KR102119861B1 - Moldable silicone resin, composition and semiconductor light emitting device thereof - Google Patents

Abstract

The present invention relates to a silicone resin, a composition capable of mold molding, and a semiconductor light emitting device thereof. First, a silicone resin capable of mold molding and a method of manufacturing the same are provided. The molar ratio of [MeSiO _3/2 ] units, [PhSiO _3/2 ] units, [R ₂ SiO _2/2 ] units, and hydroxyl groups in the silicone resin, as the silicone resin is solid at 25° C. and the melting point is less than 50° C. By controlling within a specific numerical range, a silicone resin suitable for condensation-type silicone molding materials, having a relatively low melting point, and capable of molding is obtained. The present invention also provides a silicone resin composition capable of mold molding. The silicone resin described in the present invention can be mixed with at least a crosslinking agent, an inorganic filler, and a condensation catalyst to obtain a condensed silicone molding material having good low-temperature processability and weather resistance. In addition, the present invention also provides a molded body and a manufacturing method thereof, an LED housing and a semiconductor light emitting device.

Description

Moldable silicone resin, composition and semiconductor light emitting device thereof {MOLDABLE SILICONE RESIN, COMPOSITION AND SEMICONDUCTOR LIGHT EMITTING DEVICE THEREOF}

The present invention relates to a silicone resin that can be molded, a composition, and a semiconductor light emitting device thereof, and is particularly suitably used for condensation type silicone molding materials, and has a relatively low melting point and is capable of mold molding. And a semiconductor light emitting device.

Semiconductor light emitting devices, such as LEDs, have advantages such as small size, high efficiency, long life, and excellent luminescence, and have been recently attracting wide attention. A typical semiconductor light emitting device is generally formed by molding a molded material such as polyamide or epoxy resin, housing it, placing chips and leads in the housing, and filling and sealing the housing with an encapsulment to seal it. do. Since the housing material has poor heat resistance and light resistance, yellowing occurs when used for a long period of time, resulting in problems such as a decrease in reflectance and a decrease in mechanical strength. Silicone molding material (SMC) has good heat resistance and light resistance, and has been used to manufacture a housing for a semiconductor light emitting device in place of polyamide and epoxy resin.

Silicone molding materials are mainly classified into two types: addition type and condensation type. Additive silicone molding material is to realize curing by hydrosilylation reaction. The essential components generally include alkenyl group-containing polysiloxanes, hydrogen polysiloxanes, platinum catalysts, inorganic fillers, inhibitors, and the like, and the compounding is complicated, and the alkenyl group-containing organic polysiloxanes and organic hydrogen polysiloxanes used are complex in synthesis. The cost is high. In comparison, the condensation type silicone molding material achieves curing by condensation reaction. The essential components generally include a silicone resin, a condensation reaction catalyst, an inorganic filler, etc., and the compounding is relatively simple, and the silicone resin used is easy to synthesize and has a relatively low cost.

The Chinese patent CN101519531B discloses a condensation-type silicone molding material that can manufacture an LED housing by mold molding at 120 to 190°C for 30 to 600 seconds, and also exhibits good heat resistance, light resistance, and low yellowing. The condensation-type silicone molding material includes a silicone resin having an average composition formula of R ¹ _a Si(OR ² ) _b (OH) _c O _(4-abc)/2 . Since the silicone resin is limited in its structure and performance, its melting point should be controlled to 40 to 130°C, preferably 70 to 80°C. If the melting point is less than 40°C, mold molding is difficult because the silicone resin does not become a solid or becomes a sticky solid. Since the silicone resin used has a high melting point, it is difficult to mix the silicone resin uniformly with other components at the general mixing temperature (generally 100° C. or less) when mixing the molding material. In addition, in order to improve the filling property of the molding material during molding of the molding material, it is generally necessary to control the molding temperature to a high temperature of 150 to 190°C. Due to these defects, the low-temperature processability of the condensation type silicone molding material is poor, and it is difficult to mix and mold at a relatively low temperature. In addition, the prior art including the above documents does not teach how to give the condensation type silicone molding material a desirable low-temperature processability and to further improve weather resistance.

Therefore, at present, the development of silicone resins suitable for condensation-type silicone molding materials and having a relatively low melting point and capable of mold molding becomes an urgent need, and improvement of low-temperature processability and weatherability of condensation-type silicone molding materials is also urgent.

It is an object of the present invention to provide a silicone resin suitable for condensation type silicone molding materials, having a relatively low melting point, and capable of mold molding, and a method for manufacturing the same. Another object of the present invention is to provide a condensed silicone molding material having good low-temperature processability and weather resistance. An additional object of the present invention is to provide a molded molded body made of the condensation type silicone molding material and a method for manufacturing the molded body. An additional object of the present invention is to provide an LED housing made of the condensation type silicone molding material, and also to provide a semiconductor light emitting device having the LED housing.

In order to achieve the object of the present invention, the present invention is a silicone resin shown in the average unit formula of formula (1), wherein the silicone resin is solid at 25°C and has a melting point of less than 50°C.

[MeSiO _3/2 ] _a [PhSiO _3/2 ] _b [R ₂ SiO _2/2 ] _c [HO _1/2 ] _d (1)

(In Formula 1, R represents Me or Ph. a, b, c, and d represent molar ratios, a is 0.3 to 0.9, b is 0.05 to 0.5, c is 0.05 to 0.5, d is 0.001 to 0.3, And a + b + c = 1.)

The silicone resin according to the present invention preferably has a of 0.4 to 0.8, b of 0.1 to 0.4, c of 0.1 to 0.3, d of 0 0.01 to 0.2, and a + b + c = 1.

The silicone resin according to the present invention preferably has a melting point of 25 to 40°C.

The present invention is also a method for producing a silicone resin,

(a) a first mixture comprising water, an acidic catalyst and a first organic solvent is added to a second mixture comprising chlorosilane and a second organic solvent to hydrolyze the chlorosilane, A hydrolysis process for separating an organic phase and an aqueous phase from a decomposition reaction product,

(b) neutralizing the pH of the separated organic phase to 7 to 14 and then condensing to condense the reaction,

Provided is a method for preparing a silicone resin according to the present invention, wherein the chlorosilane is a combination of MeSiCl ₃ , PhSiCl ₃ and R ₂ SiCl ₂ (where R represents Me or Ph).

The present invention is also a silicone resin composition,

(A) 100 parts by weight of the silicone resin according to any one of claims 1 to 3, or the silicone resin produced by the method according to claim 4;

(B) a hydroxyl group, an alkoxy group, an acyloxy group, an amide group, a ketoxime group or an isopropenyloxy group (isopropenyloxy) that binds to a silicon atom group) 1 to 30 parts by weight of a crosslinking agent having at least three;

(C) 1 to 800 parts by weight of an inorganic filler; And

(D) a condensation catalyst in an effective amount as a catalyst;

It provides a silicone resin composition capable of mold molding comprising a.

The silicone resin composition according to the present invention further contains 1 to 100 parts by weight of the (E) white pigment relative to 100 parts by weight of the silicone resin (A).

The present invention also provides a molded article formed by mold molding the silicone resin according to the invention, the silicone resin produced by the method according to the invention or the silicone resin composition according to the invention.

The present invention also provides a method of manufacturing a molded article comprising molding a silicone resin according to the invention, a silicone resin produced by the method according to the invention or a silicone resin composition according to the invention.

The present invention also provides an LED housing formed by mold molding the silicone resin composition according to the present invention.

The present invention also provides a semiconductor light emitting device having the LED housing according to the present invention.

In the present invention, the silicone resin according to the present invention is solid at 25° C., and has a melting point of 50° C. [MeSiO _3/2 ] units, [PhSiO _3/2 ] units, [R ₂ SiO _{2 / 2} ] By controlling the molar ratio of units and hydroxyl groups (OH) within a specific numerical range, a silicone resin suitable for condensation type silicone molding materials, having a relatively low melting point, and being moldable is obtained. In addition, the present invention can be obtained by mixing the silicone resin with at least a crosslinking agent, an inorganic filler, and a condensation catalyst to obtain a condensed silicone molding material having good low-temperature processability and weather resistance. In addition, the present invention mold-molded the condensation-type silicone molding material to produce a molded body and an LED housing. In addition, the present invention additionally manufactured a semiconductor light emitting device having the LED housing.

1 is a view showing a semiconductor light emitting device according to the present invention.

The terms "LED housing" described in the present invention, referred to as "LED case", "LED reflector", "LED reflector" and "LED bracket", have the same meaning in the present invention.

In the present invention, "room temperature" refers to 25°C unless otherwise specified.

The "effective amount as a catalyst" referred to in the present invention has a conventional meaning known in the art, and refers to a compounding amount of a catalyst capable of effectively catalyzing the smooth progression of the condensation reaction.

The term "silicone resin" as used in the present invention has the same meaning as "silicone resin that can be molded" unless otherwise specified.

The term "silicone resin composition" as used in the present invention has the same meanings as "silicone resin composition capable of mold molding" and "condensation type silicone molding material" unless otherwise specified.

In the present invention, "Ph" represents a phenyl group, and "Me" represents a methyl group.

Hereinafter, the present invention will be described in detail by specific examples. However, the scope according to the present invention is not limited to these specific embodiments.

<silicone resin>

The silicone resin according to the present invention is shown in the average unit formula of formula (1) and the silicone resin is solid at 25°C and has a melting point of less than 50°C.

[MeSiO _3/2 ] _a [PhSiO _3/2 ] _b [R ₂ SiO _2/2 ] _c [HO _1/2 ] _d (1)

(In Formula 1, R represents Me or Ph, a, b, c, d represents a molar ratio, a is 0.3 to 0.9, b is 0.05 to 0.5, c is 0.05 to 0.5, d is 0.001 to 0.3, a + b + c = 1.

In formula 1, a is preferably 0.4 to 0.8, b is preferably 0.1 to 0.4, c is preferably 0.1 to 0.3, d is preferably 0.01 to 0.2, and a + b + c = 1.

Preferably, the silicone resin according to the present invention has a melting point of 25 to 40°C.

The present inventor is that the silicone resin is solid at 25°C and has a melting point of less than 50°C. [MeSiO _3/2 ] units, [PhSiO _3/2 ] units, [R ₂ SiO _2/2 ] units and hydroxyl groups ( It has been found that by controlling the molar ratio of OH) within a specific numerical range, it is possible to obtain a silicone resin suitable for condensation type silicone molding materials and having a relatively low melting point and being moldable.

When evaluating mold moldability by stickiness at room temperature, the silicone resin according to the present invention has a surface adhesiveness at room temperature of less than 3.0 gf, more preferably less than 2.0 gf, most preferably 1.5. gf. Since the silicone resin described in the present invention has a surface tack at room temperature of less than 3.0 gf, there is no stickiness on the surface at room temperature, and is suitable for mold molding of condensed silicone molding materials. The method for evaluating the surface tack at room temperature is omitted herein in order to be described in detail in the Examples of the present invention.

In addition, the present invention is the present invention by controlling the molar ratio of [MeSiO _3/2 ] units, [PhSiO _3/2 ] units, [R ₂ SiO _2/2 ] units and hydroxyl groups (OH) in the silicone resin within a specific numerical range. It has been found that condensation-type silicone molding materials having good low-temperature processability and weather resistance when mixing the described silicone resin with at least a crosslinking agent, an inorganic filler, and a condensation catalyst can be obtained.

<Method of manufacturing silicone resin>

Method of manufacturing a silicone resin according to the present invention

(a) A first mixture comprising water, an acidic catalyst and a first organic solvent is added to a second mixture comprising chlorosilane and a second organic solvent to hydrolyze the chlorosilane, thereby A hydrolysis process for separating the organic phase from the aqueous phase,

(b) neutralizing the pH of the separated organic phase to 7 to 14 and then condensing to condense the reaction,

The chlorosilane is a combination of MeSiCl ₃ , PhSiCl ₃ and R ₂ SiCl ₂ (where R represents Me or Ph).

In the hydrolysis step (a), it is preferable that the water is deionized water.

In the hydrolysis step (a), the type of the acidic catalyst is not particularly limited. Specific examples thereof include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and boric acid; Organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, maleic acid, methanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoropropionic acid, and trifluoromethanesulfonic acid ; Solid acids such as acid clay and sulfonated ion exchange resins; Or mixtures thereof, but are not limited thereto.

In the hydrolysis step (a), the first organic solvent and the second organic solvent may be the same or different, and each independently, benzene, toluene, xylene, petroleum ether, or mixtures thereof Is selected from.

In the hydrolysis step (a), the R ₂ SiCl ₂ may be Me ₂ SiCl ₂ , Ph ₂ SiCl ₂ , MePhSiCl ₂ or any combination thereof. Preferably, the R ₂ SiCl ₂ is Me ₂ SiCl ₂ .

In the hydrolysis step (a), the amount of water, MeSiCl ₃ , PhSiCl ₃ and R ₂ SiCl ₂ is a, b, c, d in the silicone resin according to the present invention where a is 0.3 to 0.9, b is It is preferable that 0.05 to 0.5, c is 0.05 to 0.5, d is 0.001 to 0.3, and it is an amount that satisfies the requirements of a + b + c = 1.

In the hydrolysis step (a), the reaction temperature of the hydrolysis reaction may be 0 to 120°C, preferably 50 to 100°C, and the reaction time of the hydrolysis reaction may be 0.5 to 24 hours, , Preferably 1 to 12 hours.

In the condensation step (b), the neutralization is preferably performed by adding a neutralizing agent. The neutralizing agent used in the present invention is not particularly limited. Specific examples include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; Hydroxides of quaternary phosphoniums such as tetrabutylphosphonium hydroxide and tetrabutylphosphonium hydroxide; Or mixtures thereof, but are not limited thereto.

In the condensation step (b), the reaction temperature of the condensation reaction may be 0 to 120, preferably 50 to 100°C, and the reaction time of the condensation reaction may be 0.5 to 24 hours, preferably 1 to 12 hours.

In the method for producing a silicone resin according to the present invention, it is preferable that the hydrolysis step (a) and/or the condensation step (b) further include a reflux process.

In the method for producing a silicone resin according to the present invention, it is preferable to further include a step of removing the organic solvent after the condensation step (b).

<Silicone resin composition>

The silicone resin composition described in the present invention

(A) 100 parts by weight of the silicone resin according to the present invention,

(B) 1 to 30 parts by weight of a crosslinking agent having at least three hydroxyl groups, an alkoxy group, an acyloxy group, an amide group, a ketoxime group, or an isopropenyloxy group bonded to a silicon atom,

(C) 1 to 800 parts by weight of an inorganic filler,

(D) As a catalyst, an effective amount of a condensation catalyst is included.

The present invention has found that the silicone resin according to the present invention can be mixed with at least a crosslinking agent, an inorganic filler, and a condensation catalyst to obtain a condensed silicone molding material having good low-temperature processability and weather resistance. The evaluation of the low-temperature processability and weatherability is omitted here for the sake of explanation in the Examples of the present invention.

<Crosslinking system>

The silicone resin composition according to the present invention comprises a crosslinking agent (B) having at least three hydroxyl groups, alkoxy groups, acyloxy groups, amide groups, ketoxime groups or isopropenyloxy groups that are bonded to silicon atoms. In the present invention, the crosslinking agent (B) has a function of increasing the elastic modulus of the cured product of the silicone resin composition according to the present invention.

Specific examples of the crosslinking agent (B) used in the present invention

Hydroxysilanes such as methyl trihydroxysilane, ethyl trihydroxysilane, propyl trihydroxysilane, vinyl trihydroxysilane, phenyl trihydroxysilane, or tetra hydroxysilane;

Methyl trimethoxysilane, methyl triethoxysilane, methyl tripropoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, ethyl tripropoxysilane, propyl trimethoxysilane, propyl triethoxysilane , Propyl trimethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, phenyl tripropoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tripropoxysilane, tetramethoxysilane, tetraether Alkoxysilanes such as oxysilane or tetra propoxysilane;

Acyloxysilanes such as methyl triacetoxysilane, ethyl triacetoxysilane, propyl triacetoxysilane, vinyl triacetoxysilane, phenyl triacetoxysilane or tetra acetoxysilane;

Methyltris(dimethyl ketooxime)silane, ethyltris(dimethyl ketoxime)silane, propyl tris(dimethyl ketoxime)silane, vinyltris(dimethyl ketoxime)silane, phenyltris(dimethyl ketoxime) )Silane, methyltris(methylethyl ketoxime)silane, ethyltris(methylethyl ketoxime)silane, propyltris(methylethyl ketoxime)silane, vinyltris(methylethyl ketoxime)silane, phenyltris(methylethyl ketoxime) Ketoximesilane, such as silane, tetra propyl ketoxime silane, or tetra butyl ketoxime silane;

Isopropenyloxysilanes such as methyl triisopropoxysilane, ethyl triisopropoxysilane, propyl triisopropoxysilane, vinyl triisopropoxysilane, phenyl triisopropoxysilane, or tetra isopropoxysilane (isopropenyloxysilane), but is not limited thereto.

In the silicone resin composition according to the present invention, with respect to 100 parts by weight of the silicone resin (A), the amount of the crosslinking agent (B) used may be 1 to 30 parts by weight, preferably 5 to 20 parts by weight.

<Inorganic filler>

The silicone resin composition according to the present invention comprises an inorganic filler (C). In the present invention, the inorganic filler (C) has a function of improving the mechanical strength of the swelling rate of the cured product of the silicone resin composition according to the present invention.

It does not specifically limit as a kind of inorganic filler used for this invention. Specific examples include, but are not limited to, spherical silica, alumina, glass fibers, glass beads, titanium oxide, zinc oxide, and litopone.

In the silicone resin composition according to the present invention, with respect to 100 parts by weight of the silicone resin (A), the amount of the inorganic filler (C) may be 1 to 800 parts by weight, and preferably 1 to 600 parts by weight.

<Condensation catalyst>

The silicone resin composition according to the present invention comprises a condensation catalyst (D). In the present invention, the condensation catalyst (D) has a function of catalyzing within the silicone resin molecule, between the silicone resin molecules, and the condensation reaction between the silicone resin molecule and the crosslinker molecule to proceed smoothly.

The type of condensation catalyst (D) used in the present invention is not particularly limited. A concrete example

Lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium methoxide, sodium formate, potassium formate, sodium acetate, potassium acetate, sodium propionate, potassium propionate, Trimethyl benzyl ammonium hydroxide, tetra methyl ammonium hydroxide, n-hexylamine, diethylamine, triethylamine, tributylamine, imidazole, pyridine, triphenylphosphine, diazabicycloundecene (1,8- Basic compounds such as Diazabicyclo[5.4.0]undec-7-ene) or dicyandiamide;

Tetraisopropyl titanate, tetrabutyl titanate, titanium acetylacetonate, diisopropoxybis(ethyl acetoacetate) titanium [diisopropoxy-bisethylacetoacetatotitanate], triisobutoxy aluminum, Triisopropaluminum aluminum, aluminum tri acetylacetonate, aluminum bis ethyl acetoacetate, mono acetylacetonate, zirconium tetra acetylacetonate, zirconium (IV) acetylacetonate, tetrabutyrate zirconate Cobalt (cobalt naphthenate), cobalt octanoate, cobalt acetylacetonate, iron acetylacetonate, tin acetylacetonate, dimethyl hydroxy tin olate, dioctyltin maleate, di- n-butyl tin dimalate, dibutyl tin dimaleate, dibutyl tin dioctoate, dibutyl tin dilaurate, stannous acetate, stannous octanoate, zinc octylate , p-tert-butyl zinc benzoate, zinc laurate, zinc stearate or lead naphthenate, and the like, but are not limited thereto.

In the silicone resin composition according to the present invention, with respect to 100 parts by weight of the silicone resin (A), the amount of the condensation catalyst (D) used is 0.005 to 10 parts by weight, preferably 0.001 to 5 parts by weight.

<White pigment>

It is preferable that the silicone resin composition which concerns on this invention contains a white pigment (E) further. In the present invention, the white pigment (E) has a function of improving the whiteness of the cured product of the silicone resin composition according to the present invention to satisfy the property demand for high reflectivity of the housing material of the semiconductor light emitting device.

It does not specifically limit as a kind of white pigment used for this invention. Specific examples thereof include titanium dioxide, alumina, zirconia, zinc sulfide, zinc oxide, magnesium oxide, calcium oxide, barium sulfate, or a combination thereof, but are not limited thereto. From the viewpoint of obtaining a high refractive index, it is preferable that the white pigment is titanium dioxide. The titanium dioxide may be one of a rutile type, an anatase type, and a brookite type. From the viewpoint of obtaining a high refractive index, the titanium dioxide is preferably rutile.

In the silicone resin composition according to the present invention, based on 100 parts by weight of the silicone resin (A), the amount of the white pigment (E) used is 1 to 100 parts by weight, preferably 1 to 60 parts by weight.

<Other additives>

The silicone resin composition according to the present invention may also contain other additives in order to satisfy other required characteristics without departing from the object of the present invention. Other additives used in the present invention include mold releasing agents such as stearic acid, stearate, silicone oil, and waxes; And coupling agents such as KH-550, KH-560, and KH-570, but are not limited thereto. In the present invention, the amount of the other additive is not particularly limited, but may be a general amount in the art.

<Method for manufacturing silicone resin composition>

The method for producing the silicone resin composition according to the present invention is not particularly limited, and methods known in the art can be used.

In general, the method of manufacturing a silicone resin composition according to the present invention,

(a) After at least uniformly mixing the components containing the silicone resin (A), the crosslinking agent (B), the inorganic filler (C), and the condensation catalyst (D), the mixture is melt-kneaded using a melt-kneading apparatus, A melt-kneading process to form a melt-kneaded product,

(b) a granulation process in which the obtained melt-kneaded product is cooled and hardened to pulverize the cured product into particles.

In the melt-kneading step (a), it is preferable that the component also contains a white pigment (E). If necessary, the component contains another additive.

In the melt-kneading step (a), the melt-kneading device is not particularly limited, but may include a heat roll, a kneader, or an extruder, but is not limited thereto.

In the melt-kneading step (a), the melt-kneading treatment temperature is not particularly limited, but may be 20 to 100°C, and preferably 25 to 60°C.

The present inventor uses the silicone resin according to the present invention which is suitable for condensation type silicone molding materials, has a relatively low melting point, and can be molded. The silicone resin composition according to the present invention can realize melt kneading of each component even at relatively low temperatures. It has also been found that mixing is relatively uniform, and thereby exhibits good low-temperature processability.

<Mold molded body and manufacturing method thereof>

The molded article according to the present invention is formed by mold molding the silicone resin composition according to the present invention.

The method for manufacturing a molded article according to the present invention includes molding a silicone resin composition according to the present invention.

In the present invention, the mold molding is preferably transfer molding, mold press molding, injection molding or extrusion molding, and more preferably transfer molding.

In the present invention, the molding temperature of the mold molding is preferably 20 ~ 150 ℃, more preferably 50 ~ 130 ℃, most preferably 50 ~ 120 ℃. The molding time of the mold molding is preferably 20 to 600 seconds, more preferably 25 to 400 seconds, and most preferably 30 to 300 seconds.

The molded article according to the present invention may perform an aftercure treatment if necessary. The after-cure treatment temperature is not particularly limited, but may be 50 to 300°C, preferably 100 to 250°C. The after-cure treatment time is not particularly limited, but may be from 1 minute to 5 hours, and preferably from 10 minutes to 2 hours.

The present inventors use the silicone resin of the present invention which is suitable for condensation type silicone molding materials, has a relatively low melting point, and can be molded. The silicone resin composition according to the present invention can be molded on a molded body even at relatively low temperatures. It exhibits low-temperature processability and is also found to have good weatherability.

<LED case>

The LED housing according to the present invention is formed by mold molding the silicone resin composition according to the present invention. In the present invention, the mold molding method for manufacturing the LED housing described in the present invention may be the same as the method for manufacturing the molded body described above. Redundant description is omitted here.

<Semiconductor light emitting device>

The semiconductor light emitting device according to the present invention includes the LED housing according to the present invention.

According to one specific embodiment of the present invention, the semiconductor light emitting device of the present invention is shown in FIG. 1. The semiconductor light emitting device is provided with a chip (1), a lead (2), a lens (3), a sealing material (4) and a housing (5). The housing 5 is manufactured by mold molding the silicone resin composition according to the present invention.

Example

Hereinafter, the present invention will be further described by examples. However, the scope according to the present invention is not limited to the examples.

<Evaluation of average unit formula>

The average unit formula of the silicone resin is confirmed by measuring the hydrogen nuclear magnetic resonance spectrum (1H-NMR) and the silicon nuclear magnetic resonance spectrum (29Si-NMR) of the silicone resin using the AVANCE II 400MHz nuclear magnetic resonance apparatus from Bruker, Switzerland did.

<Measurement of melting point>

The melting point of the silicone resin was confirmed by measuring the DSC curve of the silicone resin using a DSC 204HP differential scanning calorimeter manufactured by Netzsch, Germany.

<Evaluation of surface adhesion at room temperature>

The silicone resin was mold-press molded into a test sample having dimensions of 10 cm × 10 cm × 2 mm, and then placed on the surface of a stainless plate having a dimension of 15 cm × 15 cm × 1 mm and having a flat surface. The stainless steel plate on which the test sample was placed is TA of Stable Micro Systems, UK. Place in the center of the stage of the TX Plus type material analysis equipment (texture analyzer), select the P35 probe, the speed before measurement is 1.0 mm/s, the measurement speed is 0.5 mm/s, the measurement speed is 10.0 mm/s, contact The measurement program was set so that the time was 2.0 s, the return distance was 5.0 mm, and the guide force was Auto-10gf. The program controls the probe to be inserted vertically downwards to a predetermined depth inside the sample, and then measures the force required to vertically pull the probe upwards from inside the sample, thereby allowing the probe sample to be at room temperature at that location. It is evaluated by measuring the surface adhesiveness (unit: gf (gf)). Using the same method, the surface tack at room temperature was measured at 10 different places of the test sample, and the average value was taken as the surface tack at room temperature of the test sample.

<Evaluation of low-temperature processability>

After mixing the components of the silicone resin composition uniformly, it was added to a kneader to perform a melt-kneading treatment at 40°C, and the obtained melt-kneaded product was cooled and hardened and pulverized into particles. The obtained particles were added to a transfer molding machine, and the particles were inserted into a metal mold having a pore size of 50 cm × 50 cm × 5 mm at 80° C. at a pressure of 7 MPa, held for 200 seconds, and mold-molded. After the mold was cooled to room temperature, the mold was opened, and the molded body was taken out as a test sample. The appearance of the test sample was observed and evaluated. It is denoted by "○" when the surface of the test sample has 5 or less cracks or voids, and "X" when the surface of the test sample has 5 or more cracks or voids.

<Weatherability evaluation>

The silicone resin composition was mold press molded into a test sample having dimensions of 10 cm×10 cm×2 mm. The test sample was placed on an ultraviolet visible spectrophotometer, the light reflectance of 350 nm to 400 nm was measured, and the initial reflectance r ₀ was indicated. Subsequently, the test sample was taken out and left for 1000 hours in an environment having a temperature of 85° C. and a relative humidity of 85%, and the light reflectances of 350 nm to 400 nm were measured again to indicate final reflectance r ₁ . Based on the formula Δr = ((r ₀ -r ₁ )/r ₀ ) × 100%, the attenuation amount Δr(%) of the reflectance was calculated, and the weather resistance of the silicone resin composition was evaluated.

<Synthesis Example 1>

In a reactor equipped with a stirrer, thermometer, and condensation reflux means, the stirrer was turned'on' and 504.0 g (28.0 mol) of deionized water, 9.0 g hydrochloric acid with a concentration of 0.05 N, and 1000.0 g of toluene were prepared. While slowly heating the reactor, the reactor was made of 747.5 g (5.0 mol) of methyl trichlorosilane, 634.5 g (3.0 mol) of phenyl trichlorosilane, 258.0 g (2. 0 mol) of dimethyl dichlorosilane, and 1000.0 g of toluene. 2 The mixture was slowly added dropwise. After the dropping of the second mixture was completed, the internal temperature of the reactor was maintained at 70°C and hydrolyzed for 3 hours under reflux to obtain a hydrolysis reaction product. The obtained hydrolysis reaction product was cooled and left to stand, and the layers were separated to separate an organic phase and an aqueous phase. After adjusting the separated organic phase to pH 9 with potassium hydroxide, put it in a reactor installed in the same manner as the reactor, set the stirrer to'on' and maintain the internal temperature of the reactor at 70°C to condense the reactant for 2 hours under reflux. Got The solvent and low boiling point material of the condensation reaction product were removed by distillation under reduced pressure to obtain about 898.0 g of a colorless transparent solid (hereinafter, silicone resin A-1).

^It was confirmed by ¹ H-NMR and ²⁹ Si-NMR that the average unit formula of the silicone resin A-1 was as shown in formula (1-1).

[MeSiO _3/2 ] _0.5 [PhSiO _3/2 ] _0.3 [Me ₂ SiO _2/2 ] _0.2 [HO _1/2 ] _0.03 (1-1)

The performance of the silicone resin A-1 is shown in Table 1.

<Synthesis Example 2>

In a reactor equipped with a stirrer, thermometer, and condensation reflux means, the stirrer was turned'on' and 540.0 g (30.0 mol) of deionized water, 10.0 g of hydrochloric acid with a concentration of 0.05 N, and 1500.0 g of toluene were prepared. While slowly heating the reactor, a second mixture of 897.0 g (6 moles) of methyl trichlorosilane, 423.0 g (2.0 moles) of phenyl trichlorosilane, 258.0 g (2.0 moles) of dimethyl dichlorosilane and 1500.0 g of toluene was added to the reactor. Dropped slowly. After completion of the dropping of the second mixture, the internal temperature of the reactor was maintained at 80° C. and hydrolysis reaction was performed for 5 hours under reflux to obtain a hydrolysis reaction product. The obtained hydrolysis reaction product was cooled and left to separate the layers to separate the organic phase and the aqueous phase. After adjusting the separated organic phase to pH 8 with potassium hydroxide, put it in a reactor installed in the same manner as the reactor, turn on the stirrer and maintain the internal temperature of the reactor at 75° C. to condense for 5 hours under reflux to condensate reactants. Got The solvent and low-boiling-point material of the condensation reaction product were removed by distillation under reduced pressure to obtain about 868.5 g of a colorless transparent solid (hereinafter, silicone resin A-2).

^It was confirmed by ¹ H-NMR and ²⁹ Si-NMR that the average unit formula of the silicone resin A-2 was as shown in formula (1-2).

[MeSiO _3/2 ] _0.6 [PhSiO _3/2 ] _0.2 [Me ₂ SiO _2/2 ] _0.2 [HO _1/2 ] _0.1 (1-2)

The performance of the silicone resin A-2 is shown in Table 1.

<Synthesis Example 3>

In a reactor equipped with a stirrer, thermometer, and condensation reflux means, the first stirrer was prepared by putting the stirrer'on' and adding 720.0 g (40.0 mol) of deionized water, hydrochloric acid with a concentration of 0.05 N, and 2000.0 g of toluene. While gradually raising the reactor, the reactor consisted of 1046.5 g (7.0 mol) of methyl trichlorosilane, 423.0 g (2.0 mol) of phenyl trichlorosilane, 129.0 g (1. 0 mol) of dimethyl dichlorosilane, and 1600.0 g of toluene. 2 The mixture was slowly added dropwise. After completion of the dropping of the second mixture, the internal temperature of the reactor was maintained at 70° C., and hydrolysis reaction was performed at reflux for 10 hours to obtain a hydrolysis reaction product. The obtained hydrolysis reaction was cooled and left standing to separate the layers and separated into an organic phase and an aqueous phase. After adjusting the separated organic phase to pH 10 with potassium hydroxide, put it in the same reactor as the above reactor, set the stirrer to'on', maintain the internal temperature of the reactor at 80° C., and condense the reactant for 10 hours under reflux. Got The solvent and low boiling point material of the condensation reaction product were removed by distillation under reduced pressure to obtain about 866.8 g of a colorless transparent solid (hereinafter, silicone resin A-3).

^It was confirmed by ¹ H-NMR and ²⁹ Si-NMR that the average unit formula of the silicone resin A-3 was as shown in Formula (1-3).

[MeSiO _3/2 ] _0.7 [PhSiO _3/2 ] _0.2 [Me ₂ SiO _2/2 ] _0.1 [HO _1/2 ] _0.1 (1-3)

The performance of the silicone resin A-3 is shown in Table 1.

<Synthesis Example 4>

In a reactor equipped with a stirrer, a thermometer, and a condensation reflux means, a stirrer was turned'on' and 1044.0 g (58.0 mol) of deionized water, 15.0 g of hydrochloric acid with a concentration of 0.05 N, and 1000.0 g of toluene were prepared. While slowly heating the reactor, the reactor was made of 1196.0 g (8.0 mol) of methyl trichlorosilane, 211.5 g (1.0 mol) of phenyl trichlorosilane, 129.0 g (1. 0 mol) of dimethyl dichlorosilane, and 2000.0 g of toluene. 2 The mixture was slowly added dropwise. After the dropping of the second mixture was completed, the internal temperature of the reactor was maintained at 70° C. and hydrolysis reaction was carried out for 1 hour under reflux to obtain a hydrolysis reaction product. The obtained hydrolysis reaction was cooled and allowed to stand to separate the layers and separated into an organic phase and an aqueous phase. After adjusting the separated organic phase to pH 9 in potassium hydroxide, put it in a reactor installed in the same manner as the reactor, select a stirrer, maintain the internal temperature of the reactor at 75° C., and condense for 10 hours under reflux to obtain a condensation reaction product. The solvent and low-boiling-point material of the condensation reaction product were removed by distillation under reduced pressure to obtain about 847.2 g of a colorless transparent solid (hereinafter, silicone resin A-4).

^It was confirmed by ¹ H-NMR and ²⁹ Si-NMR that the average unit formula of the silicone resin A-4 was as shown in Formula (1-4).

[MeSiO _3/2 ] _0.8 [PhSiO _3/2 ] _0.1 [Me ₂ SiO _2/2 ] _0.1 [HO _1/2 ] _0.2 (1-4)

The performance of the silicone resin A-4 is shown in Table 1.

<Comparative Synthesis Example 1>

In a reactor equipped with a stirrer, thermometer, and condensation reflux means, the stirrer was turned'on' and 504.0 g (28.0 mol) of deionized water, 7.0 g of hydrochloric acid at a concentration of 0.05 N, and 700.0 g of toluene were prepared to prepare a first mixed solution. While gradually heating the reactor, a second mixture of 1196.0 g (8.0 mol) of methyl trichlorosilane, 258.0 g (2.0 mol) of dimethyl dichlorosilane and 700.0 g of toluene was slowly added dropwise to the reactor. After the dropping of the second mixture was completed, the internal temperature of the reactor was maintained at 75° C. and hydrolysis reaction was performed for 5 hours under reflux to obtain a hydrolysis reaction product. The obtained hydrolysis reaction was cooled and left standing to separate the layers and separated into an organic phase and an aqueous phase. After adjusting the separated organic phase to pH 8 with potassium hydroxide, put it in a reactor installed in the same manner as the above reactor, set the stirrer to'on', maintain the internal temperature of the reactor at 80° C., and condense the reactant for 3 hours under reflux. Got The solvent and low-boiling-point material of the condensation reaction product were removed by distillation under reduced pressure to obtain about 615.7 g of a colorless transparent solid (hereinafter, silicone resin A'-1).

^It was confirmed by ¹ H-NMR and ²⁹ Si-NMR that the average unit formula of the silicone resin A'-1 was as shown in Formula (1-5).

[MeSiO _3/2 ] _0.8 [Me ₂ SiO _2/2 ] _0.2 [HO _1/2 ] _0.1 (1-5)

The performance of the silicone resin A'-1 is shown in Table 1.

<Comparative Synthesis Example 2>

In a reactor equipped with a stirrer, a thermometer, and a condensation reflux means, a stirrer was turned on and 540.0 g (30.0 mol) of deionized water, 8.0 g of hydrochloric acid with a concentration of 0.05 N, and 1700.0 g of toluene were prepared. While gradually raising the reactor, a second mixed solution consisting of 897.0 g (6.0 mol) of methyl trichlorosilane, 846.0 g (4.0 mol) of phenyl trichlorosilane and 1700.0 g of toluene was slowly added dropwise to the reactor. After the dropping of the second mixture was completed, the internal temperature of the reactor was maintained at 70°C and hydrolyzed for 3 hours under reflux to obtain a hydrolysis reaction product. The obtained hydrolysis reaction was cooled and left standing to separate the layers and separated into an organic phase and an aqueous phase. After adjusting the separated organic phase to pH 9 with potassium hydroxide, put it in a reactor installed in the same manner as the reactor, select a stirrer, maintain the internal temperature of the reactor at 75° C., and condense for 5 hours under reflux to obtain a condensation reaction product. The solvent and low boiling point material of the condensation reaction product were removed by distillation under reduced pressure to obtain about 628.4 g of a colorless transparent solid (hereinafter, silicone resin A'-2).

^It was confirmed by ¹ H-NMR and ²⁹ Si-NMR that the average unit formula of the silicone resin A'-2 was as shown in Formula (1-6).

[MeSiO _3/2 ] _0.6 [PhSi _3/2 ] _0.4 [HO _1/2 ] _0.1 (1-6)

The performance of the silicone resin A'-2 is shown in Table 1.

<Comparative Synthesis Example 3>

In a reactor equipped with a stirrer and a thermometer, turn on the stirrer and add 1008.0 g (56.0 mol) of deionized water, 816.0 g (6.0 mol) of methyl trimethoxysilane, 396.0 g (2.0 mol) of phenyl trimethoxysilane, and dimethyl A mixture consisting of 302.0 g (2.0 moles) of dimethoxysilane and 3000 g toluene was slowly added dropwise into the reactor. After the dropwise addition of the mixture, the internal temperature of the reactor was maintained at 50° C. and hydrolysis reaction was performed for 1 hour to obtain a hydrolysis reaction product. The obtained hydrolysis reaction was aged at 50°C for 1 hour, and then washed with deionized water. Subsequently, azeotropic dehydration, filtration, and distillation under reduced pressure were performed to remove the solvent and the low-boiling-point substance to obtain about 748.9 g of a colorless transparent solid (hereinafter, silicone resin A'-3).

^It was confirmed by ¹ H-NMR and ²⁹ Si-NMR that the average unit formula of the silicone resin A'-3 was as shown in Formula (1-7).

[MeSiO _3/2 ] _0.6 [PhSi _3/2 ] _0.2 [Me ₂ SiO _2/2 ] _0.2 [MeO _1/2 ] _0.04 [HO _1/2 ] _0.06 (1-7)

The performance of the silicone resin A'-3 is shown in Table 1.

Performance Synthetic example Comparative Synthesis Example One 2 3 4 One 2 3 Silicone resin A-1 A-2 A-3 A-4 A'-1 A'-2 A'-3 Appearance form (25℃) solid solid solid solid solid solid solid Melting point (℃) 27 31 34 40 28 27 22 Surface adhesion at room temperature (gf) 1.9 1.7 1.4 1.3 4.1 4.3 7.2

In Table 1, the silicone resins A-1, A-2, A-3 and A-4 obtained in Examples 1 to 4 of the present invention are [MeSiO _3/2 ] units, [PhSiO _3/2 ] units, [R ₂ SiO _2/2 ] The molar ratio of the unit and the hydroxyl group both satisfy the numerical range required by the present invention, and are solid at room temperature, while the melting point is less than 50°C, and the surface adhesion at room temperature is both less than 2.0 gf, and at room temperature. It was found that there is no stickiness on the surface and it is suitable for mold molding of condensation type silicone molding material.

In addition, as can be seen through comparison, the silicone resin A'-1 of Comparative Synthesis Example 1 and the silicone resin A-2 of Example 2 of the present invention have a molar ratio of both trifunctional siloxane units, bifunctional siloxane units, and hydroxyl groups. The same, the silicone resin A'-1 of Comparative Synthesis Example 1 does not contain PhSiO _3/2 units of the trifunctional siloxane unit, while the silicone resin A-2 of Example 2 of the present invention has a certain amount of trifunctional siloxane units The only difference is that it contains _3/2 units of PhSiO. The silicone resin A'-2 of Comparative Synthesis Example 2 and the silicone resin A-2 of Example 2 of the present invention have the same molar ratio of both hydroxyl groups, and the silicone resin A'-2 of Comparative Synthesis Example 2 is a bifunctional siloxane While it does not contain a unit and includes only a trifunctional siloxane unit, the silicone resin A-2 of Example 2 of the present invention differs only in that it contains a difunctional siloxane unit as well as a trifunctional siloxane unit. The silicone resin A'-3 of Comparative Synthesis Example 3 and the silicone resin A-2 of Example 2 of the present invention are both [MeSiO _3/2 ] units, [PhSiO _3/2 ] units, and [R ₂ SiO _{2/ 2} ] The molar ratio of the unit and the remaining condensable group (that is, hydroxyl group and/or alkoxy group) is the same, and the condensable group remaining in the silicone resin A'-3 of Comparative Synthesis Example 3 contains a certain amount of methoxy group. , The condensable groups remaining in the silicone resin A-2 of Example 2 of the present invention differ only in that they are hydroxyl groups. As can be seen from the measurement results, the silicone resins A'-1, A'-2 and A'-3 obtained in Comparative Synthesis Examples 1-3 were compared with the silicone resin A-2 obtained in Example 2 of the present invention at room temperature. They are all solid and have a melting point of less than 50°C, but the surface tack at room temperature is greater than 4.0 gf, and the surface is sticky at room temperature, and therefore is not suitable for mold molding of condensed silicone molding materials.

As described above, the present invention is [SiSiO _3/2 ] unit, [PhSiO _3/2 ] unit, [R ₂ SiO ₂ ] in silicone resin, as the silicone resin of the present invention is solid at 25° C. and has a melting point of less than 50° C. _/2 ] By controlling the molar ratio of units and hydroxyl groups within a specific numerical range, a silicone resin suitable for condensation type silicone molding materials, having a relatively low melting point, and capable of mold molding was obtained.

100 parts by weight of silicone resin A-1 prepared in Synthesis Example 1, 7 parts by weight of crosslinking agent B-1 (tetraethoxysilane), 400 parts by weight of inorganic filler C-1 (silicon dioxide), condensation catalyst D-1 (dibutyl Tin dilaurate) 1 part by weight, 40 parts by weight of white pigment E-1 (rutile type titanium dioxide) are uniformly mixed, melt-kneaded at 40°C by adding to a kneader, and then cooled and hardened, and then crushed. After being made of particles, silicone resin composition 1 was obtained through this. Table 2 shows the performance.

Except for using the silicone resin A-2 prepared in Synthesis Example 2 instead of the silicone resin A-1 in Synthesis Example 1, all other materials and manufacturing processes were the same as in Example 1 to obtain a silicone resin composition 2. Table 2 shows the performance.

The silicone resin composition 3 was obtained in the same manner as in Example 1, except that the silicone resin A-3 prepared in Synthesis Example 3 was used instead of the silicone resin A-1 in Synthesis Example 1. Table 2 shows the performance.

A silicone resin composition 4 was obtained in the same manner as in Example 1, except for the silicone resin A-4 prepared in Synthesis Example 4, instead of the silicone resin A-1 in Synthesis Example 1. Table 2 shows the performance.

[Comparative Example 1]

The silicone resin composition 1'was obtained in the same manner as in Example 1, except for the silicone resin A'-1 prepared in Comparative Synthesis Example 1 instead of the silicone resin A-1 in Synthesis Example 1. . Table 2 shows the performance.

[Comparative Example 2]

The silicone resin composition 2'was obtained in the same manner as in Example 1 except for the silicone resin A'-2 prepared in Comparative Synthesis Example 2 instead of the silicone resin A-1 in Synthesis Example 1. . Table 2 shows the performance.

[Comparative Example 3]

A silicone resin composition 3'was obtained in the same manner as in Example 1 except for the silicone resin A'-3 prepared in Comparative Synthesis Example 3 instead of the silicone resin A-1 in Synthesis Example 1, all of which were the same as in Example 1. . Table 2 shows the performance.

[Comparative Example 4]

Materials other than the silicone resin A-1 of Synthesis Example 1 prepared in the same manner as in Synthesis Example 2 of CN101519531B, except that a silicone resin having a melting point of 80.7° C. (hereinafter, silicone resin A′-4) was used. The manufacturing process was the same as in Example 1 to obtain a silicone resin composition 4'. Table 2 shows the performance.

Furtherance
(Parts by weight)
Example Comparative Example One 2 3 4 One 2 3 4 Silicone resin composition One 2 3 4 One' 2' 3' 4' Silicone resin A-1 100 A-2 100 A-3 100 A-4 100 A'-1 100 A'-2 100 A'-3 100 A'-4 100 Crosslinker B-1 10 10 10 10 10 10 10 10 Inorganic filler C-1 400 400 400 400 400 400 400 400 Condensation catalyst D-1 One One One One One One One One White pigment E-1 40 40 40 40 40 40 40 40 Low temperature processability ○ ○ ○ ○ X X X X Weatherability (%) 14.3 8.5 6.7 5.1 5.2 48.9 23.6 17.8

In Table 2, silicone resin compositions 1 to 4 of Examples 1 to 4 of the present invention and silicone resin compositions 1'to 4'of Comparative Examples 1 to 4 are all mixed with a silicone resin, a crosslinking agent, an inorganic filler, and a condensation catalyst. The silicone resins used in Examples 1 to 4 of the present invention are each sequentially the silicone resins A-1 to A-4 of Synthesis Examples 1 to 4, whereas the silicone resins used in Comparative Examples 1 to 4 are sequentially It can be seen that the differences are only in that the silicone resins A'-4 prepared by Synthesis Example 2 of Comparative Synthesis Examples 1 to 3 of the silicone resins A'-1 to A'-3 and CN101519531B. As can be seen from the measurement results, all of the silicone resin compositions 1 to 4 of Examples 1 to 4 of the present invention have low-temperature processability, while all of the silicone resin compositions 1'to 4'of Comparative Examples 1 to 4 are low temperature. There is no processability. In addition, the silicone resin compositions 1 to 4 of Examples 1 to 4 of the present invention have better weather resistance than the silicone resin compositions 2'to 4'of Comparative Examples 2 to 4.

Thus, the present invention, by mixing the silicone resin according to the present invention with at least a crosslinking agent, an inorganic filler, and a condensation catalyst, it was possible to obtain a condensed silicone molding material having good low-temperature processability and weather resistance.

1 chip
2 leads
3 lenses
4 encapsulant
5 housing

Claims (10)

As a silicone resin shown in the average unit formula of formula (1),
[MeSiO _3/2 ] _a [PhSiO _3/2 ] _b [R ₂ SiO _2/2 ] _c [HO _1/2 ] _d (1)
(In Formula 1, R represents Me or Ph, a, b, c, d represents a molar ratio, a is 0.3 to 0.9, b is 0.05 to 0.5, c is 0.05 to 0.5, d is 0.001 to 0.3, and a + b + c = 1.
The silicone resin is a solid at 25 °C, the melting point is less than 50 °C, a silicone resin capable of mold molding.
The silicone resin according to claim 1, wherein a is 0.4 to 0.8, b is 0.1 to 0.4, c is 0.1 to 0.3, d is 0.01 to 0.2, and a + b + c = 1.
The silicone resin according to any one of claims 1 to 2, wherein the silicone resin has a melting point of 25 to 40°C.
A method for manufacturing the silicone resin of claim 1,
(a) a first mixture comprising water, an acidic catalyst and a first organic solvent is added to a second mixture comprising chlorosilane and a second organic solvent to hydrolyze the chlorosilane, A hydrolysis process for separating an organic phase and an aqueous phase from a decomposition reaction product,
(b) neutralizing the pH of the separated organic phase to 7 to 14 and then condensing to condense the reaction,
Method of producing a silicone resin, wherein the chlorosilane is a combination of MeSiCl ₃ , PhSiCl ₃ and R ₂ SiCl ₂ (where R represents Me or Ph).
As a silicone resin composition,
(A) 100 parts by weight of the silicone resin of claim 1;
(B) a hydroxyl group, a alkoxy group, an acyloxy group, an amide group, a ketoxime group or an isopropenyloxy group (isopropenyloxy) that binds to a silicon atom group) 1 to 30 parts by weight of a crosslinking agent having at least three;
(C) 1 to 800 parts by weight of an inorganic filler; And
(D) a condensation catalyst in an effective amount as a catalyst;
Silicone resin composition capable of mold molding comprising a.
The silicone resin composition according to claim 5, wherein the silicone resin composition further contains 1 to 100 parts by weight of the (E) white pigment relative to 100 parts by weight of the silicone resin (A).
A molded article obtained by mold molding a silicone resin composition comprising the silicone resin of claim 1.
A method of manufacturing a molded article comprising molding a silicone resin composition comprising the silicone resin of claim 1.
An LED housing formed by mold molding the silicone resin composition according to claim 5 or 6.
A semiconductor light emitting device comprising the LED housing of claim 9.

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