JP4785085B2 - Thermosetting silicone resin composition - Google Patents

Description

  The present invention relates to a thermosetting silicone resin composition. More specifically, the present invention relates to a thermosetting silicone resin composition having excellent transparency and a high refractive index, a method for producing the same, a sheet-like molded body of the composition, and an optical semiconductor device sealed with the composition. .

  Silicone resins are superior in heat resistance and light resistance compared to materials made of organic polymers, and are therefore increasingly used in the field of electronic materials that require high durability. In particular, silicone resins are widely used in high-brightness optical semiconductor encapsulating materials, films for solar cells that require harsh usage environments and require durability, and lenses that have strict usage conditions.

  As a problem of silicone resin, it is known that the refractive index is low. The refractive index of a general silicone resin is around 1.4, which is about 0.1 lower than that of a material made of a general organic polymer. Such a silicone resin having a low refractive index is required to improve the light extraction efficiency from the viewpoint of energy saving, for example, in a high-brightness optical semiconductor sealing material. It has become a challenge.

  On the other hand, as a means for improving the refractive index of the silicone resin itself, Patent Document 1 reports a technique for introducing a bulky aromatic substituent into the silicone resin. According to this, by introducing a phenyl group having a high refractive index as a silicon substituent, it is possible to improve the refractive index from 1.4 to just over 1.5.

  In addition, a method for adjusting the refractive index of a resin by dispersing a high refractive index metal oxide such as titanium oxide, zirconia oxide or barium titanate in the resin has been studied. However, in general, it is difficult to disperse hydrophilic metal oxide particles in a hydrophobic and water-repellent silicone resin, and in particular, it is difficult to apply to applications that require transparency.

  Therefore, in Patent Document 2, in order to disperse titanium oxide particles in a silicone resin, a metal oxide fine particle dispersant obtained by copolymerizing an acrylic part having affinity for particles and a silicone part having affinity for silicone resin. Is disclosed. Patent Document 3 reports a method of dispersing titanium oxide using silicon acid or the like that is structurally similar to silicone.

On the other hand, particles prepared based on the sol-gel method have an advantage that the primary particle size is generally controllable from several nanometers to several tens of nanometers and is excellent in monodispersity. In the sol-gel method, since the reaction is usually carried out in a water-alcohol system, when dispersing the obtained particles in a resin, it is necessary to replace the dispersion medium of the particles with a solvent for dissolving the resin. However, simply trying to replace the solvent has a low affinity between the surface of the fine particles and the solvent, and the particles often aggregate. Thus, a method is disclosed in which particles prepared by a sol-gel method are treated with a surface treatment agent such as a silane coupling agent and then solvent substitution is performed (see Patent Document 4).
JP 2005-76003 A JP 2006-131547 A JP-A-9-208438 JP 2007-119617 A

  However, in the method of Patent Document 1, if the amount of phenyl group introduced is increased, the resin becomes hard and brittle, so that the utilization method is not limited, and when the amount introduced is further increased, the silicone resin itself crystallizes. As a result, there is a problem that transparency is lowered.

  When the metal oxide fine particle dispersant disclosed in Patent Document 2 is used, a relatively thin film having a thickness of about 10 μm can be kept relatively transparent. However, if the film is thicker than that, the transparency is greatly reduced. The method of Patent Document 3 has a problem in dispersion stability in addition to dispersibility.

  In addition, when a metal oxide is dispersed in a resin using a surface treatment agent according to Patent Document 4, if the compatibility between the surface treatment agent and the resin is not good, the particles aggregate and the transparency is impaired. Problem arises. Further, since the surface characteristics of the particles change due to a slight environmental change such as a change in polarity, there is a problem that it is difficult to uniformly treat the surface and is extremely difficult to handle. Further, in order to disperse the particles in the hydrophobic silicone resin, it is necessary to treat the particles with a large amount of a hydrophobic surface treatment agent. These hydrophobic surface treatment agents generally have a low refractive index, When processed in a large amount, the refractive index of the whole particle is lowered, and there is a problem that the effect of improving the refractive index is not shown even if dispersed in a resin. Moreover, it is more difficult to disperse the particles with a silicone resin having an aromatic group.

  On the other hand, if a large amount of metal oxide particles are dispersed in the resin, the resin composition itself becomes hard and brittle, and thus handling thereof is difficult. If the molecular weight of the silicone resin is increased in order to improve moldability and processability, the hydrophobicity of the resin increases, and it is generally more difficult to disperse hydrophilic high refractive index metal oxide fine particles.

  An object of the present invention is to provide a thermosetting silicone resin composition having excellent transparency and a high refractive index, a method for producing the same, a sheet-like molded body of the composition, and an optical semiconductor sealed with the composition To provide an apparatus.

  As a result of repeated studies to solve the above problems, the present inventors have found that a silicone derivative having a reactive trifunctional alkoxysilyl group at the molecular end, a metal oxide fine particle having a reactive functional group on the surface of the fine particle, By stepwise polymerization reaction, it becomes possible to integrate the silicone derivative and metal oxide fine particles having a high refractive index stepwise to improve the dispersion of the fine particles, and has excellent transparency and high refraction. It has been found that a thermosetting silicone resin composition having a high rate can be obtained, and the present invention has been completed.

That is, the present invention [1] is obtained by polymerizing a silicone derivative having a trifunctional alkoxysilyl group at the molecular end and a metal oxide fine particle having a reactive functional group on the surface of the fine particle. A thermosetting silicone comprising two or more types of silicone derivatives having a trifunctional alkoxysilyl group and performing the polymerization reaction in the presence of the metal oxide fine particles by adding the silicone derivatives in two or more stages. A thermosetting silicone resin composition , wherein the content of the metal oxide fine particles is 1 to 70 parts by weight with respect to 100 parts by weight of the silicone derivative ,
[2] The silicone derivative having a trifunctional alkoxysilyl group at the molecular end and the metal oxide fine particle having a reactive functional group on the fine particle surface are in two or more stages , and the content of the metal oxide fine particle is the silicone. A method for producing a thermosetting silicone resin composition, comprising a step of performing a polymerization reaction so as to be 1 to 70 parts by weight with respect to 100 parts by weight of the derivative ;
[3] A silicone resin sheet formed by applying the thermosetting silicone resin composition described in [1] onto a substrate and drying the composition, and [4] thermosetting described in [1]. The present invention relates to an optical semiconductor device in which an optical semiconductor element is sealed using a silicone resin composition.

  The thermosetting silicone resin composition of the present invention has an excellent effect of being excellent in transparency and having a high refractive index.

  The thermosetting silicone resin composition of the present invention is obtained by polymerizing a composition for a thermosetting silicone resin containing a silicone derivative having a trifunctional alkoxysilyl group and metal oxide fine particles having reactive functional groups on the surface of the fine particles. The silicone derivative contains two or more silicone derivatives having a trifunctional alkoxysilyl group at the molecular end, and the polymerization reaction is carried out in the presence of the metal oxide fine particles. The main feature is that it is added in two or more stages.

  Silicone resin is hydrophobic and has high water repellency, so it is difficult to disperse hydrophilic metal oxide fine particles. Therefore, in the present invention, a silicone derivative having a reactive trifunctional alkoxysilyl group at the molecular end is used as the silicone resin, and metal oxide fine particles having a reactive functional group on the fine particle surface are used as the metal oxide fine particles. By using both, the fine particles can be dispersed in a state of being bonded to the silicone resin by polymerization reaction. However, if all of the functional groups of the silicone derivative are polymerized together with the metal oxide fine particles, cross-linking through the metal oxide fine particles increases, and the resulting composition becomes hard and brittle. Therefore, by carrying out the polymerization reaction in two or more stages, the degree of crosslinking can be adjusted, and a good dispersion state of the metal oxide fine particles can be formed, which is excellent in transparency and has a high refractive index. A thermosetting silicone resin composition having the following can be obtained.

  The composition for a thermosetting silicone resin in the present invention comprises a silicone derivative having a trifunctional alkoxysilyl group at the molecular terminal (hereinafter also simply referred to as a silicone derivative), and a metal oxide fine particle having a reactive functional group on the surface of the fine particle. (Hereinafter, also simply referred to as metal oxide fine particles).

  As a silicone derivative having a trifunctional alkoxysilyl group at the molecular end, that is, a trifunctional alkoxysilane, formula (I):

Wherein, OR ¹ is an alkoxy group, R ¹ is 1 to 4 carbon atoms, a straight-chain or branch-chain alkyl group, X is 1 to 12 carbon atoms, straight-chain or branch A chain alkyl group that may contain a heteroatom at the end, or an end that is an epoxy group, primary, secondary or tertiary amino group, (meth) acryloyl group, cyclohexyl epoxy group, or aromatic group You may have
It is preferable that it is a compound represented by these.

Shows the OR ¹ in formula (I) is an alkoxy group, R ¹ is 1 to 4 carbon atoms, a straight-chain or branch-chain alkyl group. The carbon number of R ¹ is preferably 1 to 4 and more preferably 1 to 2 from the viewpoint of the reactivity on the fine particle surface and the hydrolysis rate. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and the like. Among these, R ¹ is preferably a methyl group or an ethyl group.

X in formula (I), having 1 to 12 carbon atoms, straight-chain or branch alkyl groups of chain ends may contain a hetero atom, or terminal epoxy groups, primary, secondary Alternatively, it may have a tertiary amino group, a (meth) acryloyl group, a cyclohexyl epoxy group, or an aromatic group. In the present specification, “(meth) acryloyl” is a general term for methacryloyl and acryloyl.

  Examples of the trifunctional alkoxysilane represented by the formula (I) include 2-[(3,4) -epoxycyclohexyl] ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycididoxypropyltri Methoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, (N-phenyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane Silane, 3-ureidopropyltrimethoxy Run, and the like. These may be used alone or in combination of two or more.

  In the present invention, from the viewpoint of reactivity with the metal oxide fine particles, the polymerization reaction between the metal oxide fine particles and the silicone derivative is performed in two or more stages. Specifically, in the presence of the metal oxide fine particles, In addition, the silicone derivative is added in two or more stages to cause a polymerization reaction. Silicone derivatives to be added may be the same or different depending on the stage of each polymerization reaction, but the surface of the metal oxide fine particles has high hydrophilicity, so it reacts efficiently with the surface of the fine particles in a highly polar solvent such as a water / alcohol mixed solvent. The first-stage silicone derivative that can be used is preferably a low molecular weight trifunctional alkoxysilane having a molecular weight of 160 or less. From the viewpoint of high solubility and high refractive index, molecular weights such as methyltrimethoxysilane and ethyltrimethoxysilane are preferred. Is preferably a trifunctional alkoxysilane having a molecular weight of 120 to 160. As the trifunctional alkoxysilane that is polymerized with the metal oxide fine particles in the second stage polymerization reaction, the hydrophobicity is increased by the first stage reaction. Therefore, among the compounds represented by the formula (I), the compound represented by the formula (I) Examples thereof include alkoxysilanes having relatively high hydrophobicity, such as compounds in which X is a substituent having 3 or more carbon atoms. In the present specification, the molecular weight of the silicone derivative is measured by gel filtration chromatography (GPC).

  The trifunctional alkoxysilane used in the second stage polymerization reaction preferably has a refractive index of 1.39 or more, more preferably 1.40 or more, from the viewpoint of the high refractive index of the resulting resin composition. In addition, in this specification, a refractive index is measured by the method as described in the below-mentioned Example.

  The metal oxide fine particles in the present invention are metal oxide fine particles having a reactive functional group on the fine particle surface.

  Examples of the metal oxide fine particles having reactive functional groups on the surface of the fine particles include titanium oxide, zirconium oxide, barium titanate, zinc oxide, lead titanate, silicon dioxide and the like. These may be used alone or in combination of two or more. They can be used in combination. Among these, from the viewpoint of high refractive index, at least one selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, barium titanate, and silicon dioxide is desirable. In addition, as a titanium oxide, you may use any of a rutile type titanium oxide and an anatase type titanium oxide.

  Examples of the reactive functional group in the metal oxide fine particle include a hydroxyl group, an isocyanate group, an amino group, a mercapto group, a carboxy group, an epoxy group, a vinyl type unsaturated group, a halogen group, and an isocyanurate group.

  The content of the reactive functional group on the fine particle surface of the metal oxide fine particle can be obtained from the fine particle amount, the surface area of the fine particle, the amount of the surface treatment agent reacted, etc. In the present invention, the reaction amount with the surface treatment agent is Fine particles that are 0.1% by weight or more of the weight of the fine particles are referred to as “metal oxide fine particles having a reactive functional group on the fine particle surface”. Here, the reaction amount is the content of the reactive functional group, and the content in the metal oxide fine particles is not particularly limited as long as it is 0.1% by weight or more. In the present specification, the content of the reactive functional group on the surface of the metal oxide fine particles can be measured by the method of Examples described later, and the “content of the reactive functional group” means the reactive functional group. It means “content” and / or “abundance” of a group.

  In addition, the content of the reactive functional group on the surface of the metal oxide fine particles can be reduced, for example, by reacting the fine particles with a solution obtained by dissolving methyltrimethoxysilane in an organic solvent. Moreover, the amount of reactive functional groups on the surface of the fine particles can be reduced by firing the fine particles at a high temperature.

  As the metal oxide fine particles, those produced by a known method can be used, and among them, hydrothermal synthesis method, sol-gel method, supercritical water from the viewpoint of uniformity of particle size and fine particle formation. Those obtained by at least one production method selected from the group consisting of a thermal synthesis method, a coprecipitation method, and a uniform precipitation method are preferred.

  The average particle diameter of the metal oxide fine particles is preferably 1 to 100 nm, more preferably 1 to 70 nm, and still more preferably 1 to 20 nm, from the viewpoint of transparency when the composition is a molded body. In the present specification, the average particle size of the metal oxide fine particles can be measured by measuring the particle size of the particle dispersion by a dynamic light scattering method or directly observing with a transmission electron microscope.

  The metal oxide fine particles may be prepared in a dispersion from the viewpoint of suppressing aggregation (also referred to as “metal oxide fine particle dispersion”). Examples of the dispersion medium include water, alcohol, ketone solvents, and acetamide solvents, and it is preferable to use water, methanol, methyl butyl ketone, and dimethylacetamide. The amount (solid content concentration) of the metal oxide fine particles in the dispersion is preferably 10 to 40% by weight, more preferably 20 to 40% by weight, and still more preferably 25 from the viewpoint of efficiently performing the reaction on the surface of the fine particles. ~ 40% by weight. Such metal oxide fine particle dispersions include titanium oxide, NEOSUNVEIL or QUEEN TITANIC series from Catalytic Chemicals, Tynoch from Taki Chemical Co., Ltd., ZSL series from Daiichi Rare Chemicals Co., Ltd. Commercially available products such as the series and the nano-use series of Nissan Chemical Co., Ltd. can be used.

  The content of the metal oxide fine particles is preferably 1 to 70 parts by weight, more preferably 10 to 60 parts by weight, and still more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the silicone derivative.

  In addition to the silicone derivative and the metal oxide fine particles, the composition for thermosetting silicone resin of the present invention is an anti-aging agent, a modifier, a surfactant, a dye, as long as the effects of the present invention are not impaired. You may contain additives, such as a pigment, a discoloration inhibitor, and a ultraviolet absorber.

  The thermosetting silicone resin composition of the present invention is obtained by mixing a resin solution containing a trifunctional alkoxysilane having a molecular weight of 160 or less into the metal oxide fine particle dispersion at 40 to 80 ° C. The following low-boiling solvent is distilled off, and the reaction product obtained by reacting at 100 to 110 ° C. for 10 to 60 minutes (the first stage polymerization reaction) further contains a trifunctional alkoxysilane having a refractive index of 1.39 or more. It can be prepared by polymerizing the resin solution at 40 to 80 ° C. (second stage polymerization reaction). The resin solution in the first stage polymerization reaction is preferably a water / alcohol mixed solvent, water / alcohol weight ratio of 1/1 to 1/3, from the viewpoint of hydrophilicity on the surface of the metal oxide fine particles. As a resin solution in the polymerization reaction in the second step, the solution in which the trifunctional alkoxysilane is dissolved is a trifunctional alkoxysilane with alcohol and / or ether from the viewpoint of solubility and reactivity of the trifunctional alkoxysilane. It is preferable to prepare a solution in which is dissolved.

  In addition, the obtained thermosetting silicone resin composition has an appropriate thickness by, for example, casting, spin coating, roll coating, etc. on a release sheet (for example, a polyethylene substrate) whose surface has been subjected to a release treatment. Can be formed into a sheet shape by drying at a temperature at which the solvent can be removed. Therefore, this invention provides the silicone resin sheet formed by apply | coating the thermosetting silicone resin composition of this invention on a base material, and drying. Examples of the sheet include those having a thickness of about 10 to 1000 μm. The temperature at which the resin solution is dried varies depending on the type of resin or solvent and cannot be determined unconditionally, but is preferably 80 to 150 ° C. In addition, drying may be performed in two stages. In that case, the temperature in the first stage is preferably 90 to 120 ° C., and the temperature in the second stage is preferably 130 to 150 ° C.

  The resin composition of the present invention is highly transparent because of its excellent transparency.For example, when formed into a sheet having a thickness of 10 to 500 μm, the transmittance for incident light having a wavelength of 400 to 700 nm is preferable. Is 80% or more, more preferably 85% or more, and still more preferably 90 to 100%. In the present specification, the light transmittance is measured by the method described in Examples described later.

  The refractive index of the resin composition of the present invention is, for example, preferably 1.40 to 1.62, more preferably 1.42 to 1.62, and further preferably 1.44 to 1.62, when formed into a sheet having a thickness of 10 to 500 μm.

  A preferred method for producing the thermosetting silicone resin composition of the present invention includes a step of polymerizing trifunctional alkoxysilane having a molecular weight of 160 or less and metal oxide fine particles (hereinafter referred to as step (1)), and step (1 ) And a trifunctional alkoxysilane having a refractive index of 1.39 or more and a polymerization reaction until the reaction rate reaches 20 to 70% (hereinafter referred to as step (2)). In this specification, the reaction rate (%) refers to the reaction rate at the end of the polymerization reaction between the silicone derivative and the metal oxide fine particles, and specifically, for example, in a dryer at 150 ° C. for 3 hours. The change in weight before and after being allowed to stand can be measured, and can be calculated from the formula: amount of reaction water produced (mol) / theoretical amount of produced water (mol) × 100.

  As a specific example of the step (1), for example, a trifunctional alkoxysilane having a molecular weight of 160 or less is added to a liquid obtained by adding an organic solvent such as methanol or 2-methoxyethanol to a metal oxide fine particle dispersion. A resin solution prepared by dissolving in an alcohol such as methanol, ethanol, 2-propanol, 2-methoxyethanol or the like to a concentration of preferably 20 to 50% by weight is dropped and mixed at 40 to 80 ° C., and 100 to 110 ° C. And a step of reacting for 10 to 60 minutes.

  As a specific example of the step (2), for example, a trifunctional alkoxysilane having a refractive index of 1.39 or more is further added to the polymer obtained in the step (1) with an organic solvent such as 2-propanol, tetrahydrofuran or dimethoxyethane. Preferably, a resin solution prepared by dissolving so as to have a concentration of 20 to 50% by weight is dropped and mixed, and reacted at 40 to 80 ° C. for 0.2 to 2 hours. Finally, the reaction rate of the polymerization reaction is 20 Examples include a step of reacting to reach ˜70%. In addition, the reaction liquid obtained by the process (1) and the process (2) can be used for the process of distilling a solvent off under reduced pressure and concentrating, etc., and can adjust a density | concentration and a viscosity suitably.

  The thermosetting silicone resin composition thus obtained has a high light transmittance and a high refractive index.For example, an optical semiconductor device equipped with a blue or white LED element (a backlight of a liquid crystal screen, a traffic light, It can be suitably used as an optical semiconductor element sealing material used for large outdoor displays, advertising billboards, and the like. Therefore, this invention also provides the optical semiconductor device which seals an optical semiconductor element using the said thermosetting silicone resin composition.

  The optical semiconductor device of the present invention can be produced by sealing an LED element using the thermosetting silicone resin composition of the present invention as an optical semiconductor element sealing material. Specifically, the thermosetting silicone resin composition of the present invention is directly applied to a suitable thickness on a substrate on which the LED element is mounted by a method such as casting, spin coating or roll coating, and then heated and dried. By doing so, an optical semiconductor device can be manufactured.

  The optical semiconductor device of the present invention has a light-transmitting blue and white LED element in order to contain a thermosetting silicone resin composition having a high light transmittance and a high refractive index as an optical semiconductor element sealing material. Even a semiconductor device can be used suitably because it can be extracted with high emission luminance. When the luminance of the LED element before sealing is 100%, the light extraction efficiency of the optical semiconductor device of the present invention is preferably as high as possible, but is preferably 170% or more, more preferably 170 to 190%.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited at all by these Examples.

[Molecular weight of silicone derivatives]
Obtained in terms of polystyrene by gel filtration chromatography (GPC).

[Refractive index of silicone derivative and silicone resin composition]
Using a prism coupler (SPA-4000, manufactured by Cylon), the refractive index at 25 ° C. and 633 nm is measured.

[Average particle diameter of metal oxide fine particles]
In this specification, the average particle diameter of the metal oxide fine particles means the average particle diameter of the primary particles, and is a volume-median particle calculated by measuring the particle dispersion of the metal oxide fine particles by a dynamic light scattering method. It is the diameter (D ₅₀ ).

[Reactive functional group content on metal oxide fine particle surface]
Add ethyltrimethoxysilane as a surface treating agent to the fine particle dispersion and react, and then coagulate and settle the fine particles by centrifugation or pH fluctuations, collect by filtration, wash and dry, and determine the weight loss by differential thermogravimetric analysis. To calculate the content.

[Light transmittance of silicone resin composition]
Using a spectrophotometer (U-4100, manufactured by Hitachi High-Tech), the transmission spectrum in the visible light region of 400 to 800 nm is measured, and the transmittance at 400 nm is calculated.

Examples 1-16 and Comparative Examples 1-2
In a vessel equipped with a stirrer, reflux condenser, and nitrogen introduction tube, an aqueous dispersion of zirconium oxide having an average particle size of 5 nm as a metal oxide fine particle having a reactive functional group on the fine particle surface (trade name `` NZD-3005 '' Manufactured by Sumitomo Osaka Cement Co., Ltd., solid content concentration 40% by weight, containing hydroxyl group as a reactive functional group, reactive functional group content 1.0% by weight or more) 5.0 g (the amount used with respect to 100 parts by weight of silicone derivative is Example 2) And 16 is 22 parts by weight, otherwise 29 parts by weight), 5.0 g of methanol and 5.0 g of 2-methoxyethanol are added, and the pH of the solution is adjusted to 2-3 with concentrated hydrochloric acid and stirred. The temperature was raised to 60 ° C. As a silicone derivative having a trifunctional alkoxysilyl group at the molecular end, a solution obtained by dissolving the first-stage silicone derivative shown in Table 1 in 5.0 g of methanol in 5.0 g of methanol was added to a dropping funnel over 20 minutes. Then, methanol was distilled off under reduced pressure and concentrated, followed by reaction at 100 ° C. for 30 minutes (first stage reaction). Thereafter, the mixture was cooled to 60 ° C., added with 5.0 g of 2-propanol and stirred to obtain a uniform solution, and a solution obtained by dissolving the second-stage silicone derivative shown in Table 1 in 3.0 g of tetrahydrofuran in the amount shown in Table 1. Was added dropwise using a dropping funnel over 20 minutes, reacted at 60 ° C. for 1 hour (second stage reaction), cooled to room temperature (25 ° C.), and Examples 1 to 16 and Comparative Examples 1 to 2 thermosetting silicone resin compositions AP and RS were obtained. The obtained composition was concentrated by distilling off the solvent and water under reduced pressure, and a portion was collected and the reaction rate was determined from the change in weight when left in a dryer at 150 ° C. for 3 hours. The composition is coated on a PET substrate that has been subjected to a release treatment so as to have a film thickness of 100 μm, and heated at 100 ° C. for 1 hour and 150 ° C. for 1 hour, thereby forming a molded article ( Sheet) was prepared. Table 1 shows the reaction rate at the end of the polymerization reaction, and the transmittance and refractive index of the obtained composition at 400 nm. In addition, about the composition of the comparative examples 1 and 2, the polymerization reaction of a silicone derivative and metal oxide microparticles | fine-particles did not occur, but only the condensation reaction of the silicone derivative advanced, and the favorable composition was not able to be obtained.

Example 17
In Example 1, the thermosetting silicone resin composition of Example 17 was used in the same manner as in Example 1 except that the silicone derivative in the second stage was added dropwise and then cooled to room temperature (25 ° C.) without reacting. And the molded object was obtained. Composition Q and its molded body were obtained. The amount of metal oxide fine particles used was 29 parts by weight with respect to 100 parts by weight of the silicone derivative.

Comparative Example 3
In Example 1, a solution prepared by adding 4.0 g of silicone derivative (KBM13) to 5.0 g of methanol and stirring was dropped into a metal oxide fine particle aqueous dispersion and reacted at 100 ° C., and then a silicone derivative ( KBM13) Instead of adding a solution prepared by adding 3.0 g of 2-propanol to 3.0 g with stirring and reacting at 60 ° C. by dropping, prepare 10.0 g of silicone derivative (KBM103) to 10.0 g of 2-propanol and stirring. A thermosetting silicone resin composition T was prepared in the same manner as in Example 1 except that the obtained solution was dropped into the metal oxide fine particle aqueous dispersion and allowed to react only at 60 ° C. The amount of metal oxide fine particles used was 20 parts by weight with respect to 100 parts by weight of the silicone derivative. However, the polymerization reaction between the silicone derivative and the metal oxide fine particles did not occur, and only the condensation reaction of the silicone derivative proceeded, and a good composition could not be obtained.

Comparative Example 4
In Example 1, a solution prepared by adding 4.0 g of silicone derivative (KBM13) to 5.0 g of methanol and stirring was dropped into the metal oxide fine particle aqueous dispersion, methanol was distilled off, and the reaction was performed at 100 ° C. Furthermore, instead of dropping a solution prepared by adding 3.0 g of silicone derivative (KBM13) to 3.0 g of 2-propanol and stirring the solution at 60 ° C. by adding dropwise to the metal oxide fine particle aqueous dispersion, 4.0 g of silicone derivative (KBM13) The solution prepared by adding and stirring to 5.0 g of methanol was added dropwise to the metal oxide fine particle aqueous dispersion without causing high temperature, and then 3.0 g of silicone derivative (KBM13) was added to 3.0 g of 2-propanol and stirred. A thermosetting silicone resin composition U was prepared in the same manner as in Example 1 except that the obtained solution was dropped into the metal oxide fine particle aqueous dispersion and reacted together at 60 ° C. The amount of metal oxide fine particles used was 29 parts by weight with respect to 100 parts by weight of the silicone derivative. However, the polymerization reaction between the silicone derivative and the metal oxide fine particles did not occur, and only the condensation reaction of the silicone derivative proceeded, and a good composition could not be obtained.

The silicone derivatives shown in Table 1 are as follows and are all manufactured by Shin-Etsu Chemical Co.
[Trifunctional alkoxysilane]
Methyltrimethoxysilane: trade name “KBM13”, molecular weight 136.2, refractive index 1.369
Phenyltrimethoxysilane: Trade name “KBM103”, molecular weight 198.3, refractive index 1.473
Hexyltrimethoxysilane: trade name “KBM3063”, molecular weight 206.4, refractive index 1.406
Vinyltrimethoxysilane: Trade name “KBM1003”, molecular weight 148.2, refractive index 1.397
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane: trade name “KBM303”, molecular weight 246.4, refractive index 1.448
3-Glycidoxypropyltrimethoxysilane: trade name “KBM403”, molecular weight 236.3, refractive index 1.427
p-styryltrimethoxysilane: trade name “KBM1403”, molecular weight 224.3, refractive index 1.501
3-Methacryloxypropyltrimethoxysilane: trade name “KBM503”, molecular weight 248.4, refractive index 1.429
3-Acryloxypropyltrimethoxysilane: trade name “KBM5103”, molecular weight 234.4, refractive index 1.427
N-2- (aminoethyl) -3-aminopropyltrimethoxysilane: trade name “KBM603”, molecular weight 222.4, refractive index 1.445
3-Aminopropyltrimethoxysilane: Trade name “KBM903”, molecular weight 179.3, refractive index 1.422
N-phenyl-3-aminopropyltrimethoxysilane: Trade name “KBM573”, molecular weight 255.4, refractive index 1.504
3-mercaptopropyltrimethoxysilane: Trade name “KBM803”, molecular weight 196.4, refractive index 1.440
Decyltrimethoxysilane: Trade name “KBM3103C”, molecular weight 262.5, refractive index 1.421
Ethyltrimethoxysilane: Trade name “LS-890”, molecular weight 150.3, refractive index 1.384
[Bifunctional alkoxysilane]
3-Methacryloxypropylmethyldimethoxysilane: trade name “KBM502”, molecular weight 232.4, refractive index 1.433
Dimethylmethoxysilane: Trade name “KBM22”, molecular weight 120.2, refractive index 1.371

  As a result, the compositions of the examples were good compositions with high light transmittance and refractive index. On the other hand, in the compositions of Comparative Examples 1 and 2, since the bifunctional alkoxysilane itself reacts to produce highly hydrophobic silicone, it does not react with the highly hydrophilic metal oxide fine particles or is dispersed even when reacted. Is inadequate and agglomerates to cause white turbidity. The compositions of Comparative Examples 3 and 4 have low solubility parameters and high-hydrophobic silicone derivatives reacted together, so that they do not react with the metal oxide fine particles, or even when reacted, the dispersion becomes insufficient and agglomerates. It is estimated that white turbidity occurred.

Test Example 1 (Optical semiconductor encapsulation)
Using the thermosetting silicone resin composition A (refractive index 1.61) of Example 1, sealing was performed on a blue LED (trade name “C460MB290”, manufactured by Cree) according to a conventional method. The brightness of the blue LED before and after sealing was measured with an instantaneous multi-photometry system (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.), and the light extraction efficiency was determined according to the following formula. As a reference product, a commercially available silicone elastomer (trade name “KE-1052”, manufactured by Shin-Etsu Chemical Co., Ltd., refractive index 1.40) was used.
Light extraction efficiency (%) = (Luminance after sealing / Luminance before sealing) x 100

  As a result, the light extraction efficiency of the reference product is 160%, whereas the light extraction efficiency of the thermosetting silicone resin composition A of the present invention is 186%, which shows that it is greatly improved.

  The thermosetting silicone resin composition of the present invention is suitably used for sealing a semiconductor element such as a backlight of a liquid crystal screen, a traffic light, an outdoor large display or an advertising billboard.

Claims (9)

Obtained by polymerizing a silicone derivative having a trifunctional alkoxysilyl group at the molecular end and a metal oxide fine particle having a reactive functional group on the surface of the fine particle, and the silicone derivative has a trifunctional alkoxysilyl group at the molecular end A thermosetting silicone resin composition comprising two or more types of silicone derivatives, wherein the polymerization reaction is performed by adding the silicone derivatives in two or more stages in the presence of the metal oxide fine particles , A thermosetting silicone resin composition, wherein the content of metal oxide fine particles is 1 to 70 parts by weight with respect to 100 parts by weight of the silicone derivative . The silicone derivative has the formula (I):

Wherein, OR ¹ is an alkoxy group, R ¹ is 1 to 4 carbon atoms, a straight-chain or branch-chain alkyl group, X is 1 to 12 carbon atoms, straight-chain or branch A chain alkyl group that may contain a heteroatom at the end, or an end that is an epoxy group, primary, secondary or tertiary amino group, (meth) acryloyl group, cyclohexyl epoxy group, or aromatic group You may have
The thermosetting silicone resin composition of Claim 1 formed by containing the compound represented by these.   The thermosetting silicone resin composition according to claim 1 or 2, wherein the metal oxide fine particles have an average particle diameter of 1 to 100 nm.   The thermosetting silicone resin composition according to any one of claims 1 to 3, wherein the metal oxide fine particles are at least one selected from the group consisting of titanium oxide, zirconium oxide, barium titanate, silica, alumina, and hafnium oxide. object.   The thermosetting silicone resin composition according to any one of claims 1 to 4, wherein an overall reaction rate at the end of the polymerization reaction is 20 to 70%.   6. The polymerization reaction of the fine particles and a silicone derivative having a trifunctional alkoxysilyl group at a molecular terminal in a dispersion of metal oxide fine particles having a reactive functional group on the surface of the fine particles. Thermosetting silicone resin composition. The silicone derivative having a trifunctional alkoxysilyl group at the molecular end and the metal oxide fine particle having a reactive functional group on the fine particle surface are in two or more stages , and the content of the metal oxide fine particle is 100 weights of the silicone derivative. The manufacturing method of a thermosetting silicone resin composition including the process of making it polymerize so that it may become 1-70 weight part with respect to a part .   A silicone resin sheet formed by coating the thermosetting silicone resin composition according to any one of claims 1 to 6 on a substrate and drying the composition.   The optical semiconductor device formed by sealing an optical semiconductor element using the thermosetting silicone resin composition in any one of Claims 1-6.