TW202010793A - Thermosetting silicone resin composition for reflector of LED, reflector of LED and semiconductor device using the same - Google Patents

Abstract

Disclosed is a thermosetting silicone resin composition for a reflector of a Light Emitting Diode (LED), a reflector of a LED and a semiconductor device using the same.

Description

Thermosetting silicone resin composition for light-emitting diode reflector, light-emitting diode reflector, and semiconductor device using the composition

The present invention relates to a thermosetting resin silicone composition having high light reflectivity, high heat resistance and low yellowing, and used for a light emitting diode (LED) reflector, and also relates to the use of the thermosetting silicone LED reflector and semiconductor device of the composition.

In recent years, optical semiconductor devices including optical semiconductor elements such as light emitting diodes (LEDs) have been used in various applications due to their advantages such as high energy efficiency and long life characteristics, and the demand for them continues to increase.

Such an optical semiconductor device is usually provided in a form in which an optical semiconductor element is mounted on a substrate (optical semiconductor element mounting substrate), and the optical semiconductor element is sealed with a transparent resin, which contains phosphor if necessary ( phosphor). In order to improve the efficiency of extracting light from the optical semiconductor element, a reflecting member (reflector) for reflecting light is provided on the substrate.

The reflector is usually manufactured by adding white pigment to a thermosetting resin such as epoxy resin and then performing transfer molding. The problem with this reflector is that it generates heat due to the high brightness of the optical semiconductor device and yellows due to the deterioration of the element material, so its light reflectance is significantly reduced.

Therefore, an object of the present invention is to provide a thermosetting resin composition for an LED reflector, which not only has a high light reflectivity, but also continuously shows heat resistance, low yellowing, and excellent mechanical properties during driving of an optical semiconductor element , And has excellent process applicability applicable to various processes, and also provides LED reflectors and semiconductor devices using the thermosetting resin composition.

The thermosetting silicone resin composition for an LED reflector according to the present invention contains: (A) Each molecule has at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group, and has a general formula RSiO _3/2 represents a branched-chain organopolysiloxane of the siloxane unit, where R is a substituted or unsubstituted monovalent hydrocarbon group; (B) a linear organopolysiloxane, the two ends of its molecular chain are Silicon-bonded hydrogen atoms are terminated and each molecule has at least one silicon-bonded aryl group; (C) Hydrosilylation catalyst; (D) Each molecule has at least one silicon-bonded alkenyl group Low molecular weight siloxane, which is represented by the following average formula: (R ⁵ ₃ SiO _{1/2) f} (R ⁵ ₂ SiO _2/2 ) _g (R ⁵ SiO _3/2 ) _h (SiO _4/2 ) _i Wherein each R ⁵ may be the same or different and is independently selected from substituted or unsubstituted monovalent hydrocarbon groups, wherein at least one R ⁵ in each molecule is an alkenyl group, provided that the ratio of alkenyl group to silicon atom is 0.3 to 1 (measured by ²⁹ Si NMR spectroscopy), f, g, h and i are independently 0 or a positive number, and the weight average molecular weight (Mw) of the siloxane is less than 1,000 g/mol (through size exclusion chromatography (SEC ) Measurement, tetrahydrofuran (THF) as solvent, concentration 5 mg/mL, refractive index detector relative to polystyrene as standard); and (E) white pigment.

In addition, the LED reflector according to the present invention contains the above-mentioned thermosetting silicone resin composition.

In addition, the semiconductor device of the present invention includes a reflector cured by using the above-mentioned thermosetting silicone resin composition.

Invention effect

The thermosetting silicone resin composition according to the present invention not only exhibits excellent light reflectance, but also rarely changes in its weight and hardness at high temperatures, which means that it has excellent heat resistance and mechanical properties. In addition, due to proper control of the components and their contents in the composition, the composition can have excellent process applicability suitable for various processes.

Therefore, the present invention can provide an LED reflector that is stable to the light emitted from the LED wafer and the heat generated during operation.

In addition, the present invention can improve the reliability of the semiconductor device including the LED reflector, because the LED reflector exhibits high light reflectivity and hardness at high temperature and has low yellowing.

Hereinafter, exemplary embodiments of the present invention will be described in detail. However, the exemplary embodiment of the present invention may be modified in various forms, and the scope of the present invention is not limited to the exemplary embodiment described below.

>Thermosetting silicone resin composition for LED reflector>

The present invention provides a thermosetting silicone resin composition for an LED reflector, which comprises: (A) Each molecule has at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group, and has The branched-chain organic polysiloxane of the siloxane unit represented by the general formula RSiO _3/2 , where R is a substituted or unsubstituted monovalent hydrocarbon group; (B) Linear organic polysiloxane, two of its molecular chain The terminal is terminated with silicon-bonded hydrogen atoms and has at least one silicon-bonded aryl group per molecule; (C) Hydrosilylation reaction catalyst; (D) Low molecular weight of at least one silicon-bonded alkenyl group per molecule Molecular weight siloxane, which is represented by the following average formula: (R ⁵ ₃ SiO _{1/2) f} (R ⁵ ₂ SiO _2/2 ) _g (R ⁵ SiO _3/2 ) _h (SiO _4/2 ) _i where , Each R ⁵ may be the same or different and is independently selected from substituted or unsubstituted monovalent hydrocarbon groups, wherein at least one R ⁵ per molecule is an alkenyl group, provided that the ratio of alkenyl groups to silicon atoms is 0.3 to 1, f, g, h and i are independently 0 or a positive number, the weight average molecular weight (Mw) of the siloxane is less than 1,000 g/mol; and (E) white pigment.

Hereinafter, the chemical composition of the thermosetting silicone resin composition according to the present invention will be described in detail. However, the present invention is not limited to the following exemplary embodiments, but is implemented in various forms.

Components ( A )

The component (A) is the main component of the composition of the composition according to the present invention, and is used to impart strength to the cured product obtained by curing the composition.

Component (A) represents a branched organic polysilicon having at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group per molecule and having a siloxane unit represented by the general formula RSiO _3/2 Oxane, where R is a substituted or unsubstituted monovalent hydrocarbon group.

In component (A), examples of alkenyl groups include vinyl, allyl, methallyl, butenyl, pentenyl and hexenyl groups, preferably vinyl and allyl groups, especially Preferably vinyl.

In component (A), examples of aryl groups include: phenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, benzophenyl, fluorenyl, xanthenyl, anthrone (Anthronyl); aryloxyaryl, such as o-phenoxyphenyl and p-phenoxyphenyl; alkaryl, such as o-tolyl, m-tolyl, p-tolyl, xylyl and ethylphenyl ; Aralkyl, such as benzyl, α-phenethyl and β-phenethyl. Preferably, the aryl group is phenyl.

In addition, examples of the organic group bonded to silicon in the component (A) other than alkenyl and aryl groups include substituted or unsubstituted monovalent hydrocarbon groups, and examples thereof include: methyl, ethyl, propyl , Butyl, pentyl, hexyl, heptyl, and other alkyl groups; and haloalkyl groups, such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl, particularly preferably methyl.

In the siloxane unit of the component (A) represented by the general formula RSiO _3/2 , R is a substituted or unsubstituted monovalent hydrocarbon group. The substituent of the hydrocarbon group may include the above-mentioned alkyl group, the above-mentioned alkenyl group, the above-mentioned aryl group, the above-mentioned aralkyl group and the above-mentioned haloalkyl group, and particularly preferably the above-mentioned alkyl group and the above-mentioned aryl group.

As component (A), an organic polysiloxane represented by the following average unit formula is preferred: (R ¹ R ¹ R ³ SiO _1/2)a (R ¹ ₂ SiO _2/2 ) _b (R ² SiO _3/2 ) _c (SiO _4/2 ) _d (XO _1/2 ) _e

In the above formula, each of R ¹ , R ² and R ³ may be the same or different, and are independently selected from substituted or unsubstituted monovalent hydrocarbon groups in which R ¹ , R ² or R ³ per molecule At least one of them is an alkenyl group, and at least one of R ¹ , R ^2, or R ³ in each molecule is an aryl group.

The monovalent hydrocarbon group may be more specifically exemplified by the aforementioned alkyl group, the aforementioned alkenyl group, the aforementioned aryl group, the aforementioned aralkyl group, and the aforementioned halogenated alkyl group.

The above-mentioned alkenyl group per molecule is preferably 0.1 to 40 mol%, more preferably 5 to 25 mol% of R ¹ , R ² and R ³ . This is because when the content of the alkenyl group is below the lower limit of the above range or exceeds the upper limit of the above range, its reactivity with the component (A) tends to decrease.

In addition, in order to achieve low attenuation in the cured product obtained by transmission curing due to light refraction, reflection, scattering, etc., preferably not less than 10 mole% of R ¹ , R ² and R ³ should be the above-mentioned aryl group, and in particular , In the siloxane unit represented by the general formula R ² SiO _3/2 , it is even more preferable that it is not less than 30 mole% of R ² should be represented by the above aryl group, where R except for alkenyl and aryl groups ^{2 is} preferably represented by methyl.

In addition, in the above formula, X is a hydrogen atom or an alkyl group, a is 0 or positive number, b is 0 or positive number, c is positive number, d is 0 or positive number, e is 0 or positive number, b/c is a number between 0 and 10, a/ c is a number between 0 and 0.5, d / (a + b + c + d) is a number between 0 and 0.3, and e / (a + b + c + d) is a number between 0 and 0.4.

As component (A), organic polysiloxanes having the following average unit formula are particularly preferred: (R ¹ R ¹ R ³ SiO _{1/2) a} (R ¹ ₂ SiO _2/2 ) _b (R ² SiO _3/2 ) _c

In the above formula, R ¹ is C ₁ to C ₁₂ alkyl, R ² is C ₆ to C ₂₀ aryl or C ₇ to C ₂₀ aralkyl, R ³ is C ₂ to C ₁₂ alkenyl, and a is 0 Or a positive number, b is 0 or a positive number, and c is a positive number.

Although there is no limit to the molecular weight of component (A), when converted to standard polystyrene, its weight average molecular weight (Mw) should preferably be in the range of 500 g/mol to 10,000 g/mol, and is particularly preferred In the range of 700 g/mol to 7,000 g/mol, more preferably in the range of 1,000 g/mol to 5,000 g/mol, especially 1,500 to 3,000 g/mol.

Based on the sum of the amounts of components (A) and (B), component (A) is preferably present in an amount equal to or greater than 70% by weight, more preferably 70 to 90% by weight, and particularly preferably 75 to 85% by weight.

According to an embodiment of the present invention, based on the total organosiloxane, (ie, the sum of component (A), component (B), component (C), and component (D)) is 100 parts by weight, thermosetting The silicone resin composition contains 60 to 75 parts by weight, more preferably 70 to 75 parts by weight of component (A).

Components ( B )

Component (B) is a curing agent of the composition of the present invention.

Component (B) is a linear organic polysiloxane, whose molecular chain ends are terminated by silicon-bonded hydrogen atoms, and each molecule has at least one silicon-bonded aryl group. By using linear organic polysiloxane instead of branched-chain organic polysiloxane as a curing agent, good elongation properties can be obtained.

Examples of the aryl group of component (B) are the same as those described above. Phenyl is particularly preferred.

In addition, examples of the organic group bonded to silicon in the component (B) other than the aryl group include substituted or unsubstituted monovalent hydrocarbon groups (excluding alkenyl groups), such as the above-mentioned alkyl group, the above-mentioned aralkyl group And the above-mentioned haloalkyl group is particularly preferably a methyl group.

In order to achieve low attenuation due to light refraction, reflection, scattering, etc. in the cured product obtained through curing, the content of all silicon-bonded organic groups in component (B) should be better Not less than 15 mol%, particularly preferably not less than 30 mol%. While on component (B) is not limited in viscosity at 25 ^o C, but is preferably in the range of 1 to 1,000 mPa · s, particularly preferably in the range of 2 to 500 mPa · s to. This is because when the viscosity of the component (B) is lower than the lower limit of the above range, it may be easily volatilized and the composition of the resulting composition may be unstable. On the other hand, when it exceeds the upper limit of the above range, the resulting composition Processing performance is easily deteriorated.

[式2]The organic polysiloxane represented by the following general formula is preferred as component (B):

[Form 2]

In the above formula, each R ⁴ may be the same or different, and is independently selected from a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, but does not include an alkenyl group.

Examples of the monovalent hydrocarbon group of R ⁴ include the aforementioned alkyl group, the aforementioned aryl group, and the aforementioned haloalkyl group.

Here, at least one R ⁴ per molecule must be one of the above aryl groups, preferably phenyl.

In addition, n in the above formula is an integer of 0 or more, preferably an integer in the range of 0 to 20, and particularly preferably an integer in the range of 0 to 10. This is because when the value of n exceeds the upper limit of the above range, the toughness of the resulting composition or the adhesiveness of the cured product tends to deteriorate. n is preferably from 1 to 4, especially 1, that is, component (B) represents trisiloxane.

By using M units instead of Q or T units as repeating units, good elongation properties can be obtained.

Based on the sum of the amounts of components (A) and (B), the content of component (B) is preferably 1 to 30% by weight, more preferably 10 to 30% by weight, and particularly preferably 15 to 25% by weight.

The mole of Si-H group in component (B) relative to the alkenyl group (e.g. vinyl group) in component (A) is preferably 1 to 1.2 in order to reduce reactive residual hydrogenated siloxane (silicone hydride) .

According to an embodiment of the present invention, based on the total organosiloxane, (ie, the sum of component (A), component (B), component (C), and component (D)) is 100 parts by weight, thermosetting The silicone resin composition contains 18 to 25 parts by weight, more preferably 20 to 22 parts by weight of component (B).

Components ( C )

Component (C) is a hydrosilation catalyst.

The hydrosilation catalyst of component (C) is used to promote the reaction of the alkenyl group of component (A) with the silicon-bonded hydrogen atom of component (B).

Examples of component (C) include platinum catalysts, rhodium catalysts and palladium catalysts. Platinum catalysts are preferred because they can significantly accelerate the curing of the compositions of the present invention. Examples of platinum catalysts include: platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, platinum/alkenyl siloxane complex, platinum/olefin-based complex and platinum/carbonyl complex, preferably platinum/ Alkenyl siloxane complex. Examples of alkenylsiloxanes include: 1,3-divinyl-1,1,3,3-tetramethyldisilaxane, 1,3,5,7-tetramethyl-1,3,5 ,7-tetravinylcyclotetrasiloxane, alkenylsiloxane obtained by substituting part of the methyl group of the above alkenylsiloxane through groups such as ethyl, phenyl, etc., and through allyl, hexyl An alkenyl siloxane obtained by substituting the vinyl group of the above alkenyl siloxane with groups such as alkenyl. Because of the excellent stability of the platinum/alkenylsiloxane complex, 1,3-divinyl-1,1,3,3-tetramethyldisilaxane is particularly preferred. In addition, it is expected that the addition of 1,3-divinyl-1,1,3,3-tetramethyl to the platinum/alkenylsiloxane complex due to the increased stability of the complex may be brought about by its addition Disilaxane, 1,3-diallyl-1,1,3,3-tetramethyldisilaxane, 1,3-divinyl-1,3-dimethyl-1,3- Diphenyl disilaxane, 1,3-divinyl-1,1,3,3-tetraphenyldisilaxane, 1,3,5,7-tetramethyl-1,3,5, 7-tetravinylcyclotetrasiloxane and other alkenyl siloxane and organic siloxane oligomers such as dimethyl siloxane oligomer, particularly preferably alkenyl siloxane.

The content of component (C) is not limited as long as the amount can promote the curing of the composition of the present invention. However, specifically, in the composition of the present invention, the content of component (C) is preferably 0.05 to 0.05 in terms of platinum content relative to the total amount of components (A) and (B) being 100 parts by weight 100 weight ppm (parts per million) is present, more preferably 0.1 to 10 weight ppm, particularly preferably 0.1 to 5 weight ppm. This is because when the content of the component (C) is lower than the lower limit of the above range, the composition of the present invention tends not to be completely cured. On the other hand, when it exceeds the upper limit of the above range, various effects may be given to the resulting cured product. The problem of color.

Components ( D )

Component (D) is an additive, which is a low molecular weight siloxane having at least one silicon-bonded alkenyl group per molecule, represented by the following average formula: (R ⁵ ₃ SiO _1/2)f (R ⁵ ₂ SiO _2/2 ) _g (R ⁵ SiO _3/2 ) _h (SiO _4/2 ) _i where each R ⁵ may be the same or different, and is independently selected from substituted or unsubstituted monovalent hydrocarbon groups, where each molecule At least one of R ⁵ is an alkenyl group, provided that the ratio of the alkenyl group to the silicon atom is 0.3 to 1, f, g, h, and i are independently 0 or a positive number, and the weight average molecular weight (Mw) of the siloxane Less than 1,000 g/mol, preferably less than 800 g/mol, more preferably less than 500 g/mol.

Preferably, component (D) is selected from the group consisting of D ^alkenyl ₄ , M ^alkenyl ₄ Q, M ^alkenyl ₆ Q ₂ , and M ^alkenyl ₃ T. Preferably, the alkenyl group is vinyl. Particularly preferred as component (D) are cyclotetrasiloxane D ^Vi ₄ and M ^Vi ₄ Q, especially D ^Vi ₄ .

It is assumed that component (D) is used to react with unreacted sites (Si-H), thereby avoiding additional reaction of unreacted sites due to heat or light. As a result, in the composition containing component (D), color change and mechanical strength change caused by high temperature can be significantly reduced.

In the composition according to the prior art, which does not contain component (D), the material often shows an increase in hardness after curing during high temperature storage, which can be attributed to the post-curing reaction of the remaining reactive sites and/or appears to be through Weight loss due to evaporation of low molecular weight substances that are not crosslinked into the polymer network. Due to changes in hardness and weight loss, the material is unstable under operating conditions. In the present invention, the reaction of component (D) with unreacted sites (Si-H) leads to better stability, such as small changes in hardness at high temperatures, small weight loss, and small discoloration.

Component (D) also has a filling effect, which makes it possible to reduce gas and vapor penetration. The sealant further containing component (D) provides stability to sulfur, and it is expected that this effect is obtained from the filling effect.

As a result, an LED package with excellent reliability can be obtained.

Component (D) is both reactive and small enough to react with residual hydrosiloxane. At the same time, component (D) is cross-linked into the silicone network, so the proportion of volatile components in the cured material is not increased. The amount of component (D) is preferably at most 10 parts by weight, more preferably at most 7 parts by weight, even more preferably at most 5 parts by weight relative to 100 parts by weight of the total amount of components (A) and (B). If the content of component (D) is high, the compatibility with other components is low, so the transmittance is low. Preferably, the amount of component (D) is at least 1 part by weight relative to the total amount of components (A) and (B) being 100 parts by weight. Taking into account the specific formulation and characteristics, the amount of component (D) can be appropriately selected.

According to an embodiment of the present invention, based on the total organosiloxane, (ie, the sum of component (A), component (B), component (C), and component (D)) is 100 parts by weight, thermosetting The silicone resin composition contains 1 to 5 parts by weight, more preferably 2 to 4 parts by weight of component (D).

Components ( E )

Component (E) is a white pigment.

The role of the white pigment (E) is to give the reflector a high light reflectivity, and also to reduce the linear expansion of the reflector, which is a cured product of the composition.

The white pigment (E) may be any white pigment known in the art, for example, an inorganic white pigment, an organic white pigment, a hollow particle pigment, or a mixture of two or more of the foregoing.

Non-limiting examples of inorganic white pigments include: glass, clay, mica, talc, kaolinite (kaolin), halloysite, zeolite, acid clay, activated clay, boehmite, pseudo Boehmite (psuedoboehmite), inorganic oxides, metal salts (such as alkaline earth metal salts, etc.), etc. In addition, non-limiting examples of organic white pigments include resin pigments such as styrene-based resins, benzoguanamine-based resins, urea-formaldehyde resins, melamine-formaldehyde resins, amide-based resins, and the like.

Preferably, the white pigment (E) in the present invention may be selected from titanium oxide, zinc oxide, silicon oxide, aluminum oxide, barium oxide, magnesium oxide, zirconium oxide, aluminum silicate, boron nitride, calcium carbonate, penta At least one of the group consisting of tantalum oxide, barium sulfate, magnesium carbonate, barium carbonate, and strontium titanate.

The white pigment (E) preferably has a high refractive index to increase the reflectivity of the reflector. In one example, a white pigment having a refractive index of 1.5 or higher is preferable. In this case, the white pigment having a hollow particle structure has a very high surface reflectance due to the low refractive index gas contained in the core, and therefore, the shell portion may also be composed of a material having a refractive index of less than 1.5. In addition, the white pigment (E) may be a surface-treated pigment known in the art. In one example, the surface treatment includes surface treatment with surface treatment agents such as metal oxides, silane coupling agents, titanium coupling agents, organic acids, polyols, siloxanes, and the like. When this surface treatment is performed, the compatibility of the white pigment with other components contained in the silicone resin composition according to the present invention, or the dispersibility of the white pigment can be improved.

In addition, the shape of the white pigment (E) is not particularly limited, and may be, for example, spherical, crushed, fibrous, needle-like, scale-like, or amorphous. From the viewpoint of dispersibility, a spherical shape is preferred, and a spherical shape having an aspect ratio of 1.2 or less is more preferred.

In addition, the average particle diameter of the white pigment is not particularly limited, but considering the improvement of the light reflectance of the cured product (white reflector), it may be 0.01 to 50 μm, preferably 0.1 to 50 μm. As used herein, the term “average diameter” refers to the diameter (median diameter, D ₅₀ ) measured by the laser diffraction/scattering method at 50% of the cumulative particle size distribution.

The content of the white pigment (E) in the thermosetting silicone resin composition according to the present invention is not particularly limited, and can be appropriately adjusted within a range known in the art. In one example, based on the total of component (A) to component (D) being 100 parts by weight, the content of white pigment (E) may be 1 to 300 parts by weight, preferably 20 to 250 parts by weight, more preferably 50 Up to 200 parts by weight. When the content of the white pigment is within the above range, the light reflectance of the reflector (ie, the cured product of the composition) can be further increased, and the fluidity of the thermosetting silicone resin composition can also be suppressed by adding the white pigment (E) Reduction, thereby improving workability and moldability.

In a preferred embodiment of the present invention, the white pigment (E) includes a titanium oxide-based first white pigment (E-1) having an average particle diameter (D ₅₀ ) of 0.1 to 2 μm. In view of increasing the reflectance of the cured product (white reflector) and increasing the light reflectance of the unit amount of white pigment added, the titanium oxide is preferable. The titanium oxide may be any titanium oxide known in the art, and may be, for example, rutile-type titanium oxide, anatase-type titanium oxide, brookite-type oxidation Titanium or a mixture of two or more of the foregoing.

The content of the first white pigment (E-1) is not particularly limited, but it may be at least 40 parts by weight, preferably 45 to 80 parts by weight based on the total of component (A) to component (D) being 100 parts by weight. When the composition contains at least 40 parts by weight of the titanium oxide-based first white pigment having the above-specified particle size based on the total weight of component (A) to component (D), it may exhibit 97% or Higher light reflectivity, thus maximizing the optical efficiency of the LED reflector.

Meanwhile, in the present invention, by using the above-mentioned titanium oxide-based first white pigment (E-1) in combination with pigments having various sizes and components, the viscosity and contact of the composition required in various processes can be adjusted appropriately Denaturation, hardness after heat curing, reflectivity, whiteness, etc. Therefore, the composition of the present invention may further include a second white pigment (E-2), a third white pigment (E-3), and a mixture thereof, which are different from the second white pigment in at least one of average particle size and components A white pigment (E-1).

In a preferred embodiment of the present invention, based on the total weight of the white pigment (E) is 100 parts by weight, the content of the first white pigment (E-1) and other pigments (such as E-2, The content ratio of E-3, E-2 + E-3, etc.) may be a weight ratio of 80-99.9: 0.1-20, preferably 80-99.5: 0.5-20.

The heat-curable silicone composition of the present invention may not include a linear organic polysiloxane having at least two silicon-bonded alkenyl groups and at least one silicon-bonded aryl group per molecule as a toughening unit. Assuming that a large branched-chain organic polysiloxane such as component (A) is used as the resin instead of linear organic polysiloxane, the curable silicone composition of the present invention can provide excellent hardness and toughness. In other words, the huge branched-chain organic polysiloxane is directly connected to the unreacted Si-H site.

The thermosetting silicone resin composition of the present invention may further contain a crosslinking agent commonly used in this field.

The thermosetting silicone resin composition of the present invention may further contain a curing inhibitor commonly used in this field, silica, glass, quartz, cristobalite, alumina, zinc oxide and other inorganic fillers, catalysts, and phosphors .

The composition of the present invention may further contain fine powder of organic resin (such as polymethacrylate resin) present as a selective component, heat stabilizer, dye, pigment, flame retardant, solvent, etc., as long as this does not damage the present invention the goal of.

The above composition can be prepared by mixing components commonly used in the art, for example, by mixing all components at ambient temperature. Specifically, the above components (components A, B, C, D, and E) and other additives may be mixed in a predetermined ratio through a Henschel mixer, a V-shaped mixer, a belt mixer, and a drum type Mix the mixture uniformly with a mixer, etc., then melt-knead using a roller mill, kneader, extruder, Banbury mixer, etc., cool and solidify the melt-kneaded material, and then grind the solid material to a suitable Size to prepare the composition.

Generally, in the process of manufacturing LED reflectors, the viscosity of the composition applicable to the dispensing process is 500 to 10,000 mPa·s, and the viscosity of the composition applicable to transfer molding and compression molding is 3,000 To 100,000 mPa∙s. Because of 100 to 2,000,000 mPa · s Viscosity (at 25 ^o C) prior to curing the thermosetting silicone resin composition of the alumoxane of the present invention, it can be applied to all the above as well as the dispensing process transfer molding and compression molding process. Further, when any one of the molding and compression molding the thermosetting silicone resin composition alumoxane through transfer molding, it can be quickly cured at a temperature of 100 to 170 ^o C in 30 to 600 seconds.

As described above, the thermosetting silicone resin composition of the present invention can be applied to various processes, and can be rapidly cured due to a high curing rate, indicating that it has excellent processability and moldability. In addition, it has high mechanical strength, heat resistance and light reflectance, so it can be preferably used for LED reflectors. In addition to being used for LED reflectors, the thermosetting silicone resin composition of the present invention can also be used in various light-emitting applications requiring high light reflectivity and excellent heat resistance without limitation. In one example, it can be used as a reflective member of various light-emitting devices, including electrical/electronic components, indoor lights, ceiling lights, outdoor lights, car lights, display devices, headlights, and the like.

>LED reflector>

The LED reflector according to the present invention includes the cured product of the above-mentioned thermosetting silicone resin composition.

The shape or size of the reflector is not particularly limited, and the reflector may include conventional configurations known in the art. In one example, the reflector may have a shape that is open on at least one side of the light emitting direction, or have a flat shape that is not opened.

The reflector according to the invention can be manufactured by conventional molding methods. In one example, it is through various molding methods (eg, transfer molding, compression molding, injection molding, LIM molding (injection molding), blow molding, insert molding, dam molding with a dispenser (dam molding ) Etc.), obtained by molding the above thermosetting silicone resin composition into a desired shape. In this case, the molding and curing of the composition can occur simultaneously. Alternatively, it is also possible to perform the post-curing process separately after the molding process. Among these molding methods, transfer molding or compression molding methods are preferably used.

In a specific example, the transfer molding process is preferably carried out using a transfer molding machine at a molding pressure of 5 to 20 N/mm ² at a molding temperature of 120 to 190 ^o C, especially 120 to 180 ^o C 30 to 500 seconds, especially 30 to 300 seconds.

In one particular example, the compression molding process is preferably carried out using a compression molding machine at 120 to 190 ^o C, the molding temperature is 120 to 180 [deg.] C especially of from 30 to 600 seconds, in particular from 120 to 420 seconds.

After the above molding process, a (post)curing process can be performed if necessary. The curing conditions of this process are not particularly limited, and can be appropriately adjusted within the range known in the art. , The curing process can be carried out from 30 to 30 seconds at a temperature of 100 to 170 ^o C in one example.

The reflector of the present invention manufactured as described above can exhibit high reflectance, excellent mechanical properties, and low yellowing even at high temperatures. In a preferred embodiment, the LED reflector according to the present invention may have: (i) Shore D hardness of at least 10, preferably at least 30, more preferably at least 50; (ii) at a wavelength of 450 nm Has a light reflectance of at least 90%, preferably at least 95%, more preferably at least 97%; and (iii) a yellowness index of 5 or less, preferably 3 or less.

In the present invention, an optical semiconductor element with a reflector (for example, a light-emitting diode element) can be mounted on the reflector by mounting a conventional LED element and other components known in the art, and then sealed with a sealing resin, Manufactured by bonding, bonding, etc. The optical semiconductor element (LED element) can be used in various applications. In one example, it can be used in applications including semiconductor devices, LCD displays, black light units (BLU), mobile phones, vehicle display lights, vehicle headlights, flashlights, indoor lights, traffic lights, street lights and Outdoor Light.

>Semiconductor device>

The present invention provides a semiconductor device including a reflector obtained by molding the above thermosetting silicone resin composition.

As used herein, the term "semiconductor device" includes all semiconductor devices known in the art. Specifically, the semiconductor device may include the above-described reflector (or reflector substrate), an optical semiconductor element mounted on the reflector, and a phosphor-containing transparent sealing resin layer that seals the optical semiconductor element. The optical semiconductor element may be an LED.

Examples of such semiconductor elements are semiconductor elements used in diodes, transistors, thyristors, solid-state image pickup elements, monolithic ICs (monolithic ICs), and hybrid ICs (hybrid ICs). In particular, the semiconductor element is preferably a light-emitting element.

Examples of such semiconductor devices include diodes, light-emitting diodes, transistors, thyristors, optocouplers, photosensitive coupling elements (CCD), monolithic integrated circuits, combined integrated circuits, and large integrated circuits (LSI) and Very Large Integrated Circuit (VLSI).

In the present invention, the LED reflector obtained by molding the above thermosetting silicone resin composition shows high light reflectance and mechanical properties, and exhibits excellent heat resistance and low yellowing during driving, so that the light The deterioration of the reflector surface caused is minimized. Therefore, the reliability of the optical semiconductor device (LED device) including the LED reflector can be improved.

The present invention will be described in more detail below by referring to examples. However, these examples are intended to illustrate the present invention, and the scope of the present invention is not limited to these examples.

Examples

The invention will now be illustrated by examples, which should not be construed as limiting the invention in any way.

Analytical method ²⁹ Description of Si-NMR test * Solvent: C ₆ D ₆ 99.8% d/CCl ₄ (v/v = 1:1) containing 1% w/w Cr(acac) ₃ as a relaxation reagent * Sample concentration : Add about 2 g/1.5 mL of solvent to the 10 mm NMR tube * Spectrometer: Bruker Avance 300 * Sample head: 10 mm ¹ H/ ¹³ C/ ¹⁵ N/ ²⁹ Si glassless QNP-Head (Bruker) * Test parameters: Pulprog = zgig60, TD = 64k, NS = 1024, SW = 200 ppm, AQ = 2.75 s, D1 = 4 s, SFO1 = 300.13 MHz, O1 = -50 ppm * Processing parameters: SI = 64k, WDW = EM, LB = 0.3 Hz Viscosity According to DIN EN ISO 3219, the MCR302 model rheometer manufactured by Anton Paar, D-Ostfildern is used, and the viscosity data is measured with the rotation of the cone and plate measuring system. The measurement is performed within the range where the sample behavior is Newtonian fluid. Viscosity data at a temperature of 25°C and an ambient pressure of 1013 mbar are given. Molecular weight The molecular weight is determined as weight average molecular weight (Mw) and number average molecular weight (Mn) by Size Exclusion Chromatography (SEC). Polystyrene is used as a standard. The detector is a refractive index detector. THF is used as a solvent. The sample concentration is 5 mg/mL.

Synthesis Example 1

Combine 700 g (2.91 mol) phenyltriethoxysilane, 61.6 g (0.415 mol) diethoxydimethylsilane and 77.6 g (0.416 mol) 1,3-divinyl-1,1,3, 3-Tetramethyldisilazane was mixed in a 2 liter round bottom flask. 600 g of distilled water and 3.00 g of 20% hydrochloric acid were added to the solution. The reaction mixture was refluxed for 2 hours. After cooling, 4.50 g of 25% sodium hydroxide solution was added, and the reaction mixture was refluxed for 1 hour. Neutralize the homogeneous mixture with 2.00 g of 20% hydrochloric acid. Ethanol was distilled under vacuum at 40°C, and 1 liter of ethyl acetate and 50 g of sodium chloride were added. The aqueous phase was removed and the organic phase was washed three times with saturated aqueous sodium chloride solution. The organic phase was dried using magnesium sulfate and filtered using filter press equipment. After removing the solvent in vacuo, 470 g of colorless, high-viscosity product was obtained. The weight average molecular weight (Mw) is 2,546 g/mol. The results of ²⁹ Si NMR were ViMe ₂ SiO _1/2 : 16.6%, Me ₂ SiO _2/2 : 9.7%, Ph(OR)SiO _2/2 : 12.8%, and PhSiO _3/2 : 60.9%.

Example 1

The compound of Synthesis Example 1 prepared as component A accounted for 75% by weight, and 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane as component B accounted for 25% by weight. In addition, 0.0002 parts by weight (calculated as platinum) of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyl was prepared with respect to the total amount of components A and B being 100 parts by weight The base-disiloxane complex is used as component C, and 4.99 parts by weight of D ^Vi _{4 is} used as component D.

Based on the total of components (A, B, C, and D) being 100 parts by weight, 50 parts by weight of titanium oxide (first white pigment) having an average particle diameter of 0.3 μm and 0.5 parts by weight having an average particle diameter of 0.02 μm were prepared Silicon oxide (second white pigment) as a white pigment (E) and mixed with the above components, thereby preparing a thermosetting silicone resin composition for LED reflectors according to Example 1.

Examples 2 to 11

Thermosetting silicone resin compositions for LED reflectors according to Examples 2 to 11 were prepared in the same manner as in Example 1, except that Component E was used in the amounts shown in Table 1 below.

*單位：相對於組分（A）、（B）、（C）和（D）之總和為100重量份的重量份[Table 1]

*Unit: 100 parts by weight relative to the sum of components (A), (B), (C) and (D)

[Evaluation Example]

The physical properties of the thermosetting silicone resin composition for LED reflectors prepared in Examples 1 to 11 were measured as described below, and the measurement results are shown in Table 2 below. Molding was performed using a transfer molding machine under the conditions of a molding temperature of 165° C., a molding pressure of 7 MPa, and a molding time of 300 seconds to obtain a cured product. After curing by transfer molding at 150°C for about 4 hours, a cured sample was prepared.

>Physical property evaluation results> (1) Measurement of viscosity For the thermosetting silicone resin composition prepared in each example, a 25 mm diameter flat plate was used in a rheometer system model MCR302 (Anton Paar) to measure the shear rates at 1/sec and 10/sec. Dynamic viscosity. (2) Thixotropic index The thixotropic index is calculated as the ratio of the dynamic viscosity at a shear rate of 10 /sec to the dynamic viscosity at a shear rate of 1 /sec. (3) Shore hardness (D) The hardness of the molded sample with a thickness of 6 mm was measured on the Shore Durometer hardness (D) scale. (4) Yellow index (b*) The yellow index of molded samples with a thickness of 1 mm was measured by CIE Lab colorimetry using Minolta CM5. (5) Light reflectivity The Minolta CM 5 spectrophotometer in the mode including the specular reflection module was used to measure the light reflectance at 450 nm of the transfer-molded sample with a thickness of 1 mm.

As shown in Table 2, it can be seen that the compositions according to Examples 1 to 11 of the present invention have high light reflectance, excellent mechanical properties, and low yellowing, which are required for reflectors.

[Table 2]

no.

Claims (17)

A thermosetting silicone resin composition for LED reflectors, comprising: (A) Each molecule has at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group, and has a The branched-chain organic polysiloxane of the siloxane unit represented by the general formula RSiO _3/2 , where R is a substituted or unsubstituted monovalent hydrocarbon group; (B) Linear organic polysiloxane, two of its molecular chain The terminal is terminated by silicon-bonded hydrogen atoms and has at least one silicon-bonded aryl group per molecule; (C) hydrosilylation catalyst; (D) at least one silicon-bonded alkenyl group Low molecular weight siloxane, which is represented by the following average formula: (R ⁵ ₃ SiO _{1/2) f} (R ⁵ ₂ SiO _2/2 ) _g (R ⁵ SiO _3/2 ) _h (SiO _4/2 ) _i Wherein each R ⁵ may be the same or different and is independently selected from substituted or unsubstituted monovalent hydrocarbon groups, wherein at least one R ⁵ per molecule is an alkenyl group, provided that the ratio of alkenyl group to silicon atom is 0.3 to 1 , F, g, h, and i are independently 0 or a positive number, and the weight average molecular weight (Mw) of the siloxane is less than 1,000 g/mol; and (E) white pigment, wherein, based on component (A) to group The sum of the points (D) is 100 parts by weight, and the content of the white pigment (E) is 40 to 300 parts by weight, wherein the white pigment (E) includes a titanium oxide based first particle having an average particle size of 0.1 to 2 μm A white pigment (E-1), and at least one selected from the group consisting of a second white pigment (E-2), a third white pigment (E-3), or a mixture thereof, at least the average particle size and components One is different from the first white pigment (E-1), and based on the total weight of the white pigment (E) is 100 parts by weight, the content of the first white pigment (E-1) and the first The weight ratio of the remaining pigment content other than a white pigment is 80-99.9:0.1-20. The requested item alumoxane thermosetting silicone resin composition of claim 1, wherein the composition has a viscosity of 100 to 2,000,000 mPa · s (at 25 ^o C), and when the compression is selected through transfer molding before curing and a method of molding in any molding, the composition is rapidly cured within 30 to 600 seconds at a temperature of 100 to 170 ^o C is. The thermosetting silicone resin composition according to claim 1, wherein the white pigment (E) other than the first white pigment (E-1) is selected from titanium oxide, zinc oxide, silicon oxide, At least one of the group consisting of aluminum oxide, barium oxide, magnesium oxide, zirconium oxide, aluminum silicate, boron nitride, calcium carbonate, tantalum pentoxide, barium sulfate, magnesium carbonate, barium carbonate, and strontium titanate. The thermosetting silicone resin composition according to claim 1, wherein the average particle diameter (D ₅₀ ) of the white pigment (E) other than the first white pigment (E-1) is 0.01 to 50 μm. The thermosetting silicone resin composition for an LED reflector according to claim 1, wherein the component (A) is an organic polysiloxane represented by the following average unit formula: (R ¹ R ¹ R ³ SiO _1/2)a (R ¹ ₂ SiO _2/2 ) _b (R ² SiO _3/2 ) _c (SiO _4/2 ) _d (XO _1/2 ) _e where R ¹ , R ² and R ³ Each may be the same or different, and is independently selected from substituted or unsubstituted monovalent hydrocarbon groups, wherein at least one of R ¹ , R ^2, or R ³ in each molecule is an alkenyl group and R ¹ , R ² in each molecule Or at least one of R ³ is an aryl group, X is a hydrogen atom or an alkyl group, a is 0 or a positive number, b is 0 or a positive number, c is a positive number, d is 0 or a positive number, e is 0 or a positive number, b/c Is a number between 0 and 10, a/c is a number between 0 and 0.5, d/(a + b + c + d) is a number between 0 and 0.3, and e/(a + b + c + d) is a number between 0 and 0.4. The thermosetting silicone resin composition for an LED reflector according to claim 1, wherein the component (A) is an organic polysiloxane having the following average unit formula: (R ¹ R ¹ R ³ SiO _{1 /2)a} (R ¹ ₂ SiO _2/2 ) _b (R ² SiO _3/2 ) _c where R ¹ is C ₁ to C ₁₂ alkyl, R ² is C ₆ to C ₂₀ aryl or C ₇ to C ₂₀ aralkyl, R ³ is C ₂ to C ₁₂ alkenyl, a is 0 or a positive number, b is 0 or a positive number, and c is a positive number. The thermosetting silicone resin composition for LED reflectors according to claim 1, wherein the component (B) is an organic polysiloxane represented by the following general formula:

[Formula 2] wherein each R ⁴ may be the same or different, and is independently selected from a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, excluding alkenyl groups, wherein at least one R ⁴ per molecule is an aryl group, And n is an integer of 0 or greater. The thermosetting silicone resin composition for an LED reflector according to claim 1, wherein the weight ratio of component (A) to component (B) is 70:30 to 90:10. The thermosetting silicone resin composition for an LED reflector according to claim 8, wherein the weight ratio of component (A) to component (B) is 75:25 to 85:15. The thermosetting silicone resin composition for LED reflectors according to claim 1, wherein the component (D) is selected from the group consisting of D ^Vi ₄ , M ^Vi ₄ Q, M ^Vi ₆ Q ₂ and M ^Vi ₃ T Group. The thermosetting silicone resin composition for an LED reflector according to claim 10, wherein the component (D) includes D ^Vi ₄ . The thermosetting silicone resin composition for LED reflectors according to claim 1, wherein the content of component (D) is at most up to 100 parts by weight of the total amount of components (A) and (B) 10 parts by weight. The thermosetting silicone resin composition for an LED reflector according to claim 1, wherein the molar ratio of the hydrosilyl group in the component (B) relative to the alkenyl group in the component (A) The ratio is 1 to 1.2. The thermosetting silicone resin composition for an LED reflector according to claim 1, further comprising a group selected from the group consisting of crosslinking agents, inorganic fillers, curing inhibitors, catalysts, and phosphors At least one of the group. An LED reflector comprising a cured product formed by curing the thermosetting silicone resin composition according to any one of claims 1 to 4 and 9 to 14, the reflector having 97% or more at a wavelength of 450 nm Higher light reflectivity. The LED reflector according to claim 15, which has: Shore D hardness of 10 or higher; and Yellow index of 5 or lower. A semiconductor device including the reflector according to claim 16.