JP5788839B2 - Curable resin composition, cured product thereof and optical semiconductor device using the same - Google Patents

Description

  The present invention relates to a curable resin composition useful as an optical device / material for optical parts, an insulating material for electronic devices / electronic parts, a coating material, and the like, a cured product thereof, and an optical semiconductor device.

  In general, an optical semiconductor device typified by an LED (light-emitting diode) has low power consumption and a long life, so that it is a backlight for a mobile phone, a backlight for a liquid crystal television, a lighting for an automobile, a lighting fixture, and a signboard. It is used for a wide range of applications.

  In particular, as LED devices are widely used in outdoor lighting applications and automotive applications, high durability is required for resin compositions used as LED element sealing materials, electronic device insulating materials, or coating materials. ing. That is, there is a demand for performance that prevents cracking even under severe temperature cycles, has excellent resistance to discoloration when exposed to high temperatures for a long period of time, and prevents permeation of gases such as SOx.

On the other hand, generally, the light emission characteristics of an optical semiconductor device are determined from a combination of an optical wavelength conversion material (hereinafter referred to as a phosphor) and an optical semiconductor element, and an optical semiconductor device having various purposes of color rendering depending on the weight ratio of the mixed phosphor. It is possible to obtain However, in the production of such an optical semiconductor device, it has been difficult to continuously produce light-emitting devices with stable color rendering properties. In a specific example, a sealing device in which a phosphor is added to a highly transparent curable resin composition is applied to a package substrate having a concave shape in which an optical semiconductor element is mounted and wire bonded, using a dispensing device. Although it is manufactured by curing after filling a predetermined amount, in this step, the added phosphor has a higher specific gravity than the curable resin composition, so the sealing agent is filled with the passage of time. Sinks under its own weight under the container. Therefore it is common phosphor is a material having an average particle size of less than 20μm at a density of about 4-6 g / cm ^3, the curable resin composition is the density of about 1 g / cm ^3, It can be easily understood that the phosphor precipitates over time during the sealing process time of the manufacturing process. Therefore, when filling the package substrate with the sealing agent mixed with the phosphor, a change occurs in the dispersed state of the phosphor in the initial stage and the late stage of manufacturing, and the phosphor content in the sealing agent is large in the initial stage of manufacturing. In the later stage of production, a phenomenon occurs in which the phosphor content in the sealant is reduced. Since some of the phosphor content is directly linked to the amount of light that is converted into light, there is a problem in that the initially designed color rendering properties vary and a product with stable characteristics cannot be obtained.

  As an example for solving the above problem, in Patent Document 1, silicone rubber spherical fine particles having an average particle diameter of 0.1 to 100 μm are added to a thermosetting resin composition. However, in this method, the silicone rubber spherical fine particles themselves and the surface treatment agent are often inferior in heat resistance and light resistance, which is a problem. Further, Patent Document 2 proposes a method of preventing the phosphor from being precipitated by a method in which nanoparticles having an average particle diameter of 1 nm to 25 nm are dispersed in a nano state.

  However, in these methods proposed above, although the effect of preventing phosphor settling can be obtained for a curable resin composition having a relatively high viscosity exceeding 10,000 mPa · s at room temperature, No effect is obtained with respect to the curable resin composition, and there still remains a problem that the designed color rendering properties vary and a product with stable characteristics cannot be obtained.

  That is, when filling a package substrate with a sealing agent in which a phosphor is dispersed using a low-viscosity curable resin composition, there is no change in the phosphor dispersion state between the initial stage of production and the late stage of production, and the initial stage and the production stage. There is a need for a curable resin composition for optical semiconductor devices that contains the same amount of phosphor in the later stage and can maintain stable color rendering.

Japanese Patent No. 4591690 JP 2005-524737 A

  The present invention has been made in view of the above problems, and has high resistance to repeated thermal shocks. Therefore, cracks are hardly generated even under severe temperature cycles, and has excellent resistance to discoloration. An object of the present invention is to provide a curable resin composition capable of preventing transmission and maintaining color rendering properties stably, a cured product thereof, and an optical semiconductor device.

  In order to solve the above problems, according to the present invention, at least a phosphor particle and a curable resin composition to which nanoparticles having a primary particle diameter of 1 nm to less than 100 nm are added, the nanoparticles having a volume It is dispersed in the form of secondary agglomerated particles having an average particle size of 100 nm or more and 20 μm or less in conversion Q3, and silicone powder having an average particle size of 0.5 to 100 μm is further dispersed. A curable resin composition is provided.

  Such a curable resin composition has a high resistance to repeated thermal shocks, and therefore, hardly cracks even under severe temperature cycles, has excellent discoloration resistance, and prevents permeation of gases such as SOx. And a curable resin composition capable of stably maintaining the color rendering properties.

  The curable resin composition contains at least one of a silicone resin, a modified silicone resin, an epoxy resin, and a modified epoxy resin, and the viscosity of the curable resin composition at room temperature is 100 mPa · s to 10,000 mPa · s. It is preferable that

  If it is such a curable resin composition, the effect of the sedimentation preventing action of the phosphor particles can be further obtained.

  Moreover, it is preferable that the said curable resin composition contains a silicone resin or a modified silicone resin.

  Such a curable resin composition is useful as an optical coating material such as a light emitting diode or an LED element sealing material.

（式中、Ｒは同一又は異種の非置換もしくは置換の一価炭化水素基であり、Ａｒは同一又は異種の、ヘテロ原子を有してもよいアリール基であり、ｍは０又は１以上の整数、ｎは１以上の整数である。）
（Ａ−２）下記平均組成式（２）で表される構造を有する、分岐状または三次元構造のオルガノポリシロキサン：
Ｒ′_ｎ’（Ｃ_６Ｈ_５）_ｍ’ＳｉＯ_{（４−ｎ’−ｍ’）／２} （２）
［式中、Ｒ′は、同一又は異なり、置換もしくは非置換の一価炭化水素基、アルコキシ基及び水酸基のいずれかであり、全Ｒ′のうち０．１〜８０ｍｏｌ％がアルケニル基であり、ｎ’，ｍ’は１≦ｎ’＋ｍ’≦２、０．２０≦ｍ’／（ｎ’＋ｍ’）≦０．９５を満たす正数である。］
（Ｂ）脂肪族不飽和基を有さず、１分子あたり少なくとも２個のケイ素原子に結合した水素原子を有する有機ケイ素化合物、
（Ｃ）白金族金属を含むヒドロシリル化触媒、
を含む硬化性シリコーン樹脂組成物であることが好ましい。 Further, the curable resin composition is
(A) A compound of the following (A-1) and / or an organopolysiloxane of (A-2) (A-1) having a structure represented by the following general formula (1), and at least two per molecule Compounds having aliphatic unsaturated groups:

Wherein R is the same or different unsubstituted or substituted monovalent hydrocarbon group, Ar is the same or different aryl group which may have a hetero atom, and m is 0 or 1 or more. Integer, n is an integer of 1 or more.)
(A-2) Branched or three-dimensional organopolysiloxane having a structure represented by the following average composition formula (2):
R ′ _{n ′} (C ₆ H ₅ ) _{m ′} SiO _{(4-n′-m ′) / 2} (2)
[Wherein, R ′ is the same or different and is any one of a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group and a hydroxyl group, and 0.1 to 80 mol% of all R ′ is an alkenyl group, n ′ and m ′ are positive numbers satisfying 1 ≦ n ′ + m ′ ≦ 2 and 0.20 ≦ m ′ / (n ′ + m ′) ≦ 0.95. ]
(B) an organosilicon compound having no hydrogen unsaturated group and having hydrogen atoms bonded to at least two silicon atoms per molecule;
(C) a hydrosilylation catalyst containing a platinum group metal,
It is preferable that it is a curable silicone resin composition containing.

  With such a composition, the composition of the present invention can be stably maintained in an uncured state before the addition reaction starts, and the composition can be easily cured after the addition reaction starts. Can do. The component (B) can act as a crosslinking agent by hydrosilylation addition reaction with the component (A). By having (C) component, the hydrosilylation addition reaction of (A) component and (B) component can be accelerated | stimulated.

  In addition, in the component (A-1) represented by the general formula (1), it is preferable that Ar is a phenyl group and n is an integer of 1 to 100 because it can be relatively easily produced industrially.

  Thus, in the component (A-1), when Ar in the general formula (1) is a phenyl group, the refractive index and transparency are excellent, and the crack resistance is also excellent.

Furthermore, the said (B) component is the following average compositional formula (3):
R ″ _a H _b SiO _{(4-ab) / 2} (3)
Wherein R ″ is an identical or different unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom (excluding an aliphatic unsaturated group); 7 ≦ a ≦ 2.1, 0.001 ≦ b ≦ 1.0, and 0.8 ≦ a + b ≦ 3.0.
It is preferable that it is organohydrogen polysiloxane shown by these.

  Such component (B) is particularly useful for carrying out hydrosilylation reaction with component (A).

Moreover, it is preferable that the oxygen permeability of the hardened | cured material obtained by hardening | curing the said curable silicone resin composition is 1,000 cm < ³ > / m < ² > / 24h / atm or less.

  Thus, if the oxygen permeability of the cured product is not more than the above value, suppression of gas permeation of sulfur oxides and the like can be obtained effectively.

  Moreover, in this invention, the hardened | cured material formed by hardening | curing the said curable resin composition is provided.

  The cured product of the curable resin composition of the present invention has high resistance to repeated thermal shock and resistance to discoloration, and can suppress the gas permeation amount of SOx and the like.

  Furthermore, in this invention, the optical semiconductor device using the hardened | cured material of the said curable resin composition is provided.

  By filling the package substrate with the sealant made of the cured product, it is possible to provide an optical semiconductor device that is excellent in thermal shock resistance and thermal discoloration and stably maintains color rendering.

  As described above, the curable resin composition of the present invention has high resistance to repeated thermal shocks, and therefore, hardly undergoes cracking even under severe temperature cycles, and resists discoloration when exposed to high temperatures for long periods of time. It is a resin composition that gives a cured product that has excellent properties and can prevent the passage of gases such as SOx, and the package substrate is filled with a sealing agent in which phosphor particles are dispersed in a low-viscosity curable resin composition Even in this case, it is useful as a curable resin composition that contains the same amount of phosphor particles in the early stage of production and in the late stage of production and can stably maintain color rendering.

It is a schematic sectional drawing which shows an example of this invention optical semiconductor device.

Hereinafter, the present invention will be described in more detail.
As described above, when a package substrate is filled with a sealing agent having excellent thermal shock resistance, discoloration resistance, gas barrier properties, and further dispersed with phosphor particles using a low viscosity curable resin composition. In addition, there has been a demand for a curable resin composition for an optical semiconductor device capable of maintaining color rendering properties by containing the same amount of phosphor particles in the initial stage of production and the latter stage of production.

  Therefore, as a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found that at least phosphor particles and nanoparticles having a primary particle diameter of 1 nm to less than 100 nm are added. The nanoparticles are dispersed in the form of secondary agglomerated particles having an average particle size of 100 nm to 20 μm by volume conversion Q3, and silicone powder having an average particle size of 0.5 to 100 μm The present invention has been completed by finding that a curable resin composition characterized by being dispersed can achieve the above object.

  Hereinafter, the present invention will be described in detail. In the present specification, the “average particle diameter” means a particle diameter at a volume-based integrated value of 50% in a particle size distribution obtained by a laser diffraction / scattering method.

  The present invention relates to a curable resin composition mainly used for an optical semiconductor device, to which phosphor particles and nanoparticles having a primary particle size (average particle size of primary particles) of 1 nm or more and less than 100 nm are added. In the curable resin composition, the nanoparticles are dispersed in the form of secondary aggregation in an average particle size of 100 nm or more and 20 μm or less by volume conversion Q3, and further the silicone having an average particle size of 0.5 to 100 μm It is characterized in that the powder is dispersed.

  Such a curable resin composition has a high resistance to repeated thermal shocks, and therefore is hard to crack even under severe temperature cycles, and has excellent resistance to discoloration when exposed to high temperatures for long periods of time. It becomes. Furthermore, the presence of the nanoparticles in the curable resin composition in a secondary aggregated state effectively inhibits the force with which the phosphor particles attempt to move according to gravity, thereby preventing sedimentation. As a result, even when the dispensing process takes a long time, the phosphor particles in the LED device at the beginning and the latter of the dispensing process can be made substantially the same amount, and the handling property of the sealant can be improved. Can be increased.

  The primary particle diameter of the nanoparticles is 1 nm or more and less than 100 nm, and more preferably 5 nm or more and 50 nm or less. When the primary particle size is 100 nm or more, scattering of light emitted from the optical semiconductor occurs, which causes a decrease in luminance when used as an optical semiconductor device, which is not preferable. If the thickness is less than 1 nm, handling at the time of addition is difficult, and further, it is difficult to control the particle size of the secondary aggregated particles.

  In the present invention, when nanoparticles having a primary particle size in the above range are added to the curable resin composition, the average particle size of the secondary aggregated particles is Q3 in terms of volume in the curable resin composition. It is characterized by being dispersed in a form of 100 nm or more and 20 μm or less. More preferably, it is 100 nm or more and 10 μm or less. If the average particle size of the secondary aggregated particles is less than 100 nm, the effect of preventing the sedimentation of the phosphor particles cannot be obtained, which causes color variation, which is not preferable. On the other hand, if it exceeds 20 μm, the particle size of the secondary agglomerated particles is large, so that the nozzle used in the dispensing operation is clogged and the content of the phosphor particles in the sealant may be varied, which is not preferable.

In the curable resin composition, the form of the secondary agglomerated particles having a particle size in the above range can be obtained by combining and dispersing the below-described nanoparticles and the curable resin composition. A known method can be used as a method for dispersing the nanoparticles in the curable resin composition, and there is no particular limitation.
Examples thereof include mixing with various types of mixers, mixing with a self-revolving stirrer, and kneading using a roll. During the stirring, the inside of the stirring system may be evacuated for the purpose of defoaming. Preferably, the mixing is carried out by a simple revolutionary agitator equipped with a vacuuming function. Nanoparticles preliminarily aggregated to a target particle size may be dispersed.

Although the example of the said nanoparticle is given next, it is not necessarily limited to these.
Secondary particles moderately aggregated in the curable resin composition so that the effect of preventing sedimentation of phosphor particles having various shapes and specific gravities in the target product can be obtained (average particle diameter of Q3 to 100 μm in Q3) ), And nanoparticles having a refractive index corresponding to the purpose may be used. For example, in the case of silica, silica produced by a dry method such as fumed silica or fused silica, or silica produced by a wet method such as colloidal silica, sol-gel silica, or precipitated silica can be used. Other examples include alumina, magnesium oxide, antimony oxide, aluminum hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. Among these, fumed silica and alumina, which have few volatile components and can obtain high transparency, are preferably used.

The nanoparticles can take any form, for example, spheres, flakes, needles or plates. Preferably, it is a sphere that tends to take the form of secondary aggregation.
The amount of nanoparticles added is not particularly limited as long as the effect of preventing the precipitation of phosphor particles can be obtained, but is preferably 50 parts by mass or less, more preferably 100 parts by mass of the base resin. 20 parts by mass or less. If it is the above-mentioned addition amount, there is no possibility of causing nozzle clogging during the dispensing process.

  The nanoparticles may be surface-treated with a silane coupling agent for the purpose of controlling the secondary particle diameter. By subjecting the nanoparticles to surface treatment, the cohesiveness of the secondary particles is reduced, and secondary particles having a small particle size can be obtained. Therefore, moderately agglomerated secondary particles (with an average particle diameter of 100 nm to 20 μm in Q3) are obtained so as to obtain the sedimentation preventing effect of phosphor particles having various shapes and specific gravity in the target optical semiconductor device. It suffices to select within a range. As the silane coupling agent, an alkyl group-containing silane coupling agent, an alkenyl group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a (meth) acryl group-containing silane coupling agent, an isocyanate group-containing silane coupling agent, Examples include known isocyanurate group-containing silane coupling agents, amino group-containing silane coupling agents, mercapto group-containing silane coupling agents, and the like.

  The curable resin composition of the present invention is characterized in that a silicone powder having an average particle size of 0.5 to 100 μm is dispersed together with the nanoparticles.

The advantage obtained by adding silicone powder is, firstly, improvement in mechanical properties. As can be seen from the low elasticity of silicone powder, it acts as a stress relieving agent for thermal shock that is repeatedly applied when the light emitting element is turned on / off, and therefore has high resistance to thermal shock and is subjected to severe temperature cycles. However, it provides a sealing resin that does not easily crack.
Furthermore, it is possible to modify the property of a general rubber material “having a specific tack (adhesiveness) and it is difficult to protect the LED element firmly because it is a rubber material”. That is, tack can be suppressed and the cured film can be strengthened.

  The second is improvement of discoloration resistance. Silicone powder is known to have little discoloration in a high-temperature environment, and discoloration during heating can be suppressed by blending with a sealing resin. Silicone powder does not absorb light, and unlike other organic resin powders, it does not gradually turn black upon receiving ultraviolet light from a light emitting element. As a result, discoloration of the sealing resin in a high-temperature environment can be suppressed, and furthermore, transparency can be maintained even when exposed to ultraviolet light for a long time, so that a light-emitting semiconductor device having a longer life is obtained. be able to.

  Examples of the silicone powder include silicone resin powders, which are fine polyorganosilsesquioxane powders, such as JP-B-40-16917, JP-A-54-72300, JP-A-60-13813, and JP-A-3. No. 244636, JP-A-4-88023, and a silicone composite powder having a structure in which a polyorganosilsesquioxane fine powder (resin) is coated on the surface of a silicone rubber powder, for example, JP-A-7-196815 Some of these silicone powders may be used alone or in combination of two or more. The said silicone powder can be produced with a well-known manufacturing method, and is available as a commercial item.

  As such silicone powder, those having an average particle diameter in the range of 0.5 to 100 μm are used, and more preferably 1 to 15 μm. When the average particle size is less than 0.5 μm, the powders are aggregated when dispersed in the composition, resulting in a decrease in strength of the cured product of the resin composition. Causes discoloration due to oxidation and causes deterioration of heat discoloration. On the other hand, if the average particle diameter exceeds 100 μm, it is not preferable from the viewpoint of uniform dispersion in the cured product and deterioration of the dispensing workability (specifically, stringing and clogging of the dispensing nozzle).

  The content of the silicone powder is preferably 0.1 to 500 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass in total of the components (A) and (B) described below. If the content is 0.1 parts by mass or more, improvement in the thermal shock resistance, discoloration upon heating, and gas barrier properties of the cured product of the target resin composition can be obtained, and if the content is 500 parts by mass or less. Since the composition has a high viscosity and there is no fear that the workability at the time of producing a cured product is deteriorated, it is industrially preferable.

  Examples of such silicone powder include silicone resin powder such as KMP590, KMP701, X-52-854, and X-52-1621 manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include, but are not limited to, KMP600, KMP601, KMP602, KMP605, and X-52-7030 manufactured by Shin-Etsu Chemical Co., Ltd.

  Examples of the phosphor particles include those that absorb light from a semiconductor light emitting diode having a nitride-based semiconductor as a light emitting layer and convert the light into light of a different wavelength. For example, it is mainly activated by nitride phosphor particles / oxynitride phosphor particles mainly activated by lanthanoid elements such as Eu and Ce, lanthanoid phosphor particles such as Eu, and transition metal elements such as Mn. Alkaline earth metal halogenapatite phosphor particles, alkaline earth metal halogen borate phosphor particles, alkaline earth metal aluminate phosphor particles, alkaline earth metal silicate phosphor particles, alkaline earth metal sulfides Phosphor particles, alkaline earth metal thiogallate phosphor particles, alkaline earth metal silicon nitride phosphor particles, germanate phosphor particles, or rare earth aluminate phosphors mainly activated by lanthanoid elements such as Ce Particles, rare earth silicate phosphor particles or organic and organic complex phosphor particles mainly activated by lanthanoid elements such as Eu, Ca-Al-Si-O-N Is preferably at least any one or more selected from the like oxynitride glass phosphor particles. As specific examples, the following phosphor particles can be used, but are not limited thereto.

Nitride-based phosphor particles mainly activated by lanthanoid elements such as Eu and Ce are M ₂ Si ₅ N ₈ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn) There is.) In addition, there are MSi ₇ N ₁₀ : Eu, M _1.8 Si ₅ O _0.2 N ₈ : Eu, M _0.9 Si ₇ O _0.1 N ₁₀ : Eu (M is the same as described above). .

Examples of oxynitride phosphor particles mainly activated by lanthanoid elements such as Eu and Ce include MSi ₂ O ₂ N ₂ : Eu (M is the same as described above).

M ₅ (PO ₄ ) ₃ X: R (M is the same as described above) for alkaline earth halogen apatite phosphor particles mainly activated by lanthanoid-based elements such as Eu and transition metal-based elements such as Mn. , X is at least one selected from F, Cl, Br, and I. R is Eu, Mn, and one or more of Eu and Mn.

The alkaline earth metal borate halogen phosphor particles include M ₂ B ₅ O ₉ X: R (M is the same as described above, and X is at least one selected from F, Cl, Br, and I). R is Eu, Mn, or any one of Eu and Mn).

Alkaline earth metal aluminate phosphor particles include SrAl ₂ O ₄ : R, Sr ₄ Al ₁₄ O ₂₅ : R, CaAl ₂ O ₄ : R, BaMg ₂ Al ₁₆ O ₂₇ : R, BaMg ₂ Al ₁₆ O ₁₂ : R, BaMgAl ₁₀ O ₁₇ : R (R is one or more of Eu, Mn, Eu and Mn).

Examples of the alkaline earth metal sulfide phosphor particles include La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, and Gd ₂ O ₂ S: Eu.

The rare earth aluminate phosphor particles mainly activated with a lanthanoid element such as Ce include Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al _0.8 Ga _0.2 ) ₅ O ₁₂ : Ce, (Y, Gd) ₃ (Al, Ga) ₅ O _{12 and} other YAG phosphor particles represented by the composition formula. Further, there are Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which a part or all of Y is substituted with Tb, Lu or the like.

Other phosphor particles include ZnS: Eu, Zn ₂ GeO ₄ : Mn, MGa ₂ S ₄ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is And at least one selected from F, Cl, Br, and I.).

  The phosphor particles described above contain one or more selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, Ti instead of Eu or in addition to Eu as desired. It can also be made.

  Further, phosphor particles other than the above-described phosphor particles and having the same performance and effect can also be used.

The Ca—Al—Si—O—N-based oxynitride glass phosphor particles are expressed in terms of mol%, CaCO ₃ is converted to CaO, 20 to 50 mol%, and Al ₂ O ₃ is 0 to 30 mol. %, SiO is 25 to 60 mol%, AlN is 5 to 50 mol%, rare earth oxide or transition metal oxide is 0.1 to 20 mol%, and the total of the five components is 100 mol%. Is a phosphor particle using as a base material. In addition, in the phosphor particles using oxynitride glass as a base material, the nitrogen content is preferably 15 wt% or less, and other rare earth element ions serving as a sensitizer in addition to the rare earth oxide ions are rare earth oxides. It is preferable to contain as a co-activator in content in the range of 0.1-10 mol% in fluorescent glass.

  The curable resin composition contains at least one selected from a silicone resin, a modified silicone resin, an epoxy resin, and a modified epoxy resin, and preferably has a viscosity at room temperature (in the range of 5 to 35 ° C.). 100 mPa · s or more and 10,000 mPa · s or less, more preferably 100 mPa · s or more and 5000 mPa · s or less. If it is 100 mPa · s or more, the effect of preventing sedimentation of the phosphor particles can be obtained, and the color variation can be improved. If it is 10000 mPa · s or less, there is no fear of a decrease in workability due to a decrease in the speed at the time of coating, a variation in the filling amount of the sealant due to threading of the sealant, and a device contamination in the dispensing process.

The curable resin composition of the present invention preferably further includes a silicone resin and a modified silicone resin from the viewpoints of transparency, heat resistance, and light resistance.
The curable silicone resin composition and the curable modified silicone resin composition of the present invention are useful as optical coating materials such as light-emitting diodes and LED element encapsulating materials. A composition as exemplified is preferred, but not limited thereto.

（式中、Ｒは同一又は異種の非置換もしくは置換の一価炭化水素基であり、Ａｒは同一又は異種の、ヘテロ原子を有してもよいアリール基であり、ｍは０又は１以上の整数、ｎは１以上の整数である。） Curable silicone resin composition Hereinafter, the curable silicone resin composition effective for the present invention preferably contains the following components (A) to (C). Each of these components will be described in detail.
Component (A) Component (A) used in the present invention includes the following compound (A-1) and / or organopolysiloxane (A-2). The component (A-1) is a linear diorganopolysiloxane having a main chain having repeating diarylsiloxane units. The (A-1) component organopolysiloxane may be used alone or in combination of two or more different molecular weights, types of organic groups bonded to silicon atoms, and the like.
(A-1) A compound represented by the following general formula (1) and having at least two aliphatic unsaturated groups per molecule:

Wherein R is the same or different unsubstituted or substituted monovalent hydrocarbon group, Ar is the same or different aryl group which may have a hetero atom, and m is 0 or 1 or more. Integer, n is an integer of 1 or more.)

  In the component (A-1), the aryl group as Ar in the formula (1) is an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a heteroatom such as a furanyl group (O, S, N). In addition, the aryl group may have a substituent such as a halogen atom (for example, chlorine atom, bromine atom, fluorine atom). Ar is preferably an unsubstituted aromatic hydrocarbon group, particularly preferably a phenyl group.

  As the unsubstituted or substituted monovalent hydrocarbon group as R in the formula (1) of the component (A-1), the following aliphatic unsaturated groups and monovalent hydrocarbon groups other than the aliphatic unsaturated groups An alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group; a chloromethyl group, 3, 3, Examples thereof include haloalkyl groups having 1 to 4 carbon atoms such as 3-trifluoropropyl group; aryl groups having 6 to 10 carbon atoms such as phenyl group and tolyl group. Among monovalent hydrocarbon groups other than aliphatic unsaturated groups, alkyl groups having 1 to 6 carbon atoms and phenyl groups are preferable, and methyl groups are particularly preferable.

  The aliphatic unsaturated group as R in the formula (1) can stably maintain the uncured state of the composition of the present invention before the start of the addition reaction, and the composition after the start of the addition reaction. What is necessary is just to be able to harden a thing easily, for example, an ethylenically unsaturated group and an acetylenic unsaturated group are mentioned. The aliphatic unsaturated groups may be the same or different and contain at least two in one molecule. Thus, as for (A-1) component, what contains an aliphatic unsaturated group in both ends is more preferable.

Here, the “ethylenically unsaturated group” refers to an organic group containing a carbon-carbon double bond and further containing or not containing a hetero atom such as an oxygen atom or a nitrogen atom. Specific examples thereof include a vinyl group. An alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms such as an allyl group, a 5-hexenyl group, a propenyl group and a butenyl group; an alkadienyl group having 4 to 10 carbon atoms such as a 1,3-butadienyl group; A combination of an alkenyl group and a carbonyloxy group, such as an acryloyloxy group (—O (O) CCH═CH ₂ ), a methacryloyloxy group (—O (O) CC (CH ₃ ) ═CH ₂ ); an acrylamide group ( And a combination of the alkenyl group and the carbonylamino group, such as —NH (O) CCH═CH ₂ ).

  The “acetylenically unsaturated group” means an organic group containing a carbon-carbon triple bond and further containing or not containing a hetero atom such as an oxygen atom or a nitrogen atom. Specific examples thereof include an ethynyl group and propargyl. Examples thereof include a combination of an alkynyl group and a carbonyloxy group such as an alkynyl group having 2 to 20, preferably 2 to 10 carbon atoms, such as a group; and an ethynylcarbonyloxy group (—O (O) CC≡CH).

  Among these, from the viewpoints of productivity and cost when obtaining the raw material of the component (A-1), reactivity of the component (A-1), etc., the aliphatic unsaturated group is preferably the alkenyl group, vinyl group , An allyl group and a 5-hexenyl group are more preferable, and a vinyl group is particularly preferable.

  In the component (A-1), the polymerization degree n of the diarylsiloxane unit is an integer of 1 or more, preferably an integer of 1 to 100, more preferably an integer of 1 to 20, and 2 to 10 More preferably, it is an integer.

  Component (A-1) is an aliphatic unsaturated group-containing end-capping after, for example, hydrolyzing / condensing bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane, or simultaneously with hydrolysis / condensation. It can be obtained by sealing the end with an agent.

(A-2) Component The curable silicone resin composition that is effectively used in the present invention may contain the component (A-2) for the purpose of obtaining hardness after curing.
The component (A-2) used is preferably added in combination with the component (A-1). The component (A-2) is a branched or three-dimensional organopolysiloxane represented by the following average composition formula (2).
R ′ _{n ′} (C ₆ H ₅ ) _{m ′} SiO _{(4-n′-m ′) / 2} (2)
[Wherein, R ′ is the same or different and is any one of a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group and a hydroxyl group, and 0.1 to 80 mol% of all R ′ is an alkenyl group, n ′ and m ′ are positive numbers satisfying 1 ≦ n ′ + m ′ ≦ 2 and 0.20 ≦ m ′ / (n ′ + m ′) ≦ 0.95. ]

As understood from the fact that 1 ≦ n ′ + m ′ ≦ 2 in the average composition formula (2), this organopolysiloxane has R′SiO _3/2 units, (C ₆ H ₅ ) SiO ₃ in the molecule. _{/ 2} units, branched or three-dimensional network structures containing one or more of SiO ₂ units.

Here, in the formula (2), C ₆ H ₅ is a phenyl group, R ′ is a substituted or unsubstituted monovalent hydrocarbon group, alkoxy group or hydroxyl group excluding the phenyl group, preferably having 1 to 1 carbon atoms. 20, particularly preferably 1 to 10 unsubstituted or substituted monovalent hydrocarbon group, alkoxy group or hydroxyl group. Specific examples of such hydrocarbon group include methyl group, ethyl group, propyl group, butyl group. Group, pentyl group, hexyl group, cyclohexyl group, heptyl group and other alkyl groups; tolyl group, xylyl group, naphthyl group and other aryl groups excluding phenyl group; benzyl group, phenethyl group and other aralkyl groups; vinyl group, allyl group Group, butenyl group, pentenyl group, hexenyl group, unsaturated hydrocarbon group such as alkenyl group such as heptenyl group; chloromethyl group, 3-chloropropyl group, Examples thereof include halogenated alkyl groups such as 3,3,3-trifluoropropyl group, etc. As the alkoxy group, in addition to unsubstituted alkoxy groups such as methoxy group, ethoxy group, propoxy group, phenoxy group, methoxyethoxy group And alkoxy-substituted alkoxy groups such as ethoxyethoxy group.

In the present invention, it is preferred that 0.1 to 80 mol%, preferably 0.5 to 50 mol%, of these total R ′ are alkenyl groups. If the alkenyl group content is 0.1 mol% or more, the required hardness as a silicone resin can be obtained, and if it is 80 mol% or less, there is no possibility that the silicone resin becomes brittle due to too many crosslinking points. . N ′ and m ′ are 1 ≦ n ′ + m ′.
≦ 2, preferably 1.2 ≦ n ′ + m ′ <1.9, 0.2 ≦ m ′ / (n ′ + m ′) ≦ 0.95, preferably 0.25 ≦ m ′ / (n ′ + m ′) ) ≦ 0.90, but if n ′ + m ′ is greater than 1 and less than or equal to 2, the necessary hardness and strength can be obtained. Moreover, if there is more content of a phenyl group than this, the hardness and intensity | strength required as a silicone resin can be obtained. As the alkenyl group, a vinyl group is preferable.

  The compounding amount of the component (A-2) is a sufficient amount so that the hardness of the resin composition after curing becomes a target value, but is usually 100 parts by mass of the component (A-1). (A-2) A component is the quantity used as 0 mass part-500 mass parts.

Component (B) Component (B) is an organosilicon compound (SiH group) having hydrogen atoms (ie, SiH groups) bonded to at least two silicon atoms per molecule and having no aliphatic unsaturated group. Containing organosilicon compound), it undergoes a hydrosilylation addition reaction with component (A) and acts as a crosslinking agent. (B) A component may be used individually by 1 type, or may use 2 or more types together. As the component (B), any known compound can be used as long as it is a silicon compound having at least two SiH groups per molecule.

  The organic group bonded to the silicon atom in the component (B) is an unsubstituted monovalent hydrocarbon group or halogen atom (for example, chlorine atom, bromine atom, fluorine atom), epoxy, which does not have an aliphatic unsaturated group. A monovalent hydrocarbon group substituted with a group-containing group (for example, epoxy group, glycidyl group, glycidoxy group), alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group) or the like. Examples of such a monovalent hydrocarbon group include 1 to 6 carbon atoms specifically exemplified as an unsubstituted or substituted monovalent hydrocarbon group for R in formula (1) of the component (A-1). A haloalkyl group having 1 to 4 carbon atoms; an aryl group having 6 to 10 carbon atoms. The organic group is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, more preferably a methyl group or a phenyl group. Moreover, when it has an epoxy group containing group and / or an alkoxy group as a substituent of a monovalent hydrocarbon group, adhesiveness can be provided to the hardened | cured material of the composition of this invention.

As long as the component (B) is an organosilicon compound having at least two SiH groups per molecule, the molecular structure of the organosilicon compound is not particularly limited. For example, linear, cyclic, branched, three-dimensional Various conventionally produced organohydrogenpolysiloxanes such as a network structure (resinous) can be used.
The organohydrogenpolysiloxane has at least 2, preferably 3 or more (usually about 3 to 200, preferably about 4 to 100) SiH groups in one molecule. When the organohydrogenpolysiloxane has a linear structure or a branched structure, these SiH groups may be located only in either one of the molecular chain terminal and the molecular chain non-terminal part, or both. May be located.

  The number (degree of polymerization) of silicon atoms in one molecule of the organohydrogenpolysiloxane is preferably about 2 to 1,000, more preferably about 3 to 200, and still more preferably about 4 to 100. Further, the organohydrogenpolysiloxane is preferably liquid at 25 ° C., and the viscosity at 25 ° C. measured by a rotational viscometer is preferably 1 to 1,000 mPa · s, more preferably 10 to 100 mPa · s. Degree.

(B) As an organosilicon compound of a component, what is shown by the following average composition formula (3) can be used, for example.
R ″ _a H _b SiO _{(4-ab) / 2} (3)
Wherein R ″ is an identical or different unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom (excluding an aliphatic unsaturated group); 7 ≦ a ≦ 2.1, 0.001 ≦ b ≦ 1.0, and 0.8 ≦ a + b ≦ 3.0, preferably 1.0 ≦ a ≦ 2.0, 0.01 ≦ b ≦ 1.0 And a positive number satisfying 1.5 ≦ a + b ≦ 2.5.)

  Examples of R ″ include 1 to 1 carbon atoms specifically exemplified as an unsubstituted or substituted monovalent hydrocarbon group other than the aliphatic unsaturated group in formula (1) in the component (A-1). 6 alkyl groups or haloalkyl groups having 1 to 4 carbon atoms, and aryl groups having 6 to 10 carbon atoms. R ″ is preferably an alkyl group having 1 to 6 carbon atoms, or 6 carbon atoms. Is an aryl group of 10 to 10, more preferably a methyl group or a phenyl group.

Examples of the organohydrogenpolysiloxane represented by the above average composition formula (3) include a cyclic compound containing at least four organohydrogensiloxane units represented by the formula: R ″ HSiO, and the formula: R ″ ₃ SiO (HR "SiO) _c SiR" ₃ compound, formula: HR " ₂ SiO (HR" SiO) _c SiR "H compound, formula: HR" SiO (HR "SiO) _c (R" ₂ SiO) _d Examples thereof include compounds represented by SiR ″ ₂ H. In the above formula, R ″ is as described above, and c and d are positive numbers of 1 or less.

Alternatively, the organohydrogensiloxane represented by the above average composition formula (3) includes a siloxane unit represented by the formula: HSiO _1.5 , a siloxane unit represented by the formula: R ″ HSiO, and / or a formula: R ″ ₂ HSiO. It may contain a siloxane unit represented by _0.5 . The organohydrogensiloxane may contain _{monoorganosiloxane} units not containing SiH groups, diorganosiloxane units, triorganosiloxane units and / or SiO _4/2 units. R ″ in the above formula is as described above. Of all the organosiloxane units contained in the organohydrogensiloxane represented by the above average composition formula (3), 30 to 100 mol% is methylhydrogensiloxane units. Preferably there is.

Specific examples of the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, and tris (hydrogen). Dimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-capped methylhydrogenpolysiloxane with molecular chain terminals, trimethylsiloxy group-capped dimethylsiloxane with molecular chain terminals Methyl hydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group-capped diphenylsiloxane, methylhydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group-capped methylphenylsiloxane, Cylhydrogensiloxane copolymer, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer, both ends of molecular chain trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane / diphenylsiloxane Polymer, Molecular chain both ends dimethylhydrogensiloxy group-capped methylhydrogenpolysiloxane, Molecular chain both ends dimethylhydrogensiloxy group-capped dimethylpolysiloxane, Molecular chain both ends dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane Copolymer, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, both ends of molecular chain, dimethyl at both ends of molecular chain Didroxysiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked diphenylpolysiloxane, molecular chain both ends dimethylhydrogen Siloxy group-capped diphenylsiloxane / methylhydrogensiloxane copolymer, in each of these exemplary compounds, an organohydrogenpolysiloxane in which a part or all of the methyl group is substituted with another alkyl group such as ethyl group or propyl group, An organosiloxane copolymer comprising a siloxane unit represented by the formula: R ″ ₃ SiO _0.5 , a siloxane unit represented by the formula: R ″ ₂ HSiO _0.5 , and a siloxane unit represented by the formula: SiO ₂ , R " Siloxane units of the formula HSiO _0.5: organosiloxane copolymers consisting of siloxane units represented by SiO _2, wherein: "siloxane units of the formula HSiO: _R" R represented by _{SiO 1.5} Examples thereof include an organosiloxane copolymer composed of either or both of a siloxane unit and a siloxane unit represented by the formula: HSiO _1.5 , and a mixture composed of two or more of these organopolysiloxanes. R ″ in the above formula has the same meaning as described above.

  The blending amount of the component (B) is an amount sufficient to cure the present composition in the presence of the hydrosilylation catalyst of the component (C). Usually, the amount of the component (A) relative to the aliphatic unsaturated group in the component (A) B) The amount of SiH groups in the component is 0.2 to 5, preferably 0.5 to 2.

(C component)
(P) Hydrosilylation addition of silicon atom-bonded aliphatic unsaturated group in component (A) and SiH group in component (B) as a (platinum group metal-based) hydrosilylation catalyst containing a white metal of component (C) Any catalyst that accelerates the reaction may be used. (C) A component may be used individually by 1 type, or may use 2 or more types together. Examples of the component (C) include platinum group metals such as platinum, palladium and rhodium, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, coordination compounds of vinylsiloxane or acetylene compounds, tetrakis Although platinum group metal compounds, such as (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium, are mentioned, A platinum compound is especially preferable.

  The compounding amount of the component (C) may be an effective amount as a hydrosilylation catalyst, and preferably 0.1 to 1,000 ppm in terms of the mass of the platinum group metal element with respect to the total mass of the components (A) and (B). More preferably, it is the range of 1-500 ppm.

Composition comprising (A) ~ (C) component of the present invention preferably has oxygen permeability after heat curing is not more than ^{1,000cm 3 / m 2 / 24h /} atm. When the oxygen transmission rate after heat curing is not more than ^{1,000cm 3 / m 2 / 24h /} atm, it is possible to effectively obtain the effect in which the suppression of gas permeability, such as sulfur oxides present invention, the structure one Even when a sulfur exposure test is performed on an LED device in which a sealant is filled and cured in a package with silver plating on the part, sulfur passes through the sealing resin and silver plating sulfidation proceeds. Therefore, there is no risk of black silver sulfide. ^Preferably, at most ^{500cm 3 / m 2 / 24h /} atm. For this reason, the brightness | luminance of an LED device can be kept favorable. The lower limit of the oxygen permeability is not particularly limited, is usually ^{0cm 3 / m 2 / 24h /} atm or higher. The method for measuring the oxygen transmission rate is as described later.

Other Components In addition to the components (A) to (C) and the phosphor particles, nanoparticles, and silicone powder, other optional components can be blended in the composition of the present invention. Specific examples thereof include the following. Each of these other components may be used alone or in combination of two or more.

(A) Aliphatic unsaturated group-containing compound other than component In addition to the component (A), an aliphatic unsaturated group-containing compound that undergoes addition reaction with the component (B) may be added to the composition of the present invention. . Such aliphatic unsaturated group-containing compounds are preferably those involved in the formation of a cured product, and examples thereof include organopolysiloxanes having at least two aliphatic unsaturated groups per molecule. The molecular structure may be any of linear, cyclic, branched, three-dimensional network, etc.

  Specific examples of the aliphatic unsaturated group-containing compound include butadiene, monomers such as diacrylates derived from polyfunctional alcohols; polyethylene, polypropylene or styrene and other ethylenically unsaturated compounds (for example, acrylonitrile or butadiene). Polyolefins such as copolymers thereof; oligomers or polymers derived from functionally substituted organic compounds such as esters of acrylic acid, methacrylic acid, or maleic acid. This aliphatic unsaturated group-containing compound may be liquid or solid at room temperature.

Addition Reaction Control Agent An addition reaction control agent can be blended with the composition of the present invention to ensure pot life. The addition reaction control agent is not particularly limited as long as it is a compound having a curing inhibitory effect on the hydrosilylation catalyst of the component (C), and conventionally known ones can also be used. Specific examples thereof include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; sulfur-containing compounds; acetylene alcohols (for example, 1-ethynylcyclohexanol, 3,5- Acetylene compounds such as dimethyl-1-hexyn-3-ol); compounds containing two or more alkenyl groups; hydroperoxy compounds; and maleic acid derivatives.

  The degree of the curing inhibitory effect of the addition reaction control agent varies depending on the chemical structure of the addition reaction control agent. Therefore, it is preferable to adjust the addition amount to an optimum amount for each of the addition reaction control agents to be used. By adding an optimal amount of addition reaction control agent, the composition has excellent long-term storage stability at room temperature and heat curability.

Adhesion imparting agent Moreover, this composition may contain the adhesion imparting agent for improving the adhesiveness. Examples of the adhesion-imparting agent include silane coupling agents and hydrolysis condensates thereof. As silane coupling agents, epoxy group-containing silane coupling agents, (meth) acrylic group-containing silane coupling agents, isocyanate group-containing silane coupling agents, isocyanurate group-containing silane coupling agents, amino group-containing silane coupling agents , A known compound such as a mercapto group-containing silane coupling agent is used, and is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 100 parts by mass in total of the component (A) and the component (B). -10 mass parts can be used.

In order to suppress the occurrence of coloring and oxidative degradation of the cured antioxidant , a conventionally known antioxidant can be blended in the composition of the present invention, for example, 2,6-di-t-butyl- 4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,2'- And methylene bis (4-methyl-6-tert-butylphenol), 2,2'-methylene bis (4-ethyl-6-tert-butylphenol), and the like. These can be used singly or in combination of two or more.
In addition, when using this antioxidant, the compounding quantity will not be restrict | limited especially if it is an effective amount as antioxidant, It is 10-10 normally with respect to the total mass of the composition of this invention. It is preferable to blend about 000 ppm, especially about 100 to 1,000 ppm. When the blending amount is within the above range, the antioxidant ability is sufficiently exhibited, and a cured product having excellent optical characteristics can be obtained without occurrence of coloring, white turbidity, oxidative degradation, or the like.

Light stabilizer Furthermore, it is also possible to use a light stabilizer for imparting resistance to light degradation caused by light energy such as sunlight and fluorescent lamps. As this light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidation degradation is suitable, and the antioxidant effect is further improved by using it together with the antioxidant. Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine and the like.

  Furthermore, an inorganic filler such as fumed silica or nano-alumina may be added to the composition of the present invention in order to improve the strength and suppress sedimentation of the particles, and if necessary, dyes, pigments, flame retardants, etc. May be incorporated into the composition of the present invention.

<Hardened product>
The curable resin composition of the present invention can be cured by a known curing method under known curing conditions. Specifically, the composition can be cured usually by heating at 80 to 200 ° C, preferably 100 to 160 ° C. The heating time is about 0.5 minutes to 5 hours, and may be about 1 minute to 3 hours. When accuracy such as LED sealing is required, it is preferable to lengthen the curing time. There is no restriction | limiting in the form of the hardened | cured material obtained, For example, any of a hardened | cured material of a gel hardened | cured material, an elastomer hardened | cured material, and a resin composition may be sufficient.

<Optical semiconductor device>
The cured product of the curable resin composition of the present invention is excellent in heat resistance, cold resistance, and electrical insulation, similar to a cured product of a normal addition-curable silicone composition. An example of an optical semiconductor device using such a cured product of the composition of the present invention is shown in FIG. The optical semiconductor element 3 is wire-bonded by a wire 2, and the sealing material 1 made of the composition of the present invention is applied to the optical semiconductor element 3, and the applied sealing agent 1 is subjected to known curing conditions. It can be sealed by curing by a known curing method, specifically as described above.

  In the optical semiconductor device 10 of the present invention, the optical semiconductor element 3 encapsulated by the encapsulant 1 made of the composition of the present invention includes, for example, an LED, a semiconductor laser, a photodiode, a phototransistor, and a solar cell. And CCD.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example etc. In addition, in the following example, the symbol which shows the average composition of a silicone oil or a silicone resin shows the following units. The number of moles of each silicone oil or each silicone resin indicates the number of moles of vinyl groups or SiH groups contained in each component.
^MH : (CH ₃ ) ₂ HSiO _1/2
M: (CH ₃ ) ₃ SiO _1/2
M ^Vi : (CH ₂ ═CH) (CH ₃ ) ₂ SiO _1/2
M ^Vi3 : (CH ₂ ^═CH ) ₃ SiO _{1/2
^{D H: (CH 3) HSiO}} 2/2
^Dφ : (C ₆ H ₆ ) ₂ SiO _2/2
D: (CH ₃ ) ₂ SiO _2/2
D ^Vi : (CH ₂ ═CH) (CH ₃ ) SiO _2/2
^Tφ : (C ₆ H ₆ ) SiO _3/2
Q: SiO _4/2

(Formulation example 1)
((A-1) component) average composition ^{formula: M} _Vi 2 D ^φ _2.8 Silicone oil: 100 parts by weight,
((B) component) average composition ^formula: M ^H _D methylhydrogensiloxane represented by _{^{H 2 D φ 2 M H:}} 51.3 parts by weight,
(Component (C)) Toluene solution containing 1% by mass of chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex as platinum atom content: 0.06 parts by mass,
Ethynylcyclohexanol: 0.05 part by mass and γ-glycidoxypropyltrimethoxysilane: 3 parts by mass were thoroughly stirred to prepare silicone composition 1.
It was 700 mPa * s when the viscosity at the room temperature of the composition 1 was measured.
It was 210 cm < ³ > / m < ² > / 24h / atm when the oxygen transmission rate after hardening of the composition 1 was measured.

(Formulation example 2)
((A-1) component) Average composition formula: MD _3.4 D ^Vi _6.5 D ^φ _8.6 M silicone oil: 23 parts by mass, average composition formula: M ^Vi ₂ D ^φ _2.8 silicone oil : 80 parts by mass,
((B) component) average composition ^formula: M ^H _D methylhydrogensiloxane represented by ^{_{H 2 D φ 2 M H:}} 30 parts by weight,
(Component (C)) Toluene solution containing 1% by mass of chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex as platinum atom content: 0.06 parts by mass,
Ethynylcyclohexanol: 0.05 parts by mass and γ-glycidoxypropyltrimethoxysilane: 3 parts by mass were thoroughly stirred to prepare silicone composition 2.
It was 3000 mPa * s when the viscosity at the room temperature of the composition 2 was measured.
It was 400 cm < ³ > / m < ² > / 24h / atm when the oxygen transmission rate after hardening of the composition 2 was measured.

(Formulation example 3)
((A-1) component) average composition ^{formula: M} _Vi 2 D ^φ _2.8 silicone oil: 31 parts by weight,
(Component (A-2)) Branched organopolysiloxane represented by T ^φ _0.75 D ^Vi _0.25 (solid at 25 ° C., content of silicon atom-bonded vinyl group = 20 mol%, silicon atom Content ratio of silicon-bonded phenyl group in all bonded organic groups = 50 mol%, weight-average molecular weight in terms of standard styrene = 1600): 59 parts by mass (component (B)) Average composition formula: M ^H D ^H ₂ D ^φ Methyl hydrogen siloxane represented by ₂ ^MH : 6.4 parts by mass,
(Component (C)) Toluene solution containing 1% by mass of chloroplatinic acid / 1,3-divinyltetramethyldisiloxane complex as platinum atom content: 0.06 parts by mass,
Ethynylcyclohexanol: 0.05 parts by mass and γ-glycidoxypropyltrimethoxysilane: 3 parts by mass were thoroughly stirred to prepare silicone composition 3.
It was 3200 mPa * s when the viscosity at the room temperature of the composition 3 was measured.
It was 250 cm < ³ > / m < ² > / 24h / atm when the oxygen transmission rate after hardening of the composition 3 was measured.

Example 1
100 parts by mass of Composition 1 of Formulation Example 1 and 2 parts by mass of nanoalumina (manufactured by Nippon Aerosil Co., Ltd., product name: AEROXIDE AluC805, average primary particle size 13 nm) as a nanoparticle are equipped with a vacuum degassing mechanism. Then, the particle size of the nanoparticles that were uniformly dispersed was measured using a self-revolving stirrer (product name: ARV-310, manufactured by Sinky Corporation). Next, 5 parts by mass of silicone resin powder (manufactured by Shin-Etsu Chemical Co., Ltd., product name X-52-1621, average particle size 5 μm) was similarly mixed uniformly using a self-revolving stirrer equipped with a vacuum degassing mechanism. Further, 8 parts by mass of YAG-based phosphor particles having a specific gravity of 5 g / cm ³ were uniformly dispersed using a self-revolving stirrer similarly equipped with a vacuum degassing mechanism to prepare a curable resin composition (a). did.

(Example 2)
100 parts by mass of Composition 2 of Formulation Example 2 and 2 parts by mass of nanosilica (product name: Reosirol DM30S, average primary particle size 7 nm) as nanoparticles were added as self-equipped with a vacuum degassing mechanism. Using a revolving stirrer (product name: ARV-310, manufactured by Shinky Corp.), the particle size of the secondary aggregated nanoparticles was measured by uniform dispersion. Subsequently, 5 parts by mass of silicone composite powder (manufactured by Shin-Etsu Chemical Co., Ltd., product name KMP-600, average particle size 5 μm) was similarly mixed uniformly using a self-revolving stirrer equipped with a vacuum degassing mechanism. Further, 8 parts by mass of YAG-based phosphor particles having a specific gravity of 5 g / cm ³ were uniformly dispersed using a self-revolving stirrer similarly equipped with a vacuum degassing mechanism to prepare a curable resin composition (b). did.

(Example 3)
100 parts by mass of Composition 3 of Formulation Example 3 and 2 parts by mass of nano-alumina (manufactured by Nippon Aerosil Co., Ltd., product name: AEROXIDE AluC805, average primary particle size 13 nm) as a nanoparticle are equipped with a vacuum degassing mechanism. The particle size of the nanoparticles that were uniformly dispersed and secondary agglomerated at this time was measured using a self-revolving stirrer (product name: ARV-310, manufactured by Shinky Corporation). Next, 5 parts by mass of silicone resin powder (manufactured by Shin-Etsu Chemical Co., Ltd., product name X-52-1621, average particle size 5 μm) was similarly mixed uniformly using a self-revolving stirrer equipped with a vacuum degassing mechanism. Further, 8 parts by mass of YAG-based phosphor particles having a specific gravity of 5 g / cm ³ are uniformly dispersed using a self-revolving stirrer similarly equipped with a vacuum degassing mechanism to prepare a curable resin composition (c). did.

Example 4
Nano-alumina (Nippon Aerosil (Nippon Aerosil), which was slightly surface-treated with a (meth) acrylic group-containing silane coupling agent for the purpose of reducing secondary aggregation as 100 parts by mass of the composition 1 of Formulation Example 1 as nanoparticles. Co., Ltd., product name: AEROXIDE AluC805, average primary particle size 13 nm) 2 parts by mass uniformly using a self-revolving stirrer (product name: ARV-310, manufactured by Shinkey Co., Ltd.) equipped with a vacuum degassing mechanism The particle size of the dispersed and secondary agglomerated nanoparticles was measured. Next, 5 parts by mass of silicone resin powder (manufactured by Shin-Etsu Chemical Co., Ltd., product name X-52-1621, average particle size 5 μm) was similarly mixed uniformly using a self-revolving stirrer equipped with a vacuum degassing mechanism. Further, 8 parts by mass of YAG-based phosphor particles having a specific gravity of 5 g / cm ³ were uniformly dispersed using a self-revolving stirrer similarly equipped with a vacuum degassing mechanism to prepare a curable resin composition (d). did.

(Comparative Example 1)
A composition (e) was prepared in the same manner as in Example 1 except that the nanoparticles and the silicone powder were not added.

(Comparative Example 2)
A composition (f) was prepared in the same manner as in Example 2, except that the nanoparticles and the silicone powder were not added.

(Comparative Example 3)
A composition (g) was prepared in the same manner as in Example 3, except that the nanoparticles and the silicone powder were not added.

(Comparative Example 4)
A composition (h) was prepared in the same manner as in Example 1 except that the nanoparticles were not added.

(Comparative Example 5)
Composition (i) was prepared in the same manner as in Example 1 except that no silicone powder was added.

(Comparative Example 6)
Nano-alumina (Nippon Aerosil Co., Ltd., product name: AEROXIDE AluC805, average primary particle size) sufficiently surface-treated with a (meth) acrylic group-containing silane coupling agent for the purpose of preventing secondary aggregation 13 nm) A composition (j) was prepared in the same manner as in Example 1 except that 2 parts by mass were used.

(Comparative Example 7)
As silicone resin powder, the same as Example 1 except that 5 parts by mass of the coarse particles of product name X-52-854 manufactured by Shin-Etsu Chemical Co., Ltd. were cut to an average particle size of 0.4 μm was used. Composition (k) was prepared by operation.

  Evaluation in curable resin composition (a)-(k) prepared by the said Example and comparative example was performed in the following way.

Confirmation of dispersion state of phosphor particles The dispersion state after 6 hours of phosphor stirring and mixing was visually confirmed.

Nanoparticle size distribution measurement Nanoparticle size distribution measurement was performed using SALD-7100 manufactured by Shimadzu Corporation. The measurement solution was not particularly diluted, and a stock solution in which nanoparticles were dispersed was used. A part of the measurement solution was collected in a 50 μm indentation cell, and a slide glass was placed thereon to form a sample cell, which was set in a measurement unit and measured. The measurement was performed three times by the same procedure. The particle size distribution from 10 nm to 300 μm was measured by volume conversion Q3, and the average value of the average particle size (d50) was determined.

Measurement of oxygen permeability The oxygen permeability was measured according to JIS-K7126-2 (measurement temperature 23 ° C, sample thickness 1 mm).

As an optical semiconductor element for measuring chromaticity coordinates (x) , an LED chip 3 having a light emitting layer made of InGaN and having a main light emission peak of 450 nm is assembled into an SMD5050 package (I-CHIUN PRECISION INDUSTRY CO., Resin part PPA). The light emitting semiconductor device as shown in FIG. 1 was used.
In each of the Examples and Comparative Examples, the sealing resin was measured so that 1 g of the phosphor particles was weighed against 10 g of the produced curable resin composition, and after uniform mixing, the sedimentation of the phosphor particles was not affected. Immediately transfer 5 cc amount to 10 cc syringe for dispensing, apply prescribed amount to the SMD5050 package without waiting time, and continuously apply 5 cc sealant 1 to 1 cc, did. The package filled with the sealing agent in a series of processes is heated and cured at 150 ° C. for 4 hours to form an optical semiconductor package, and each of the 10 optical semiconductor devices obtained in the initial stage of the coating process and the later stage of the coating process is arbitrarily sampled did. Ten light emitting semiconductor devices were measured using a total luminous flux measurement system HM-9100 (manufactured by Otsuka Electronics Co., Ltd.), and the chromaticity coordinates (x) were measured to obtain an average value (applied current IF = 20 mA). The values of chromaticity coordinates (x) at the initial stage of the coating process and the latter stage of the coating process were compared.

As an optical semiconductor element for measuring the total luminous flux (Lm) , an LED chip having a light emitting layer made of InGaN and having a main light emission peak of 450 nm is mounted on an SMD5050 package (I-CHIUN PRECISION INDUSTRY CO., Resin part PPA). Each was mounted and wire bonded, and a light emitting semiconductor device as shown in FIG. 1 was used.
For the purpose of preventing the influence of phosphor settling, the package was filled with the curable resin composition prepared in each of the examples and comparative examples without adding the phosphor, and heat-cured at 150 ° C. for 4 hours as described above. An optical semiconductor package is obtained, and each of the 10 optical semiconductor devices obtained in this process is arbitrarily sampled, and the total luminous flux (Lm) is obtained using the total luminous flux measurement system HM-9100 (manufactured by Otsuka Electronics Co., Ltd.). Measurement was performed to obtain an average value (applied current IF = 20 mA), and values of total luminous flux were compared in order to obtain the light extraction efficiency by adding each silicone powder (the following formula).
(Light extraction efficiency) = {(Total luminous flux value after powder addition) / (Total luminous flux value before powder addition)} × 100-100 (%)

Moreover, 10 light-emitting semiconductor devices measured as described above were allowed to stand for 24 hours in a 180 ° C. dryer. Thereafter, the total luminous flux value was similarly measured using the total luminous flux measurement system, and the average value was obtained (applied current IF = 20 mA). The values at this time were compared and determined as the total luminous flux remaining rate (%) after the heat resistance test (the following formula).
(Total luminous flux remaining rate after heat test) = {(total luminous flux value after heating at 180 ° C. for 24 hours) / (initial total luminous flux value)} × 100 (%)
The total luminous flux remaining rate after the heat resistance test obtained here was compared, and the quality of heat resistance improvement by each silicone powder addition was determined.
(Total luminous flux remaining ratio after heat resistance test) = {(Total luminous flux remaining ratio after heat resistance test of powder added sample) / (Total luminous flux residual ratio after heat resistance test of sample before powder addition)} × 100-100 (% )
From the above formulas, both the light extraction efficiency and the total luminous flux ratio that take a positive value mean that it is brighter than the reference, and the one that takes a negative value means that it is darker than the reference. .

Temperature cycle test (TCT) condition temperature: -40 ° C to 125 ° C
Number of cycles: 1,000
Ten light-emitting semiconductor device manufactured, then placed in a temperature cycle tester was counted the number of unlit LE D package after 1,000 cycles as NG. That is, when the numerical value in Table 1 is 0, the package is lit and excellent in reliability, and when it is 10, all the packages are not lit and inferior in reliability.

Sulfurization test of package A 100 mL transparent glass bottle was filled with 0.2 g of sulfur powder and an LED package sealed with each composition and sealed. After sealing, it was put into a dryer at 70 ° C., taken out after 24 hours, and discoloration of the silver-plated portion of the package was confirmed with a microscope. Discolored black (NG).

  As shown in the table above, a resin composition in which phosphor particles are dispersed in a resin composition in which nanoparticles and silicone powder secondary-aggregated to a particle diameter of 100 nm to 20 μm are dispersed (Examples 1 to In Example 4), no sedimentation of the phosphor particles was confirmed even after 6 hours had passed after the dispersion of the phosphor particles, and the total luminous flux values and color coordinates in the early and late stages of the dispensing process were small. In other words, color variation was small throughout the process, and a good optical semiconductor device could be manufactured.

  On the other hand, in Comparative Examples 1 to 3 in which the nanoparticles and the silicone powder were removed from the resin compositions shown in Examples 1 to 3, the light extraction efficiency was low compared to the Examples, and the phosphor was confirmed to settle. The color coordinate difference was large throughout the process and the color variation was large, and the thermal shock was inferior.

  Further, in Comparative Example 4 in which the nanoparticles were excluded from the composition of Example 1, although the thermal shock resistance was excellent, the sedimentation of the phosphor was confirmed, and the color coordinate difference was large and the color variation was large throughout the process. Yes, a good optical semiconductor device could not be manufactured.

  Further, in Comparative Example 5 in which silicone powder was removed from the composition of Example 1, the difference in color coordinates between the initial stage and the late stage of the dispensing process was small, but a good optical semiconductor device with poor thermal shock was produced. I couldn't.

  Further, in Comparative Example 6 in which nanoparticles subjected to sufficient surface treatment instead of the nanoparticles having the composition of Example 1 were added, the secondary particle diameter was 70 nm because secondary aggregation of the nanoparticles was suppressed. It has become smaller. For this reason, the sedimentation of the phosphor was confirmed after mixing and stirring the phosphor, and the difference in color coordinates was large throughout the process, and thus the color variation was large.

  Further, Comparative Example 7 in which a silicone powder having a small average particle diameter was added instead of the silicone powder having the composition of Example 1 was excellent in thermal shock, but the light extraction efficiency after addition of the silicone powder and the total luminous flux remaining after the heat resistance test. Both rates declined.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

DESCRIPTION OF SYMBOLS 1 ... Sealing material in which phosphor particles are dispersed, 2 ... Wire, 3 ... Optical semiconductor element 10 ... Optical semiconductor device

Claims (8)

A curable resin composition to which at least phosphor particles and nanoparticles having a primary particle diameter of 1 nm to less than 100 nm are added, wherein the nanoparticles have a volume conversion Q3 and an average particle diameter of 100 nm to 20 μm. It is those which are dispersed in the form of the following agglomerated particles state, and are not of a silicone powder having an average particle size 0.5~100μm are dispersed,
The curable resin composition is
(A) The following compound (A-1) and / or organopolysiloxane (A-2)
(A-1) A compound having a structure represented by the following general formula (1) and having at least two aliphatic unsaturated groups per molecule:

Wherein R is the same or different unsubstituted or substituted monovalent hydrocarbon group, Ar is the same or different aryl group which may have a hetero atom, and m is 0 or 1 or more. Integer, n is an integer of 1 or more.)
(A-2) Branched or three-dimensional organopolysiloxane having a structure represented by the following average composition formula (2):
R ′ _{n ′} (C ₆ H ₅ ) _{m ′} SiO _{(4-n′-m ′) / 2} (2)
[Wherein, R ′ is the same or different and is any one of a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group and a hydroxyl group, and 0.1 to 80 mol% of all R ′ is an alkenyl group, n ′ and m ′ are positive numbers satisfying 1 ≦ n ′ + m ′ ≦ 2 and 0.20 ≦ m ′ / (n ′ + m ′) ≦ 0.95. ]
(B) an organosilicon compound having no hydrogen unsaturated group and having hydrogen atoms bonded to at least two silicon atoms per molecule;
(C) a hydrosilylation catalyst containing a platinum group metal,
Curable resin composition which is curable silicone resin composition der wherein Rukoto including. The curable resin composition further curable resin composition according to claim 1, wherein the modified silicone resin, at least one epoxy resin and modified epoxy resin is Dressings containing. The curable resin composition according to claim 1 or 2, wherein the curable resin composition has a viscosity at room temperature of 100 mPa · s to 10,000 mPa · s. In (A-1) component shown by the said General formula (1), Ar is a phenyl group and n is an integer of 1-100, The any one of Claims 1-3 characterized by the above-mentioned. Curable resin composition. The component (B) is the following average composition formula (3):
R ″ _a H _b SiO _{(4-ab) / 2} (3)
Wherein R ″ is an identical or different unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom (excluding an aliphatic unsaturated group); 7 ≦ a ≦ 2.1, 0.001 ≦ b ≦ 1.0, and 0.8 ≦ a + b ≦ 3.0.
The curable resin composition according to claim 1, which is an organohydrogenpolysiloxane represented by the formula: To any one of claims 1 to 5, wherein the oxygen permeability of the cured product obtained by curing the curable silicone resin composition is ^{1,000cm 3 / m 2 / 24h /} atm or less The curable resin composition described. Hardened | cured material formed by hardening | curing curable resin composition of any one of Claims 1-6 . An optical semiconductor device using the cured product according to claim 7 .

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