instead of an epoxy group is also used; however, in terms of curability, the epoxy group is more excellent. Further, at least one _r1 group is preferably present per molecule. Group, and the mother molecule is better to exist 2 to! (8) Rl. The R1 group is preferably present at the end of the molecule. For example, when a molecule has a linear structure, it is preferred to have 'Ri' at the end of the parent of the molecule. R2 represents an example of a monovalent nicotinyl group selected from the group consisting of a mercapto group, a CJC20 monovalent hydrocarbon group, and a CjC6 alkoxy group, and includes a alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; and a cycloalkyl group such as a cyclopentane group. Or a cyclohexyl group; an aryl group, such as a phenyl group; an anthracene group such as a tolyl group; and a crosslinked ring group such as a dec. 9 201041975. Examples of the Cl to C6 alkoxy group include a methoxy group and an ethoxy group. R2 is preferably a mercapto group or a stupid group. Each R3 represents a Cl to Cm monovalent hydrocarbon group. Specific examples include the same groups as listed in the above R2 description. a represents a value in the range of 〇·25 to 0.75, and preferably a value of 〇.4 to 曰7. If the value of a is less than the lower limit of the range, the curing rate of the composition tends to decrease because the epoxy group is compared with J. On the contrary, if a 2 exceeds the upper limit of the above range, it is undesirable because the amount of the epoxy group is extremely large, and the resin to = is easily gelled. b denotes the value in the ' and is preferably the value of 〇3 to 〇6. c represents the value in the dry circumference, and is preferably a value of 〇 to 0.2. If the value of c exceeds the upper limit of this range, it is poor.耐r 1, &> The light fastness of the cured product tends to change 八 L i) to indicate each knot _ where a+b+c=1. The composition of the average existence ratio of 70 is obtained by a condensation reaction: a linear organopolyoxane which is subjected to hydrolysis and hydrolysis by the following formula (3): R3I ~ Si - 〇 - R3I * si - 〇 R3I Si - (3) Sub (wherein R3 is as defined above for the hydrolyzable group, 'and 坩 is 0 to x represents an integer such as alkoxy or ii prime U), 10 201041975 is represented by τ Epoxy-containing stone

(4) I further wherein R1 and R2 are a radical or a CJ c6 alkoxy group, and the 疋 restriction condition is at least one

And according to the situation, the expression of >5:

(5) (wherein m R3 is as defined above, the restriction is that at least one R2 is a hydroxyl group or c! to a c6 alkoxy group). The polystyrene equivalent average molecular weight of component (A) is typically in the range of 3, just up to 10,000, and preferably 3, 〇〇〇 to 6, 〇〇〇. Further, the base equivalent is typically in the range of 2 GG g/mol to g/m () 1 and oxygen: 300 g/mol to 600 g/m 〇l. &佳 <Component (B) > Second polyfluorene oxide resin having an epoxy group-containing non-aromatic group The average composition formula (2) shown below is represented. From (Rl-"_)d'". )e (2) 11 201041975 In the formula (2) Yin, the ruler 2 and the r3 represent 0, 】 or 2 as above.士疋义. Each of the Z's subscripts "d" is the first - heart...", and the "fourth" unit (the τ unit) of the second layer of the second bismuth resin is attached to the ... And X is 2 (as early as possible) and usually coexists in its molecule. These oxalates are “as early as 7° (the ratio in the manufacturing method described below) depends on the degree of solution and the degree of condensation, and the degree of water in the body of the body is 疋.疋: D unit: 熥10:30:60 to 98.1.1 夕e η & 旲 比较 better in the range of 98.1.1, more preferably 40:3 〇: 30 to 98. η better 60 :20:20 to 96·2·2, s Review - -1·1 range. 6·2·2 and better at 80:10:10 to 95:3:2 d: in 〇_5 a value in the range of i 〇.8, and preferably from 0·5 to 〇.7, value: the value of d is less than the lower limit of the range, the composition becomes difficult to be singulated and the value of the right d exceeds the upper limit, then The resin becomes difficult to synthesize and the composition is easily gelled. e represents the value of 〇m5 in the range of Q 2jl Q 5 with the constraint d + e = 1. Method of manufacturing component (B) and manufacturing component (A The method differs in that during the preparation of the resin, the linear organopolycarbon having the above formula (3) in the organolithic component (A) represented by R, X2Si is used in the condensation reaction. The organically-derived and calcined 3% oxy group represented by the general formula (4) is subjected to hydrolysis and condensation. To produce the first-polyoxyl resin of component (B). Therefore, component (B) is substantially free of component (A) (R), and component (B) is considered to have A function similar to that in the cured product, thereby increasing the strength of the cured product. Therefore, the t composition of the present invention is capable of forming a cured product having a good hardness and a thermal shock resistance and a similar property of 12 201041975, even if it is not A combination of epoxy resins is used, and in particular, an alicyclic epoxy resin widely used for capsule conductor reading is not used. Since the cured product does not contain the day of the month, it does not undergo thermal discoloration. The polystyrene equivalent average molecular weight of the fraction (B) is typically in the range of from 3 to 1,000,000, and preferably from 3,000 to 7,000. The epoxy equivalent of the component (B) is typically In the range of 1 〇〇/111〇1 to 6〇〇g/m〇1, and preferably 250 g/m〇i to 4〇〇g/m〇1. Particularly desirable are components. The epoxy equivalent of (B) is from about 3 〇g/m 〇1 to 3 〇〇g/m〇i and is less than the epoxy equivalent of the component (A). The blending of the knive component (B) Typically, it is in the range of 10 parts by mass to 5 parts by mass, preferably 1 part by mass to 30 parts by mass, per part by mass of the component (8) and the component (B). If the component (b) If the amount exceeds the upper limit of the range, the cured product of the resin composition is liable to be degraded by ultraviolet light in the case where the light-emitting element emits ultraviolet light. In addition, the cured product tends to crack when subjected to a long-time addition of Q heat. <Component (C) > Examples of the curing agent (C) include an amine-based curing agent, an age-based curing agent, and an acid anhydride-based curing agent, and among these curing agents, the acid anhydride-based curing agent is Preferably. Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4- Mixture of methyl-hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride 13 201041975, tetrahydrophthalic anhydride, Nadic anhydride' methyl-resistance, norbornane-2,3-dicarboxylic anhydride and methylnorbornane-2,3-dicarboxylic anhydride. The amount of the curing agent (C) blended is from 〇4 mol to 丨5 mol and preferably 0.5 mol per mol of the epoxy group in the combination of the component (A) and the button (B). A functional group exhibiting reactivity with an epoxy group to 1.2 moles (in the case of an acid anhydride curing agent, an acid hydride group having _c〇_〇_c〇_). <Component (D) > Examples of the curing catalyst (D) include a curing catalyst based on a quaternary phosphonium salt, such as tetrabutyl sulphate of tetramethyldithiosilicate and tetraphenylboronic acid Base scale 'based on organophosphine-based curing catalysts, such as triphenylphosphine and diphenylphosphine' based on a secondary amine-cure catalyst such as 1,8-diazabicyclo (5,4, fluorene) eleven carbon-7 - alkene, triethanolamine and benzoguanidine dimethylamine; a curing catalyst based on a quaternary ammonium salt, such as 1,8-diazabicyclo(5,4,yttrium)undecyl-7-enphenolate, -diazabicyclo^〆...)·] carbonic acid salt and 1,8-diazabicyclo(5,4,0)Ί carbon-7-ene tosylate; and imidazole-based curing catalyst For example, 2-methyl-n-β and 2-propenyl-4-methyl-p-methane. Among these curing catalysts, a quaternary phosphonium salt and a quaternary ammonium salt are preferred. The curing catalyst (D) is blended. The amount is typically in the range of from 1 part by mass to 3 parts by mass and preferably from 5 parts by mass to 0.5 parts by mass per 1 part by mass of the component (Α) and the component (Β). The amount of curing catalyst is less than this range 'The catalyst may not provide sufficient acceleration of the reaction between the epoxy resin and the curing agent. Conversely 'if the amount of curing catalyst exceeds the upper limit of the above range, the curing catalyst may be tested during curing or during the flow test at 14 201041975 Causes discoloration during the period. In addition to the above components, such as antioxidants, used to change the turbidity, sputum, oxidized silk, inorganic fillers (such as dioxide I, fine powder), decane coupling agent The additives of the thermoplastic agent and the diluent may also be included in the composition of the present invention, and the restriction condition is that the present invention is not harmful. The antioxidant based on the hindered phenol And the phosphating agent is preferably used as an antioxidant. The ultraviolet absorbing 基于 基于 1 based on the hindered amine is preferably used as the i-line absorber. The sulphur-based coupling agent based on the sulfhydryl group is preferably used as a breaker coupling agent. It may be relatively easy to combine the components (A) to (D), or the additives selected as appropriate, and then at about C, which is low enough to prevent curing. Melt mixing is carried out to make. 'Melting mixing can be carried out using a conventional method. For example, the above group can be combined in a reactor, and the glyco-, ', and the intermediate can perform melt mixing in a batch process, or can be Each of the above components is supplied to a mixing device such as a kneader or a three-roll mill, in which melt mixing is performed in a continuous manner. The resin composition thus obtained for encapsulating an optical semiconductor element can be obtained by the above method The resin composition in the form of a molten mixture is injected into a mold or an outer casing in which the force generating member is mounted, and then the resin composition is subjected to a B_staging at a predetermined temperature, and then the composition is solidified for use. In addition, the resin composition can also be used to protect the lED mounted on the substrate by applying the composition to the LEEM by using a perfusion method, a printing method, a transfer molding method, an injection molding method, or a compression molding method. 201041975 In the case of infusion or injection molding to coat and protect a light-emitting semiconductor device such as an LED, the composition of the present invention is preferably in a liquid form. In other words, the viscosity of the composition of the tree sorghum (reported as measured using rotational viscosity at 25 ° C) is preferably from 10 mPa.s to 1,000,000 mPa.s and more preferably 1 〇〇 mPa, s Up to 1,000,000 mPa*s. On the other hand, in the case where the light-emitting semiconductor device is manufactured by transfer molding or the like, 'a liquid resin of the above type can be used, or the production can be solidified by increasing the viscosity (B-stage treatment) and then The solid is granulated and subsequently molded. EXAMPLES The present invention is described in more detail below based on a series of examples and comparative examples, but the present invention is by no means limited by the examples presented below. [Synthetic component (A)] In the synthesis example, the average value of n in the composition of the product 夕 上, 丄 初 初 由 由 由 系 系 系 平均值 平均值 平均值 平均值 平均值 平均值 平均值 平均值 平均值 平均值 平均值 平均值 平均值 平均值 平均值The plot of the molecular weight distribution measured by Gpc is calculated by dividing the sum of the multiplication + product (ie, the multiplicative product) of the peak area of the η by the total area of all the peaks. For example, in the case where the range of η in the product is 2 to 20, the average value of η is η 升 箄 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ Area ^ 槚)··· + 2〇χ (η is the peak area of 20)] / [(η is the peak area of 2) + (η Τ by 槚) + .·. + (η is the peak area of 20) ]. <Synthesis Example 1> g (5.996 mol) wherein in each of 0 to 8 was charged to the reaction flask, 1,695.6

MeO(Me)2Si〇(Me2Si〇)mSi(Me)2〇Me (16 201041975 integer, and the average value of m is 1.5), 3, 〇〇〇ml isopropanol and 1,470 g (5·966 mol) 3-(3,4-Epoxycyclohexyl)ethyltrimethoxysulfonate (KBM303, manufactured by Shin-Etsu Chemical Co., Ltd.), followed by addition of 72 g of 25% aqueous solution of tetradecylammonium hydroxide and 648 g of water The resulting mixture was stirred at room temperature for 3 hours. After the reaction was completed, 3, 〇〇〇 ml of toluene was added to the reaction system. The reaction mixture was then neutralized with an aqueous solution of sodium dihydrogen phosphate and the separated organic layer was washed with hot water using a separating funnel. Then, the benzene was removed under reduced ’ ’ to produce a target resin ("resin 1") having a structure represented by the following average composition formula. - The polystyrene equivalent average molecular weight measured by a GPC is . The epoxy equivalent is 403 g/mo, 1 = the result obtained by measurement using MSi_NMR is shown in the figure and the edge appearing around π ah reflects the formation of the T unit of the stone atom, ''·, PPm to about -58 ppm appears at the end of the bee- " combination of the elements. Therefore, the display == into... and the first structural unit (the combination of the Mo's %D unit and the unit in the average composition of the 's'. Ears, Ding Zao - and about 10

Wherein each of η is an integer of 2 to 10, and the thousandth mean of 0, 1 or 2 is 3.5, and the soap 70 coexists in the first unit. 17

X 201041975 <Synthesis Example 2> The reaction flask was charged with 1,500 g (ι·975 mol) of H〇(Me)2Si〇(Me2SiO)mSi(Me)2〇H (where m each was 3 to An integer of 18, and the average value of m is 8), 973.2 g (3,950 m) of 3_(3,4 epoxycyclohexyl)ethyltrimethoxydecane (KBM303, manufactured by Shin_Etsu Chemical Co., Ltd.) and 2, 3 〇〇 ml of isopropanol, followed by addition of 49 g of a 25% aqueous solution of tetradecylammonium hydroxide and 449 1 g of water, and the resulting mixture was incubated at room temperature for 3 hours. After the completion of the reaction, 2,3 〇〇 m of toluene was added to the reaction system, and the reaction mixture was neutralized with an aqueous solution of sodium dihydrogen phosphate. The separated organic layer was then washed with hot water using a separatory funnel. The benzene was removed under reduced pressure to give a target resin ("resin 2") having a structure represented by the following average composition formula. The average molecular weight of the polystyrene equivalent measured by GPC was 5,600. The epoxy equivalent weight was 57 〇 g/mM.

And η are each an integer of 5 to 20, and the average value of η is 1 〇, and the unit of χ 〇, 1 or 2 coexists in the first unit. <Synthesis Example 3 >" To the reaction flask, 933.30 g (3.95 mol) of 3_glycidoxypropyltrimethoxydecane (KBM4〇3, manufactured by Shin_Etsu Chemicai Co., Ltd.), L500 g was charged. (1 975 Moer 18 201041975 HO(Me)2SiO[(Me)2SiO]mSi(Me)2OH (where m is 3 to an integer ' and the average value of m is 8) and 2,3〇〇ml Propyl alcohol, followed by addition of 92-15 g of a 25% aqueous solution of tetradecylammonium hydroxide and 444 96 g of water, and the resulting mixture was stirred at a temperature for 3 hours. After the completion of the reaction, 2,3 Torr of toluene was added to the reaction system, and The reaction mixture was neutralized with an aqueous solution of sodium dihydrogen phosphate, and the separated organic layer was washed with hot water using a separating funnel, and toluene was removed under reduced pressure to give a target resin having a structure represented by the following average composition formula ("resin 3 The polystyrene equivalent average molecular weight measured by GPC was 4,300. The epoxy equivalent was 570 g/m〇1.

0,5

0.5 wherein n is an integer of 5 to 20' and the average value of n is 1 〇, and a unit in which χ is 0, 1 or 2 coexists in the first unit. [Synthetic component (Β)] <Synthesis Example 4> The reaction flask was charged with 187.00 g (1 566 mol) of dimethyldimethoxydecane (KBM-22, manufactured by Shin-Etsu Chemical Co., Ltd.). ), 766.67 g (3.111 mol) 3_(3,4_epoxycyclohexyl)ethyltrimethoxy zebra (KBM303 manufactured by Shin-Etsu Chemical Co., Ltd.) and 90 〇!! 11 isopropyl alcohol, followed by 2169 § 25% aqueous solution of tetramethylammonium hydroxide and 195.11 g of water were added, and the resulting mixture was stirred at room temperature for 3 hours. Anti 201041975

After completion, 1, 〇〇〇ml of hydrazine was added to the reaction system, and the reaction mixture was neutralized with an aqueous solution of sodium hydrogen hydride. The separated organic layer was then washed with hot water using a separatory funnel. Toluene was removed under reduced pressure to give a target resin ("resin 4") having a structure represented by the following average composition formula. The polystyrene equivalent average molecular weight measured by GPC was 4,200. The epoxy equivalent is 267 g/mol 〇

Units in which X is 0, 1, or 2 coexist in the first unit. <Synthesis Example 5> A reaction flask was charged with 187.00 g (1 566 mol) of dimethyldimethoxydecane (KBM-22, manufactured by Shin-Etsu Chemical Co., Ltd.).

After completion, add 1,000 ml of hydrazine to the reaction system.

- The ear resin is removed under pressure, and the target resin of the structure is represented by the average composition formula ("Resin w is removed under reduced pressure, added to the reaction system, and the phosphate separatory funnel is used with hot water F More than hydrazine-produced with the following IT addition 12.97 g of 25% tetramethylammonium hydroxide water-soluble and the mixture was stirred at room temperature for 3 hours. Anti->ml benzene was added to the reaction system, and

The measured polystyrene equivalent average molecule # is 3,10 C fat ("resin 5"). The amount of GpC is 3,100. Epoxy equivalent weight is 20 201041975

Units in which x is 0, 1, or 2 coexist in the first unit. <Synthesis Example 6> 187 The reaction flask was charged with 187.00 g (l.566 mol) of dimethyl dimethyl ketone oxide (KBM-22, manufactured by Shin-Etsu Chemical Co., Ltd.), 735.24 g (3.111 mol) 3-glycidoxypropyltrimethoxy smash (KBM403' manufactured by Shin-Etsu Chemical Co., Ltd.) and 900 ml of isopropanol, followed by addition of 20.98 g of 25% tetramethylammonium hydroxide Aqueous solution and 188-82 g of water were added, and the resulting mixture was stirred at room temperature for 3 hours. After the reaction was completed, 1,000 ml of toluene was added to the reaction system, and the reaction mixture was neutralized with a pot of dioxon aqueous solution. The organic layer was then washed with hot water using a separatory funnel. The terpene was removed under reduced pressure to give a target resin ("resin 6") having a structure represented by the following average composition, and the polystyrene equivalent average molecular weight measured by GPC was 3,5 Å. The cyclic thiol equivalent is 295 g/mol.

21 201041975 A unit in which x is 〇, 1 or 2 coexists in the first unit. &lt;Examples 1 to 6, Comparative Example 1, Reference Example 丨 and 2&gt; Using the resin obtained above, a composition was prepared using the formulation shown in Table 。. In Table 1, the values listed for each component (except the curing agent) indicate "parts by mass". The other components used in the composition are listed below. (C) Curing agent: 4-methylhexahydrophthalic acid liver (rIKAciD®, manufactured by New Japan Chemical Co., Ltd.) (D) Curing catalyst··Quaternary phosphonium salt (uCAT5003, manufactured by San-Apro Co., Ltd.) Shi Xiyuan coupling agent: 3-mercaptopropylmethyldimethoxydecane (KBM-802 'made by Shin-Etsu Chemical Co., Ltd.) Epoxy resin · · 3', 4'-epoxy ring 3,4_epoxycyclohexyl alkanoic acid (CELL® XIDE 2021P, manufactured by Daicel Chemical (10) Her (6) Co., Ltd.) &lt;Example 1 &gt; For 80 parts by mass of resin 1, 20 parts by mass of resin 4, relative Each of the epoxy groups in each of the mole resins 1 and 4 provides an amount of i mole anhydride groups || a curing agent and a mixture of 100 parts by mass of the resin i and 4 and a curing agent, 39 parts by mass of a curing catalyst and 0.25 parts by mass of a decane coupling agent was melt-mixed to obtain a composition. Melt mixing is first done at 6 Torr. The molten solidifying agent and the curing catalyst in the oven were then mixed with other components for 2 minutes using a mixer (product name: Thinky Mixer, manufactured by Thmky Co., Ltd.), and then at 2, 20 Torr. Perform defoaming for 1 minute at rpm to execute. &lt;Example 2&gt; 22 201041975 For 80 parts by mass of the resin i, 2 parts by mass of the resin 5, and a curing agent in an amount of the oxime anhydride group relative to all the epoxy groups in each of the mole resins 1 and 5. And a mixture of the resin i and 5 and the curing agent per 100 parts by mass, 39 parts by mass of the curing catalyst, and 25 parts by mass of the decane coupling agent were melt-mixed in the same manner as in Example 1 to obtain a composition. <Example 3> A curing agent in an amount of 1 part by mass of the resin 2, 2 parts by mass of the resin 4, and 1 part of the epoxy group per mole of the epoxy group 2 & A mixture of 100 parts by mass of the resins 2 and 4 and a curing agent, an oxime portion E1 catalyst, and a ruthenium 25 f portion of Shi Xixuan coupling agent were melt-mixed in the same manner as in Example to obtain a composition. &lt;Example 4&gt; 80 parts by mass of the resin 2, 2 parts by mass of the resin 5, and a lipizing agent in an amount of 1 mole of the anhydride group per mole of the epoxy group in each of the 2 to 5 molar resins The mixture of the mother 1GG and the amount of the curing agent 〇3 9 parts by mass of the curing catalyst and the 25 parts by mass of the sulphur coupling agent were mixed by the same manner as in the example ι to obtain a composition. . <Example 5&gt; The amount of the i-molar acid group which provides the amount of the i-mole anhydride group with respect to the 80 mass-residual resin 3, 2 parts by mass of the resin 6, and the total epoxy group per 1 mol of the resin. 4 1 GG gm parts of a mixture of resins 3 and 6 and a curing agent 〇 ^ fm & 1 Mb of a catalyst and hydrazine &gt; 25 parts by mass of a sulphur coupling agent were melt-mixed in the same manner as in Example 以获得 to obtain a composition. &lt;Example 6&gt; 23 201041975 For 80 parts by mass of the resin 1, 2 〇皙々, the aliquot of the resin 4, with respect to all of the epoxy oxime and the scaffolding k in each of the j-mol resin 1 and A curing agent for 1 mole of anhydride group and a mixture of #1 parts by mass of resin 1 and 4 and a curing agent 〇 39 f amount (4) (10) The agent was melt-mixed in the same manner as in the practice of Μ 1 to obtain a composition. &lt;Comparative Example 1 &gt; The meaning of 100 parts by mass of the resin b relative to the epoxy group in the molar resin i to provide a 1 molar solvent group; the curing agent and 100 parts by mass of the resin i The mixture with the curing agent 〇 '39 parts by mass of the curing catalyst and 0.25 parts by mass of the sulphur coupling agent were melt-mixed in the same manner as in Example 1 to obtain a composition. &lt;Reference Example 1&gt; For 78-volume resin i, 22 parts by mass of epoxy resin, per 1 : ear? All of the epoxy groups in the fat 1 and the epoxy resin are used as a curing agent for the molybdenum acid group and 0.39 parts by mass of the compound per gram by mass of the epoxy resin and the curing agent. The ground η catalyst and the G.25 mass "burning coupler" were mixed and mixed in the same manner as in Example i to obtain a composition. &lt;Reference Example 2&gt;: 90 parts by mass of resin 2, 1 G f parts of epoxy resin 1 for each 丄 24 201041975 [Table 1]

Note to Table 1: Unit mass parts excluding (cT~i agent) &lt;Evaluation Test 1&gt; The following tests were performed on each composition, and the results are shown in Table 2. (1) Physical properties. The composition was cured by heating at i 00 〇 c for 2 hours, and then post-cured by heating at 150 t for 4 hours, thereby forming a rod-shaped cured product having a finality of 5 mm. Measuring the appearance of the rod-shaped cured product , hardness (Shore D ( Shore D )), flexural modulus of elasticity, and flexural strength (JIS K-6911). (2) Heat discoloration resistance: a rod shape prepared in the same manner as in the above (1) The cured product was subjected to high temperature aging (at 15 Torr: T ^ 000 hours), and then the appearance was also measured. (3) UV resistance: The composition was pressure molded at 1 ° C for 30 minutes to produce a measurement. A cured product of 6 cm x 6 cm x 2 mm (thickness), and then the cured product was post-cured at 150 ° C for 4 hours to prepare a sample. Under UV irradiation (using a high pressure mercury lamp: 30 mW/cm 2 , 365 nm) for 12 hours After the amount of 25 201041975 measured transmittance. Transmittance is measured by scanning at 800 nm to 300 nm, at the beginning of 400 nm The initial transmittance was regarded as 100%. (4) For each composition, a slide was prepared by adhering a polytetrafluoroethylene tape (thickness: 180 / im) to the periphery of the slide, and then the composition was The object was poured into the obtained concave groove, followed by curing by heating at 100 ° C for 2 hours, and then at 15 Torr. (: post-curing for 4 hours, thereby forming a film-cured product. Using ultra-microhardness The microhardness of the cured product of the film was measured by DUH-W201S 'manufactured by Shimadzu Co., Ltd. [Table 2] After curing (appearance) Hardness (Shore D) Flexural modulus (N/mm 2 ) Example 1 Example 2 Example 3 Example 4 Colorless, transparent, colorless, transparent, colorless, transparent, colorless, transparent Example J__ colorless, transparent embodiment colorless, transparent 75 1200 72 800 58 580 56 1250 41 77 Comparative Example 1 Colorless, transparent reference EXAMPLES Colorless, transparent Reference Example 2 Colorless, transparent 690 1180 78 76 45 680 510 Unmeasured *2 Flexural strength (N/mm UV resistance (%) Thermal discoloration (150 ° C, 1000 hours) Surface display Microhardness (MPa) 35 97 Colorless, transparent 2798 28 99 Colorless transparent Colorless transparent 4326983397 colorless and transparent not measured not measured * 1 * 2939593 colorless transparent colorless transparent cracks, yellowing yellowing yellowing

*1 : ^The product is now grandfather, and the flexural strength cannot be measured. *2: The cured product was rubbery and the flexural strength could not be measured&lt;Evaluation Test 2&gt; - The manufacture and evaluation of the LED device were carried out using the compositions from Examples 1 and 3 to &amp; 3 and Comparative Example 1. Each of them, using the square system described below, was used to prepare three 26 201041975 LED devices having compositions. Use a pre-molded (4) package with a thickness of i mm, a length of 3 sides and a 2.6 mm diameter opening (the bottom of the opening is keyed with silver). Use a silver paste to fix the InGaN-based blue-emitting element to The y H connects the external electrode to the light emitting element using a gold wire. The above composition is then injected into the package opening. By heating for 1 hour under the war and then at 150. (: heating was further carried out for 2 hours to cure the composition, thereby completing the preparation of the LED device. The prepared LED device was subjected to a temperature cycle test under the conditions listed below, and under conditions of 65 ° and 95% RH. A 50G hour LED luminescence test (LED wavelength: 45 〇 nm) was carried out, and then the adhesion failure at the package interface, the presence of cracks and the presence of discoloration were visually evaluated. The results are shown in Table 3. - Temperature cycle test conditions __ Jubilee ring: 20 minutes at -40 ° C and then 2 重复 2 cycles repeated cycles: 1,000 - Adhesive strength - using each of the compositions from Examples 1 and 3 and Comparative Examples In one case, an adhesive test piece was prepared by the following method, that is, a thin coating of the composition was applied onto a silver-plated copper foil, a 2 mm square wafer was placed on the composition, and heated by 100 hours for 1 hour. Then, the composition was cured by heating under heating for 2 hours, thereby completing the preparation of the adhesive test piece. Using the die bond strength tester (device name: Dage series 4〇〇〇 bond strength tester) test speed : 200 Mm/s, test Degree: 10.0 From melon, «Measurement temperature: 25. (:) Measure the adhesion strength of the cracked test piece prepared by the test. 27 201041975 [Table 3] ^Warm and high humidity test (lack of adhesion strength (kg/ Mm resin composition ^^ cycle test (defective political Wanding Example 1 Example 3 Comparative Example 1 -- --------- 0/3 0/3 3/3 (cracking) --- ---- 0/3 0/3 3/3 (discoloration occurs) -~__ 1.7 2.8 1.1 The results from Tables 2 and 3 are apparent, obtained from the composition of Comparative Example 1 lacking component (B) The cured product exhibited poor flexural strength and heat discoloration in which the composition was discolored under light from LEd. Further, the cured product obtained from the composition of the reference example containing the epoxy resin instead of the component (B) was After heating, it undergoes yellowing. In contrast, the cured product obtained from the composition of the examples of the present invention exhibits high hardness and does not substantially change color. Further, the microhardness values listed in Table 2 are apparent, and the examples are The composition produced hardness higher than that of the composition of the comparative example and the reference example under the same conditions. The cured product of the hardness of the cured product is 'and also exhibits a faster curing rate. Industrial Applicability The composition of the present invention cures quickly and produces a cured product exhibiting excellent heat discoloration resistance and excellent UV resistance, and thus is very suitable for use. Resin for encapsulating an optical element in a capsule. [Schematic description of the drawing] Fig. 1 shows a Si-NMR chart of Synthesis Example 29. [Key element symbol description] of the polyoxyl resin obtained in the Μ ..., 28

Claims (1)

201041975 VII. Patent application scope: ι·A composition for the knee-bag encapsulation optical lane threat __ From 7.4, this garment is especially a composition of a bovine conductor, which composition contains the following components (A) (B), (c), and (d): (A) a poly-non-oxygen resin having a non-aromatic group containing an epoxy group, which is shown by the following, a squirrel, _, 卞Q The composition formula (1) indicates that the amount is from 5 〇 parts by mass to 90 parts by mass, and R—SiO(3.^Q a R3 I SiO Ο Ο bf R3—SiO(3.y)/2 (1) _ R1 represents a non-aromatic group containing an epoxy group, and each R2 is independently selected from members of a group consisting of a &amp; base, a (:! to c2G monovalent hydrocarbon group, and a oxy group, and each R3 represents a Ci to C2 fluorene monovalent hydrocarbon group, X and y each independently represent an integer of 〇, 1 or 2, a represents a value in the range of 〇·25 to 0.75, b represents a value in the range of 〇·25 to 0.75, and c represents a value in the range of 0 to 0.3. The value a+b+cd ' and η represents an integer of 2 to 20, (Β) a second polyfluorene oxide resin having an epoxy group-containing non-aryl group, represented by the average composition formula (2) shown below, The amount is from 50 parts by mass to 50 parts by mass ~ R —SiO(3.z)/2 J ^ Restriction Ra Γ/e (2) where R1, R2 and R3 are as defined above, each z independently represents an integer of 0, 1 or 2, 29 201041975 d denotes a value in the range of 0.5 to 0.8, and e represents a value in the range of 0·2 to 0,5, and the constraint is d+e=l, (C) a curing agent having a function reactive with an epoxy group a group having an amount of from 0.4 moles to 1.5 moles of the functional group reactive with the epoxy group per mole of all epoxy groups in the component (A) and the component (B), and (D) The amount of the curing catalyst is in the range of 0.01 parts by mass to 3 parts by mass per 1 part by mass of the combination of the component (A) and the component (B). 2 The composition of the first aspect of the patent application, wherein The η in the average composition formula (1) is an integer of 3 to 20. 3. The composition of the first aspect of the patent application, wherein the polystyrene equivalent average molecular weight of the component (Α) is 3,000 to 1 Torr, 〇 Within the scope of 〇〇 4. As in the composition of claim 1, the epoxy equivalent of the component (Α) is in the range of 200 g/mol to 800 g/mol, and the component (B) Epoxy The amount is at least 30 g/mol and less than the epoxy equivalent of the component (A). 5. The composition of claim 1, wherein R1 represents &amp; (3-epoxycyclohexyl)ethyl Or a γ-glycidoxyalkyl group. 6. The composition of claim 1, wherein R3 is a methyl group. 7_ The composition of claim 1, wherein the epoxy equivalent of the component (a) is in the range of 300 g/mol to 600 g/mol, and the epoxy equivalent of the component (B) is In the range of 250 g/mol to 400 g/mol. 8. The composition of claim 1, wherein component (c) is 201041975 anhydride. 9. The composition of claim 1 of the patent scope' further comprising a base-based coupling agent based on a base. 10. A semiconductor device comprising an optical semiconductor element and a cured product obtained by curing a composition according to any one of claims 1 to 9 and encapsulating the optical semiconductor Component 0 Ο Eight, schema: (such as the next page) 31