JP6526376B2 - Resin composition for optical semiconductor parts, sealing material or sealing material for optical semiconductor parts, and cured product - Google Patents

Description

  The present invention relates to a resin composition for an optical semiconductor component excellent in storage stability, comprising a thermosetting organosilicon compound with improved reactivity, which is used for sealing or sealing for an optical semiconductor component, The present invention relates to a sealing material or sealing material for semiconductor parts and a cured product excellent in transparency, heat resistance and appearance.

Conventionally, for example, a transparent epoxy resin composition is used to seal an optical semiconductor device such as an LED. These transparent epoxy resin compositions contain an alicyclic epoxy resin, a curing agent and a curing catalyst, and are used to seal an optical semiconductor element by a molding method such as casting molding or transfer molding.
In general, epoxy resin compositions are excellent in handleability because the hardness of the cured product is high, and for example, in low-power white LED sealing applications, the required durability can be obtained, so in low-power applications Many are used.
However, with the recent increase in brightness and output of LEDs, cured products of conventional transparent epoxy resin compositions discolor when continuously used by short-wavelength blue light and ultraviolet light, and obtain sufficient life. It was difficult. Moreover, the problem that a crack generate | occur | produces in hardened | cured material has arisen by repetition of the rapid temperature change accompanying lighting and light extinction.
Recently, in order to solve these problems, LEDs cured with a resin composition based on a silicone resin having excellent weather resistance are being used instead of epoxy resins. For example, a report (Patent Document 1) of an addition-curable silicone composition for protective encapsulation of an optical device or semiconductor device by the addition reaction of a hydrosilyl group and an olefin has been made.

  However, while the silicone composition as described above has high flexibility derived from the silicone skeleton, it has the disadvantages that the hardness of the cured product is low, the surface is easily sticky, and the strength is low. In addition, the gas barrier property is low, and blackening due to sulfidation of silver used in silver-plated portions of substrates and die-attach materials becomes a problem due to the influence of outgas components from parts and gases entering from the outside, particularly sulfur-containing gases. ing. In addition, they have the disadvantage of low adhesive strength as compared to epoxy resins. In addition, for applications that require transparency, such as LED encapsulants, the reaction catalyst is reduced to the minimum necessary to avoid deterioration and coloring due to long-term use, compared to epoxy resins etc. And the curing reaction time was long. Furthermore, silicone resins are economically undesirable because they are very expensive.

Therefore, in recent years, there have been increasing reports of resin compositions (Patent Documents 2 to 8) in which a curing agent is blended with a silicone resin having an epoxy group synthesized relatively inexpensively compared to the addition-curable silicone composition. There is. For example, a resin composition in which a curing agent is mixed with a silicone resin having a glycidyl isocyanuryl group (Patent Document 9) has a curing reaction time equivalent to that of a conventional epoxy resin, and the cured product has a silicone skeleton It is known that it has high fertility derived from. However, although they have relatively high heat resistance and UV resistance, they are not satisfactory as compared with the addition-curable silicone resin.
On the other hand, a large number of compositions containing a curable organosilicon compound utilizing the same addition reaction of a hydrosilyl group and an olefin as the addition-curable silicone resin have also been reported (Patent Documents 10 to 14). By using a compound having an olefin skeleton as an organic compound, it becomes cheaper than the addition-curable silicone resin, and by introducing an alicyclic skeleton or a heterocyclic skeleton, relatively high heat resistance and ultraviolet resistance can be imparted. Are known. However, since the ratio of the organic skeleton site (a site other than the siloxane site in the curable organosilicon compound) is larger than that of the conventional silicone resin, the above curable organosilicon compound has a gas barrier property and adhesiveness unique to the organic skeleton. Although improved, the heat resistance and the ultraviolet resistance were inferior. Furthermore, even with respect to deterioration due to long-term use, it is inferior to conventional addition-curable silicone resins, so the amount of catalyst that can be added is also small, and the curing time was long like conventional addition-curable silicone resins. Thus, a sealing material and sealing material having heat resistance and weather resistance like conventional addition-curable silicone resins, excellent in gas barrier properties and adhesiveness, and having a short curing time comparable to epoxy resins are required. ing.

Unexamined-Japanese-Patent 2000-198930 (patent 3523098) gazette JP 2005-343998 (patent 4198091) JP 2008-248170 A JP, 2009-203258, A JP, 2010-6956, A JP, 2010-53204, A JP, 2010-65161, A JP, 2010-138380, A JP, 2009-275206, A JP, 2002-317048 (patent 4066229) JP, 2008-274185, A JP, 2009-084478, A Unexamined-Japanese-Patent No. 2010-242043 JP, 2011-42732, A

  In order to solve these current problems, the present invention has excellent light transmittance after heating of the cured product and light transmittance after ultraviolet irradiation, and is excellent in storage stability with a short curing time (gel time). It is an object of the present invention to provide a resin composition for an optical semiconductor component, a sealing material or a sealing material for an optical semiconductor component, and a cured product thereof.

As a result of intensive studies to achieve the above object, the inventors of the present invention have found that resin compositions containing a thermosetting organosilicon compound, a hydrosilylation catalyst, and a phenol compound have a short curing time <, storage stability It has been found that the present invention is applied to a sealing material or sealing material for optical semiconductor parts.
That is, the present invention provides the following resin composition for optical semiconductor parts, a sealing material or sealing material for optical semiconductor parts, and a cured product.
(1) A resin composition comprising (A) thermosetting organic silicon compound, (B) hydrosilylation catalyst, and (C) phenolic compound, wherein the (A) thermosetting organic silicon compound is contained in one molecule. And at least one unsaturated bond group and at least one hydrosilyl group in the following formula (1)

A resin composition for an optical semiconductor component characterized by having a heterocycle represented by
(2) The thermosetting organic silicon compound (A) is an organic compound having two or more unsaturated bonding groups in one molecule of (a1) and a heterocycle represented by the formula (1); ) The compound according to the above (1), which is a compound obtained by reacting an organohydrogenpolysiloxane having two or more hydrosilyl groups in one molecule in the presence of the (B) hydrosilylation catalyst at 60 to 120 ° C. Resin composition for optical semiconductor parts,
(3) The resin composition for an optical semiconductor component according to the above (1) or (2), which is a liquid having a viscosity of 2,000 to 50,000 mPa · s at 25 ° C. of the (A) thermosetting organosilicon compound. ,
(4) The resin composition for an optical semiconductor component according to any one of the above (1) to (3), wherein the (C) phenol compound is a hindered phenol compound,
(5) A sealing material or sealing material for an optical semiconductor component comprising the resin composition for an optical semiconductor component according to any of the above (1) to (4), and (6) the optical semiconductor component according to the above (5) To provide a cured product characterized in that the sealing material or the sealing material is heat-cured.

  The resin composition for optical semiconductor parts of the present invention contains a thermosetting organosilicon compound, a hydrosilylation catalyst and a phenol compound. Therefore, the cured product can maintain high optical properties and high stability, that is, high light transmittance after heating or after ultraviolet irradiation, and the resin composition is useful as a sealing material or sealing material for optical semiconductor parts. It is.

Hereinafter, the present invention will be described in detail.
[(A) thermosetting organic silicon compound]
The thermosetting organosilicon compound (A) which is the main component of the resin composition for optical semiconductor parts of the present invention has one or more unsaturated bond groups and one or more hydrosilyl groups in one molecule, and Following formula (1)

And the heterocyclic ring represented by
In the formula (1), “—” described in the middle of the bond out of the ring from each of the three N atoms and one, two or three of the three bonds are It is a skeleton of the organohydrogenpolysiloxane mentioned, and 0, 1 or 2 out of 3 is an unsaturated bond group.

The thermosetting organosilicon compound (A) is an organic compound having two or more unsaturated bonding groups in one molecule of the component (al) and a heterocycle represented by the formula (1), and a component (a2) Can be produced by reacting an organohydrogenpolysiloxane having two or more hydrosilyl groups in one molecule of (B) in the presence of (B) a hydrosilylation catalyst at 60 to 120 ° C., and at 25 ° C. It is preferable that the liquid has a viscosity of 2,000 to 50,000 mPa · s.
The viscosity at 25 ° C. is more preferably 2000 to 30000 mPa · s. When the viscosity is 2,000 to 50,000 mPa · s, it is easy to handle and the optical properties of the resulting cured product are preferable.
The viscosity can be measured, for example, at 25 ° C. according to JIS K 5600-2-3 using a cone-plate viscometer.
The organic compound of the component (al) is a heterocycle-containing compound having two or more unsaturated bond groups capable of hydrosilylation reaction in one molecule, and, for example, the following chemical formula (1-1)

The isocyanuric acid derivative represented by these can be used.
In the above formula (1-1), R ¹ represents a hydrogen atom, an unsaturated hydrocarbon group, a saturated hydrocarbon group having 1 to 5 carbon atoms, or a cyclic ether group, and R ² independently represents an unsaturated hydrocarbon Groups, which may be the same or different.
The unsaturated hydrocarbon group of R ¹ and R ² preferably has 2 to 6 carbon atoms, and examples thereof include a vinyl group, an allyl group, a propenyl group and a butenyl group. Examples of the cyclic ether group in R ¹ include an epoxy group, an oxetane residue, a tetrahydrofuran residue, and a tetrahydropyran residue. The saturated hydrocarbon group having 1 to 5 carbon atoms is a methyl group to a pentyl group.

Specific examples of the organic compound of the component (al) include triallyl isocyanurate, diallyl glycidyl isocyanurate, diallyl methyl isocyanurate, diallyl isocyanurate, tris (2-acryloyloxy) isocyanurate, trimethallyl isocyanurate, Examples include allyl isocyanurate prepolymer, triallyl cyanuric acid and the like. These can be used singly or in combination of two or more. Among these, triallyl isocyanurate is preferable in terms of heat resistance and UV resistance.
The organohydrogenpolysiloxane of the component (a2) contains a hydrogen atom (that is, a hydrosilyl group) bonded to two or more silicon atoms in one molecule, preferably three or more silicon atoms. It contains a hydrogen atom to be bonded. The organohydrogenpolysiloxane may be linear, branched, or three-dimensional network resinous.
As organohydrogenpolysiloxane, for example, the following formulas (2) to (6)

In the above formulas (2) to (6), each R ³ independently represents a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms, or a phenyl group. They may be identical or different. Moreover, repeating unit n or (m + n) shows 1-25, and it is preferable from a viewpoint of a viscosity and handling that it is 1-20. However, in the formulas (3) and (4), n or (m + n) represents 2 to 25 and is preferably 2 to 20 from the viewpoint of viscosity and handling.
Examples of the chain aliphatic hydrocarbon group having 1 to 10 carbon atoms include chain alkyl groups such as a methyl group, an ethyl group, a propyl group and an n-butyl group, and the like. As an aliphatic hydrocarbon group, cycloalkyl groups, such as a cyclopropyl group, cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, are mentioned, for example.

The organohydrogenpolysiloxane of component (a2) can be used alone or in combination of two or more. Further, from the viewpoint of light transmittance after heating and light transmittance after ultraviolet irradiation, compounds in which R ³ is a methyl group having 1 carbon atom are preferable, but from the viewpoint of gas barrier properties, all or part of R ³ Is preferably a compound containing a phenyl group, and from the viewpoint of crosslink density, it is preferable to have a branched polyfunctional structure such as that of formula (5) or a branched polyfunctional structure such as that of formula (6). .
Organohydrogenpolysiloxane (a2) can be obtained by known methods, for example, R ⁴ SiHCl ₂ and R ⁴ SiHCl (wherein, R ⁴ is free of aliphatic unsaturation is independently unsubstituted Or at least one chlorosilane selected from substituted monovalent hydrocarbon groups) can be obtained by cohydrolysis in combination. In addition, the organohydrogenpolysiloxane may be one obtained by equilibrating the thus obtained cohydrolyzed polysiloxane.

  In the production of the thermosetting organosilicon compound (A), it is preferable to react 1 to 1.2 equivalents of the organohydrogenpolysiloxane of the component (a2) with 1 equivalent of the unsaturated bond group of the (al) organic compound. . If it is 1 equivalent or more, when it is set as hardened | cured material, the unreacted unsaturated bond group in (al) organic compound can be almost eliminated and there is no fear of coloring, and if it is 1.2 equivalent or less, it is set as hardened | cured material Sometimes the number of unreacted hydrosilyl groups can be kept low. By setting the content in the above range, there is no possibility that the hardness, heat resistance, etc. of the cured product will be deteriorated, so that the function of the cured product can be improved.

[(B) hydrosilylation catalyst]
(B) The hydrosilylation catalyst is, as described above, an organic compound having two or more unsaturated bonding groups and a heterocyclic ring in one molecule of component (al), and two or more in one molecule of component (a2). The organohydrogenpolysiloxane having a hydrosilyl group is used in a hydrosilylation reaction, and is usually carried as it is with the thermosetting organosilicon compound of component (A) into the resin composition for optical semiconductor parts of the present invention. You may add more as needed.
(B) The hydrosilylation catalyst can use a catalyst commonly used to promote the hydrosilylation reaction between a silicon atom (hydrosilyl group) to which a hydrogen atom is bonded (hydrosilyl group) and a hydrocarbon having an unsaturated bond, and generally a siloxane The catalyst is not particularly limited as long as it is a known catalyst used for the hydrosilylation reaction of
As the above-mentioned (B) hydrosilylation catalyst, for example, a transition metal catalyst containing platinum, rhodium, palladium, ruthenium, iridium and the like can be used, and among them, platinum and a platinum compound are preferably used.

Examples of platinum compounds include hexachloroplatinate (IV) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, etc. preferable. These can be used alone or in combination of two or more.
The amount of the hydrosilylation catalyst (B) used is preferably in the range of 0.01 to 100 ppm by mass, based on the total mass of the components (al) and (a2) as a platinum group metal. More preferably, it is 1 to 30 mass ppm.
If it is 0.01 mass ppm or more, the reaction can be favorably advanced, and if it is 100 mass ppm or less, gelation and coloring at the time of reaction can be prevented.

[Reaction conditions of hydrosilylation reaction]
The hydrosilylation reaction of the organic compound of component (al) with the organohydrogenpolysiloxane of component (a2) in the presence of a hydrosilylation catalyst (B) can be carried out by any known method.
The hydrosilylation reaction can be carried out without solvent, but from the viewpoint of reaction control, it is preferable to carry out in a dilution solvent which does not affect the reaction. The dilution solvent is not particularly limited except that it has no unsaturated bond group and does not participate in the hydrosilylation reaction.
Examples of the dilution solvent include alcohols such as methanol, ethanol, 2-propanol and butanol; aliphatic hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane and ethylcyclohexane: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like Aliphatic ketones such as cyclopentanone; aromatics such as benzene, toluene, orthoxylene, metaxylene, paraxylene, chlorobenzene and dichlorobenzene; N, N-dimethylformamide, N, N-dimethylacetamide and N- Aliphatic amides such as methyl pyrrolidone; and ethers such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether. These can be used alone or in combination of two or more.
Further, the reaction temperature of the hydrosilylation reaction is preferably 60 to 120 ° C., more preferably 80 to 110 ° C. By setting the temperature to 60 ° C. or higher, the reaction proceeds well and does not significantly delay. Further, by setting the temperature to 120 ° C. or less, the reaction can be easily controlled, and gelation and coloring can be prevented.

[(C) phenolic compound]
The phenol compound used in the present invention is characterized as having an effect as a reaction accelerator and also acting as an anti-wrinkle agent on the surface of the cured product.
As described above, since the thermosetting organosilicon compound has a large proportion of the organic skeleton site, coloring and deterioration are likely to occur due to the synthetic reaction or exposure to heat and UV light as compared with the silicone resin.
Although the method of reducing the said (B) hydrosilylation catalyst is mentioned as a coloring avoidance measure, the reaction fall by reducing the amount of catalysts and heat resistance fall will occur. In addition, the hydrosilylation reaction is easily influenced by substances that become catalyst poisons, such as sulfur compounds, present in the air and in impurities contained in the resin composition, and is further influenced by a small amount of catalyst. It will be easier. Furthermore, there is also a problem that a difference in curing reaction occurs between the surface and the inside due to the influence of oxygen, and wrinkles occur on the surface. On the other hand, when the amount of the catalyst is increased to solve these problems, the reactivity and heat resistance are improved, and the catalyst poison is less affected. Furthermore, although the appearance wrinkles are reduced or not generated, the transparency is reduced due to coloring and the storage stability is reduced, and both are in a trade-off relationship.

Therefore, when the (C) phenol compound of the present invention is added, the reaction promoting effect and the surface wrinkle preventing effect can be seen, and the above problem can be solved even when the (B) hydrosilylation catalyst is small.
Especially as a phenol compound used for this invention, the hindered phenol compound used as antioxidant and a polymerization inhibitor is preferable. In addition, hindered phenol compounds that do not contain a sulfur atom or the like that can be a catalyst poison for the hydrosilylation reaction are more preferable. Examples of hindered phenol antioxidants include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tris- (3 , 5-Di-tert-butyl-4-hydroxybenzyl) -isocyanurate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2 , 4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 3,9 -Bis [2- [3- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5 ] Examples thereof include decane and 2,2'-methylenebis (6-tert-butyl-4-methylphenol), and commercially available products include IRGANOX 245, IRGANOX 259, IRGANOX 1010, IRGANOX 3114, and IRGANOX manufactured by BASF Japan Ltd. 1076, IRGANOX 1330, IRGANOX 3114, ADEA's AO-60, AO-20, AO-50, AO-330, Sumitomo Chemical's SUMILIZER GA-80, SUMILIZER MDP-S, etc. . These can be used alone or in combination of two or more.
The amount of the phenolic compound (C) used is preferably in the range of 1 to 1,000 mass ppm, preferably 50 to 500 mass ppm, based on the amount of the thermosetting organic silicon compound (A). More preferable. If it is 1 mass ppm or more, the reaction can be favorably promoted and wrinkles on the surface of the cured product can be prevented. If it is 1,000 mass ppm or less, coloring can be prevented even during reaction, long-term heat and ultraviolet light exposure.

  The composition of the present invention may further contain additives such as dyes, pigments, surfactants, oxide nanoparticles, nitride nanoparticles, dye-proofing agents, metal fillers and heat-resistant agents. In addition, as long as the curability is not impaired, it is also possible to use a solvent, a reactive diluent or the like to improve the viscosity adjustment and the handling property.

[Sealing material or sealing material for optical semiconductor parts]
The present invention provides a sealing material or sealing material for an optical semiconductor component containing a thermosetting organosilicon compound. Specific examples of the optical semiconductor component which can use the above-mentioned sealing material or sealing material for an optical semiconductor component include an LED, a photo sensor, a photo IC, a photo transistor, a position detecting element, an image sensor, an infrared detecting element, and a color sensor Etc. are raised.
Among them, the sealing material or sealing material for an optical semiconductor component of the present invention is preferably used for an LED.
Examples of LEDs include red LEDs, green LEDs, and yellow LEDs made of compound semiconductor GaP, compound semiconductor GaAs and compound semiconductor GaN, as well as recent LEDs having high luminous efficiency and short wavelength.
Moreover, the above-mentioned composition can be used also for existing LED sealing, and is most suitable for a high efficiency LED having a luminous efficiency of 100 lm / W or more at a wavelength of blue or ultraviolet region developed recently. .
[Cured product]
For example, after the LED, which is a typical example of an optical semiconductor component, is sealed or sealed in a mold using the above-described encapsulant or sealing material for an optical semiconductor component, the cured product of the present invention is obtained by heat curing. be able to. The conditions for heat curing are 80 to 200 ° C. for 0.5 to 10 hours, preferably 100 to 180 ° C. for 1 to 6 hours.

  Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following examples unless the gist is exceeded.

Synthesis Example 1
(A) Synthesis of Thermosetting Organosilicon Compound (Resin A) Triallyl isocyanurate as component (a1) in a 500-ml, four roceparable flask equipped with a thermometer, a condenser, a nitrogen introduction pipe, and a stirring frame. 38.0 parts by mass of [product name: Taike, manufactured by Nippon Kasei Kogyo Co., Ltd.] and 50 parts by mass of toluene were added and stirred at normal temperature. There, a solution of platinum divinyl tetramethyl disiloxane complex in xylene solution (trade name: SIP 6831.2, manufactured by Gelest Inc.) was used as a hydrosilylation catalyst to be the component (B) in the resin composition for optical semiconductor parts of the present invention. 15 parts by mass was added and heated to 80 ° C. using a mantle heater. Organohydrogenpolysiloxane (trade name: HMS-301, manufactured by Gelest Inc., molecular weight 1,900-2,000, functional group equivalent weight 245 (catalog value)) as component (a2) dissolved in 100 parts by mass of toluene there. 112.0 parts by mass was dropped into the reaction solution over 1 hour. The temperature of the reaction solution was raised to 100 ° C. and stirred for 5 hours as it was. The solvent such as toluene and xylene in the obtained reaction mixture was distilled off under reduced pressure to obtain a thermosetting organosilicon compound (Resin A). The obtained resin was a colorless and transparent liquid, and the viscosity at 25 ° C. was 6,500 mPa · s.

Synthesis Example 2
(B) Synthesis of Thermosetting Organosilicon Compound (Resin B) Triallyl isocyanurate as component (a1) in a 500-ml, four roceparable flask equipped with a thermometer, a condenser, a nitrogen introduction pipe, and a stirring frame. 19.7 parts by mass of [product name: Taike, manufactured by Nippon Kasei Kogyo Co., Ltd.] and 50 parts by mass of toluene were added and stirred at normal temperature. There, a solution of platinum divinyl tetramethyl disiloxane complex in xylene solution (trade name: SIP 6831.2, manufactured by Gelest Inc.) was used as a hydrosilylation catalyst to be the component (B) in the resin composition for optical semiconductor parts of the present invention. 15 parts by mass was added and heated to 80 ° C. using a mantle heater. Organohydrogenpolysiloxane (trade name: DMS-H11, manufactured by Gelest Inc., molecular weight 1,000-1, 100, functional group equivalent 550 (catalog value)) as component (a2) dissolved in 100 parts by mass of toluene there. 130.3 parts by mass was dropped into the reaction solution over 1 hour. The temperature of the reaction solution was raised to 100 ° C. and stirred for 5 hours as it was. A solvent such as toluene or xylene in the obtained reaction mixture was distilled off under reduced pressure to obtain a thermosetting organosilicon compound (Resin B). The obtained resin was a colorless and transparent liquid, and the viscosity at 25 ° C. was 10,500 mPa · s.

[Examples 1 to 5 and Comparative Examples 1 to 5]
Each component was mixed by the compounding ratio shown in Table 1, and it was set as the resin composition for optical semiconductor components, and the resin composition for comparison.

<Measurement item>
(1) Cured product characteristics The above resin composition is poured into a cell prepared by sandwiching a 1 mm thick silicone rubber sheet as a spacer in two glass plates, and heating at 150 ° C. for 2 hours and 180 ° C. for 2 hours Then, it was cured to prepare a plate-like cured product having a thickness of 1 mm.
The work made by a plate-like cured product properties were evaluated by the following method, and the results are shown in Table 1.
(1-1) Appearance The plate-like cured product was visually observed to evaluate color and transparency.
(1-2) Light transmittance (initial value)
The light transmittance of 400 nm of the plate-like cured product immediately after curing was measured using an ultraviolet visible spectrophotometer (V-570) manufactured by JASCO Corporation.
(1-3) Light transmittance after ultraviolet irradiation The plate-like cured product was irradiated with ultraviolet light for 100 hours using a cut filter that cuts light of a wavelength of 300 nm or less with an ultraviolet irradiation device, and then the light transmittance of 400 nm was measured. .
(1-4) Light transmittance after heating The plate-like cured product was placed in an oven at 150 ° C. for 200 hours and heated, and then the light transmittance of 400 nm was measured.
(1-5) Hardness The above resin composition is poured into a cell prepared by sandwiching a 5 mm thick silicone rubber sheet as a spacer in two glass plates, and the resin composition is cured under the following two conditions to obtain a 5 mm thick plate A rod-shaped cured product was produced.
The surface hardness of the produced plate-like cured product was measured using a Shore A hardness tester.
Condition 1: Heat for 2 hours at 150 ° C. Condition 2: Heat for 2 hours at 150 ° C., 2 hours at 180 ° C.
(1-6) The above resin composition was poured into a mold having a diameter of 4 cm and a thickness of 1 cm, and heated at 150 ° C. for 2 hours to produce a cured product without covering the top of the mold. . The presence or absence of wrinkles on the surface of the cured product was observed.

(2) Storage stability of resin composition
(2-1) Initial Viscosity and Viscosity Change Rate The initial viscosity of the above resin composition and the viscosity at 25 ° C. after storage for 120 hours at 25 ° C. were measured using a cone and plate viscometer according to JIS K 5600-2-3. did. Moreover, the viscosity change rate was calculated using the following formula.
Viscosity change rate (%)
= [(Viscosity after storage for 120 hours)-(initial viscosity)] x 100 / [initial viscosity]
(2-2) Gel Time-Influence of Catalyst Poisoning A resin composition containing a sulfur compound as a substance to be a catalyst poison was prepared, and gel time at 150 ° C. was measured initially and after storage at 25 ° C. for 120 hours. The measuring method of gel time was performed according to the gelation time A method prescribed | regulated to 7.5.1 of JISC2161. Also, the gel time change rate was calculated using the following equation.
Gel time change rate (%)
= [(Gel time after storage for 120 hours)-(initial gel time)] x 100 / [initial gel time]
Table 1 summarizes the measurement items described above and the measurement values obtained in Examples 1 to 5 and Comparative Examples 1 to 5.

  As apparent from Table 1, as in Examples 3 and 5, even if the sulfur compound to be a catalyst poison is present, the phenol compound of the component (C) is present, so the hardness of the cured product is lowered. It has been shown that the occurrence of wrinkles on the surface and no increase in gel time has occurred. On the other hand, in Comparative Examples 3 to 5 in which a sulfur compound is present, since the phenol compound of the component (C) is not present, the hardness of the cured product decreases, generation of wrinkles on the surface of the cured product, gel time of the resin composition In addition, it is shown that the light transmittance of the cured product after heating is lowered. In Comparative Examples 1 and 2, since no sulfur compound to be a catalyst poison is present, the decrease in the hardness of the cured product and the increase in the gel time of the resin composition do not so much even if the phenol compound of component (C) is not present. Not big. However, in Comparative Example 1, wrinkles are generated on the surface of the cured product, and the hardness (condition 1) is somewhat low. In Comparative Example 2, no wrinkles are generated on the surface of the cured product, and the hardness is the same as that of the example. It is shown that sex is bad.

  The cured product of the resin composition for optical semiconductor parts of the present invention has high optical properties and high stability. That is, in addition to maintaining high light transmittance after heating and light transmittance after ultraviolet irradiation, it is less susceptible to catalyst poisons (eg, sulfur compounds), and has characteristics excellent in curing reaction and storage stability. doing. In addition, since the curing reaction time can be significantly shortened, it is useful as a sealing material or sealing material for optical semiconductor components.

Claims (6)

(A1) an organic compound having two or more unsaturated bonding groups in one molecule and a heterocycle represented by the following formula (1), and (a2) an organohydro having two or more hydrosilyl groups in one molecule A resin composition comprising (A) a thermosetting organosilicon compound which is a hydrosilylation reaction product with genpolysiloxane , (B) a hydrosilylation catalyst, and (C) a hindered phenol compound, wherein The curable organosilicon compound has one or more unsaturated bond groups and one or more hydrosilyl groups in one molecule, and the following formula (1)

A polysiloxane having a heterocyclic ring represented by
The amount of the (B) hydrosilylation catalyst used is 0.01 to 100 ppm by mass based on the total mass of the (a1) and (a2) as a platinum group metal ,
The resin composition for an optical semiconductor component, wherein the amount of the (C) hindered phenol compound used is 1 to 1000 mass ppm with respect to the amount of the (A) thermosetting organic silicon compound.   The resin according to claim 1, wherein the amount of the (C) hindered phenol compound used is 1 to 500 mass ppm with respect to the amount of the (A) thermosetting organic silicon compound. Composition. The amount of the (B) hydrosilylation catalyst used is 0.1 to 30 mass ppm as a platinum group metal based on the total mass of the (a1) and (a2). Resin composition for optical semiconductor parts.   The resin composition for an optical semiconductor component according to any one of claims 1 to 3, which is a liquid having a viscosity of 2,000 to 50,000 mPa · s at 25 ° C of the (A) thermosetting organosilicon compound.   The sealing material or sealing material for optical semiconductor components which consists of a resin composition for optical semiconductor components in any one of Claims 1-4.   (A1) an organic compound having two or more unsaturated bonding groups in one molecule and a heterocyclic ring represented by the formula (1), and (a2) an organohydro having two or more hydrosilyl groups in one molecule After reacting the genpolysiloxane with the (B) hydrosilylation catalyst at 60 to 120 ° C. to produce the (A) thermosetting organic silicon compound, the (C) hindered phenol compound is added The manufacturing method of the resin composition for optical semiconductor components in any one of Claims 1-4.