KR101588525B1 - Curable compositon - Google Patents

Abstract

The present application relates to a curable composition and its use. In the present application, a polyorganosiloxane containing Q units is used as a bonding material or an encapsulating material to a semiconductor element such as an LED, for example, by using a component having a specific structure, and exhibits excellent crack resistance, It is possible to provide a device having excellent reliability without deterioration in luminance.

Description

CURABLE COMPOSITON [0001]

The present application is directed to curable compositions and uses thereof.

LED (Light Emitting Diode) is a device used in various fields such as a light source of a display device and illumination.

As an LED encapsulant, epoxy resin having high adhesiveness and excellent durability is widely used. However, the epoxy resin has a low transmittance to light in the range of blue to ultraviolet rays, and has a problem in that heat resistance and light resistance are inferior. Thus, for example, Patent Documents 1 and 2 propose a technique for improving the above problems. However, the sealing materials known to date have insufficient heat resistance, gas barrier properties and crack resistance at high temperatures.

Patent Document 1: Korean Patent Publication No. 2008-0070816 Patent Document 2: JP-A-2008-198930

The present application provides curable compositions and uses thereof.

The curable composition of the present application includes, for example, a polyorganosiloxane (A) having an average composition formula of the following formula (1) and a polyorganosiloxane (B) containing a hydrogen atom bonded to one or more silicon atoms can do. The curable composition may also comprise a hydrosilylation catalyst as an additional component.

[Chemical Formula 1]

_{^{(R 4 3 SiO 1/2}} ) e (R 5 2 SiO 2/2) f (SiO 4/2) g (OR) x

In formula (1), R ⁴ and R ⁵ are substituents directly bonded to the silicon atom, each independently represents an epoxy group or a monovalent hydrocarbon group, at least two of them are alkenyl groups, R is hydrogen or a monovalent hydrocarbon group , e, f and g are positive numbers, x is zero or a positive number, f / (f + g) is 0.05 to 0.3 and e / g is in the range of 0.5 to 1.5.

Exemplary curable compositions can include components that are cured by hydrosilylation, for example, by reaction of aliphatic unsaturated bonds with hydrogen atoms bonded to silicon atoms. For example, the curable composition may comprise a crosslinked polyorganosiloxane comprising an aliphatic unsaturated bond and a polyorganosiloxane comprising a hydrogen atom bonded to a silicon atom.

The term "M" units in this specification, expressions in the industry (R ₃ SiO _1/2) means the so-called monofunctional siloxane units in the case represented by and, the term "D" units of the formula in the industry (R ₂ SiO _{2 / 2)} so-called transfer means a functional siloxane units in the case represented by and, the term "T" unit "means a so-called trifunctional siloxane unit in the case of the formula (RSiO _3/2) in the industry, and the term Q "units may refer to so-called Tetrafunctional siloxane units in the case of the formula (SiO _4/2). The R is a functional group bonded to silicon (Si), and may be, for example, a hydrogen atom, an epoxy group or a monovalent hydrocarbon group.

As used herein, the term " epoxy group " may refer to a monovalent moiety derived from a cyclic ether or a cyclic ether containing three ring constituent atoms, unless otherwise specified . As the epoxy group, a glycidyl group, an epoxy alkyl group, a glycidoxyalkyl group or an alicyclic epoxy group can be exemplified. The alicyclic epoxy group may be a monovalent residue derived from a compound containing a structure containing an aliphatic hydrocarbon ring structure and having a structure in which two carbon atoms forming the aliphatic hydrocarbon ring also form an epoxy group. As the alicyclic epoxy group, an alicyclic epoxy group having 6 to 12 carbon atoms can be exemplified, and for example, 3,4-epoxycyclohexylethyl group and the like can be exemplified.

As used herein, the term " monovalent hydrocarbon group " may mean a monovalent residue derived from a compound consisting of carbon and hydrogen or a derivative of such a compound, unless otherwise specified. For example, the monovalent hydrocarbon group may contain from 1 to 25 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. In one example, the monovalent hydrocarbon group of the above formula (1) may be selected from monovalent hydrocarbon groups excluding an aryl group.

The term "alkyl group" as used herein may mean an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified. The alkyl group may be linear, branched or cyclic. In addition, the alkyl group may be optionally substituted with one or more substituents.

The term "alkenyl group" as used herein may mean an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms unless otherwise specified. The alkenyl group may be linear, branched or cyclic and may optionally be substituted with one or more substituents.

The term "alkynyl group" as used herein may mean an alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms unless otherwise specified. The alkynyl group may be linear, branched or cyclic and may optionally be substituted with one or more substituents.

The term " aryl group " as used herein includes, unless otherwise specified, a benzene ring or a compound containing a structure in which two or more benzene rings are connected or condensed or bonded while sharing one or two or more carbon atoms, or May refer to a monovalent residue derived from the derivative. The range of the aryl group referred to in the present specification may include a so-called aralkyl group or an arylalkyl group as well as a functional group ordinarily referred to as an aryl group. The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group, dichlorophenyl, chlorophenyl, phenylethyl, phenylpropyl, benzyl, tolyl, xylyl group or naphthyl group.

The polyorganosiloxane (A) contained in the curable composition of the present application may be a low refractive polyorganosiloxane (hereinafter referred to as component (A)). The term low refractive polyorganosiloxane in the present application may mean a polyorganosiloxane that contains little or no aryl groups in the molecule. For example, the term "low refractive polyorganosiloxane" means that the molar ratio (Ar / Si) of the total silicon atoms (Si) to the aryl group (Ar) of the polyorganosiloxane is 0.3 or less, 0.2 or less, May mean a polyorganosiloxane of substantially zero.

Component (A) is used for imparting appropriate strength and hardness to the cured product of the composition, and may include at least M, D and Q units. The component (A) may have an average composition formula of the formula (1).

When component (A) is a low-refractive-index polyorganosiloxane, R ⁴ , R ⁵ and R in formula (1) may each be a monovalent hydrocarbon group other than an aryl group.

In the present specification, the term "polyorganosiloxane having a specific average composition formula" means that when a mixture of two or more components as well as a polyorganosiloxane, which is a single component represented by the average composition formula thereof, and an average composition of the components of the mixture are taken, But also a mixture of polyorganosiloxanes in the form of an average composition formula.

The ratio (Ak / Si) of the number of moles (Ak) of alkenyl groups to the number of moles (Si) of silicon atoms in the component (A) may be 0.01 to 0.4. For example, R < ⁴ > And R ⁵ are each independently an alkenyl group or an alkyl group, and R ⁴ And R < ⁵ > may be an alkenyl group. In one example, the ratio (Ak / T) is 0.7 of the molar amount (Ak) of the alkenyl group compared R ⁴ total molar amount of the alkyl group and the alkenyl group of the formula 1 R ⁴ (T = mole number + number of moles of alkenyl groups in the alkyl group) Less than or equal to 0.5, less than or equal to 0.4, less than or equal to 0.3, less than or equal to 0.2, less than or equal to 0.1, or less than or equal to 0.07. The lower limit of the molar ratio (Ak / T) is not particularly limited, and may be, for example, about 0.01. This makes it possible to maintain the reactivity appropriately and prevent the unreacted component from leaking to the surface of the cured body. In addition, the hardness, crack resistance and thermal shock resistance of the cured product can be kept excellent.

In the average composition formula of the formula (1), e, f and g represent molar ratios of the respective siloxane units. For example, when the sum (e + f + g) is converted into 1, e is in the range of 0.2 to 0.8, f may be in the range of 0.02 to 0.3, and g may be in the range of 0.2 to 0.8. F / (f + g) in the formula (1) can be adjusted to be in the range of 0.05 to 0.4, 0.06 to 0.35 or 0.07 to 0.35 in order to maximize the strength, crack resistance and thermal shock resistance of the cured product. Further, the formula (1) can be adjusted so that e / g ranges from 0.4 to 1.5, 0.4 to 1.0, 0.4 to 0.8, or 0.4 to 0.65.

In Formula (1), x represents the amount of a condensing functional group, for example, a hydroxyl group or an alkoxy group contained in the polysiloxane. In the formula (1), x is 0 or a positive number. For example, x / g in the formula (1) may be determined to be 0.2 or less, 0.15 or less, 0.1 or less, or substantially 0. Through this, it is possible to maintain the compatibility of each component of the curable composition, to form a cured product having excellent transparency after curing, and to maintain excellent moisture resistance of the cured product, If applied, the long-term reliability of the device can be secured.

The component (A) may have a viscosity of 500 cP or more, or 5000 cP or more, or 50,000 cP or 1,000,000 cP or more at 25 占 폚, so that the workability before curing and the hardness characteristics after curing can be appropriately maintained.

The component (A) may have a weight average molecular weight (Mw) of, for example, 500 to 20,000 or 500 to 10,000. As used herein, the term " weight average molecular weight " may refer to a conversion value for standard polystyrene measured by GPC (Gel Permeation Chromatograph). Unless otherwise specified, the term " molecular weight " can mean weight average molecular weight. By controlling the molecular weight of the component (A) to 500 or more, the moldability before curing and the strength after curing can be effectively maintained, and the viscosity can be maintained at an appropriate level by controlling the molecular weight to 20,000 or 10,000 or less.

The method of producing the component (A) is not particularly limited, and a conventional method known in the art can be applied.

The curable composition of the present application may further include a linear polyorganosiloxane having an average composition formula of the following formula (2) (hereinafter referred to as component (C)), and the component (C) may also be a low refractive polyorganosiloxane . The linear polyorganosiloxane may have an average composition formula of the following formula 2:

(2)

_{^{(R 1 3 SiO 1/2}} ) a (R 2 2 SiO 2/2) b

In the general formula (2), R ¹ and R ² are substituents directly bonded to a silicon atom, and each independently represents an epoxy group or a monovalent hydrocarbon group, and R ¹ and R ² Is an alkenyl group, and a and b are positive numbers.

For example, the ratio (Ak / Si) of the number of moles (Ak) of alkenyl groups to the number of moles (Si) of silicon atoms in component (C) may be in the range of 0.001 to 0.4. It is possible to control the molar ratio to appropriately maintain the reactivity and prevent the unreacted component from leaking to the surface of the cured body. In addition, the hardness, crack resistance and thermal shock resistance of the cured product can be kept excellent.

In the average composition formula of the formula (2), a and b represent molar ratios of the respective siloxane units. When a total sum (a + b) thereof is converted into 1, a is within a range of 0.00005 to 0.3 and b is within a range of 0.7 to 0.9995 .

Component (C) has an essentially linear molecular structure, but may also be partially branched. There is no particular limitation on the bonding position of the alkenyl group in the component (C). For example, these substituents may be placed on the molecular terminal and / or side chains.

There is no particular limitation on the viscosity of the component (C), but a viscosity within a range of 100 to 1,000,000 mPa 占 퐏 or 100 to 100,000 mPa 占 퐏 at 25 占 폚 may be appropriate.

Component (C) may also have a molecular weight within the range of 500 to 50,000 or 1,500 to 30,000. Moldability, hardness and strength characteristics and the like can appropriately be maintained in this range.

The proportion of the component (C) is not particularly limited and may be, for example, 200 parts by weight or less, or 10 to 150 parts by weight, based on 100 parts by weight of the polyorganosiloxane (A). Within the above range, the properties such as the viscosity of the composition and the hardness of the cured product can be kept excellent.

The curable composition of the present application may contain a polyorganosiloxane (hereinafter referred to as component (B)) containing a hydrogen atom bonded to a silicon atom. The component (B) is a crosslinking agent for crosslinking the composition by reacting with an aliphatic unsaturated bond, for example, one or more hydrogen atoms bonded to a silicon atom, and the hydrogen atom of the component (B) The aliphatic unsaturated bond such as the alkenyl group of one component (A) and / or the component (C) may undergo addition reaction to promote cross-linking and curing. The kind of the component (B) is not particularly limited, and may be a high refractive index polyorganosiloxane containing a predetermined amount or more of an aryl group, or a low refractive index polyorganosiloxane. Component (B) may be a solid or a liquid. Further, the component (B) may have a linear structure, that is, a structure consisting of only M and D units. In the case of a linear structure, the hydrogen atom may be bonded to a silicon atom present at the end of the linear structure. Such component (B) can exhibit excellent reactivity with aliphatic unsaturated bonds. Further, crack resistance of the cured product can be improved, and gas permeability can be maintained at a low level.

The ratio (H / Ak) of the number of moles (H) of the hydrogen atoms contained in the component (B) to the number of moles (Ak) of the alkenyl groups contained in the composition may be 0.1 to 10, or 1 to 5, or 2 to 3 . By controlling the ratio (H / Si) to 0.1 or more, excellent curability of the composition can be maintained, and it is possible to control cracking resistance and thermal shock resistance by controlling the ratio to 10 or less.

Component (B) may be solid or liquid as described above. If the component (A) is a liquid, the viscosity at 25 占 폚 may be 300 mPa 占 퐏 or less or 300 mPa 占 퐏 or less. By controlling the viscosity of the component (B) as described above, excellent workability of the composition and hardness characteristics of the cured product can be maintained. Component (B) may have a molecular weight of less than 1,000 or less than 800, for example. If the molecular weight of the component (B) is 1,000 or more, the strength of the cured product may deteriorate. The lower limit of the molecular weight of the component (B) is not particularly limited, and may be 250, for example.

As the component (B), various kinds of polyorganosiloxanes may be used as long as the above characteristics are satisfied. For example, as the component (B), a compound of the following formula (3) can be used.

(3)

In formula (3), R is independently hydrogen, an epoxy group or a monovalent hydrocarbon group, and n may be a number within a range of 1 to 50.

N in Formula 3 may be in the range of, for example, 1 to 40, 1 to 30, 1 to 20, 1 to 10, 1 to 8, 1 to 6, 1 to 4 or 1 to 2.

As the component (B), a compound of the following formula (4) may also be used.

[Chemical Formula 4]

R ₃ SiO (HRSiO) _r (R ₂ SiO) _s OSiR ₃

R in the formula (4) is independently hydrogen, an epoxy group or a monovalent hydrocarbon group, r is a number of 0 to 100, and s is a number of 0 to 100.

In one example, the ratio (H / Si) of the number of moles (H) of silicon atom-bonded hydrogen atoms to the number of moles (Si) of the total silicon atoms contained in component (B) may be from 0.2 to 0.99 or from 0.3 to 0.98. It is possible to control the molar ratio (H / Si) to 0.2 or 0.3 or more to maintain excellent curability of the composition, and to adjust to 0.99 or 0.98 or less to maintain excellent crack resistance and thermal shock resistance.

The content of the component (B) depends on the total aliphatic unsaturated bond-containing functional group contained in the curable composition, for example, the polyorganosiloxane with respect to the number of moles (Ak) of the alkenyl group contained in the component (A) (H / Ak) of the number of moles (H) of the hydrogen atoms of the hydrogen atoms (C) to (B) is 0.01 to 1.0 or 0.1 to 0.3.

By blending at such a molar ratio (H / Ak), excellent workability and workability are exhibited before curing, and the cured product exhibits excellent crack resistance, hardness characteristics, thermal shock resistance and adhesiveness and exhibits opacity and surface stickiness in harsh conditions Or < / RTI > When the component (B) is used, its content can be appropriately selected in consideration of, for example, the ratio of the component (A), the amount of the aliphatic unsaturated bond, and the like.

The curable composition of the present application may comprise a hydrosilylation catalyst. The hydrosilylation catalyst may be used to promote the hydrogen saccharification reaction. As the hydrosilylation catalyst, any of common components known in the art can be used. Examples of such catalysts include platinum, palladium or rhodium catalysts. In the present application, a platinum-based catalyst can be used in consideration of catalytic efficiency and the like. Examples of such catalysts include chloroplatinic acid, platinum tetrachloride, an olefin complex of platinum, an alkenylsiloxane complex of platinum or a carbonyl complex of platinum , But is not limited thereto.

The content of the hydrosilylation catalyst is not particularly limited as long as it is contained in the so-called catalytic amount, that is, an amount that can act as a catalyst. Typically, it can be used in an amount of 0.1 ppm to 200 ppm or 0.2 ppm to 100 ppm based on the atomic weight of platinum, palladium or rhodium.

The curable composition of the present application may further include an adhesion imparting agent in view of further improvement of adhesiveness to various substrates. The adhesive property-imparting agent is a component capable of improving the self-adhesiveness of the composition or the cured product, and can improve the self-adhesiveness particularly to metals and organic resins.

Examples of the adhesion-imparting agent include at least one kind selected from the group consisting of an alkenyl group such as vinyl group, a (meth) acryloyloxy group, a hydrosilyl group (SiH group), an epoxy group, an alkoxy group, an alkoxysilyl group, a carbonyl group, Or silanes having two or more functional groups; Or an organosilicon compound such as cyclic or linear siloxane having 2 to 30 or 4 to 20 silicon atoms, but the present invention is not limited thereto. In the present application, one kind or more than two types of adhesion-imparting agents as described above may be further mixed and used.

When the adhesive property-imparting agent is included in the composition, it may be contained at a ratio of, for example, 0.1 to 20 parts by weight, relative to 100 parts by weight of the solid content of the curable composition. However, the content may be appropriately changed .

The curable composition of the present application may contain, if necessary, 2-methyl-3-butyne-2-ol, 2-phenyl-3-1- 5-dimethyl-3-hexene-1-in, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane or ethynylcyclohexane; Inorganic fillers such as silica, alumina, zirconia or titania; A carbon functional silane having an epoxy group and / or an alkoxysilyl group, a partial hydrolysis condensation product thereof, or a siloxane compound; A thixotropy imparting agent such as pyrogenic silica which can be used in combination with polyether and the like; filler; A phosphor; Silver, a metal powder such as copper or aluminum, or a conductivity imparting agent such as various carbon materials; A coloring agent such as a pigment or a dye, and the like.

The present application also relates to semiconductor devices, for example, optical semiconductor devices. An exemplary semiconductor device may be one encapsulated by an encapsulant comprising a cured body of the curable composition. Examples of the semiconductor device sealed with the encapsulation material include a diode, a transistor, a thyristor, a photocoupler, a CCD, a solid-state image pickup element, a monolithic IC, a hybrid IC, an LSI, a VLSI and an LED (Light Emitting Diode). In one example, the semiconductor element may be a light emitting diode.

As the light emitting diode, for example, a light emitting diode formed by laminating a semiconductor material on a substrate can be exemplified. Examples of the semiconductor material include, but are not limited to, GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN or SiC. As the substrate, sapphire, spinel, SiC, Si, ZnO, or GaN single crystal may be exemplified.

In manufacturing the light emitting diode, a buffer layer may be formed between the substrate and the semiconductor material, if necessary. As the buffer layer, GaN or AlN or the like can be used. The method for laminating the semiconductor material on the substrate is not particularly limited, and for example, MOCVD, HDVPE, or liquid phase growth can be used. Further, the structure of the light emitting diode may be, for example, a mono junction having a MIS junction, a PN junction, a PIN junction, a heterojunction, a double heterojunction, or the like. In addition, the light emitting diode can be formed with a single or multiple quantum well structure.

In one example, the emission wavelength of the light emitting diode may be, for example, 250 nm to 550 nm, 300 nm to 500 nm, or 330 nm to 470 nm. The emission wavelength may mean the main emission peak wavelength. By setting the emission wavelength of the light emitting diode to the above range, a white light emitting diode having a longer lifetime, high energy efficiency and high color reproducibility can be obtained.

The light emitting diode may be encapsulated using the above composition. Encapsulation of the light emitting diode can be carried out only with the above composition, and in some cases other encapsulant can be used in combination with the composition. In the case of using two types of sealing materials together, after sealing with the composition, the surroundings may be sealed with another sealing material, or the sealing material may be first sealed with another sealing material, and then the periphery thereof may be sealed with the composition. Examples of other sealing materials include epoxy resins, silicone resins, acrylic resins, urea resins, imide resins, and glass.

Examples of the method for encapsulating the light emitting diode with the curable composition include a method in which the composition is previously injected into a molded mold, the lead frame or the like having the light emitting diode fixed thereto is immersed in the mold and the composition is cured, A method in which a composition is injected into a mold and cured is used. As a method of injecting the composition, injection by a dispenser, transfer molding, injection molding, or the like can be exemplified. Examples of other sealing methods include a method in which a composition is dropped on a light emitting diode, applied by screen printing, screen printing or a mask to cure the composition, or a cup in which a light emitting diode is disposed on the bottom, And a method of curing can be used.

The curable composition may also be used as a die bond material for fixing the light emitting diode to the lead terminal or the package, a passivation film on the light emitting diode or a package substrate, if necessary.

When curing of the composition is required, the curing method is not particularly limited and may be carried out by, for example, holding the composition at a temperature of 60 to 200 DEG C for 10 minutes to 5 hours, The stepwise curing process may be performed through the above process.

The shape of the encapsulant is not particularly limited and can be, for example, a lens-like lens shape, a plate shape or a thin film shape.

Further, it is possible to further improve the performance of the light emitting diode according to a conventionally known method. As a method of improving the performance, for example, a method of providing a reflective layer or a condensed layer of light on the back surface of a light emitting diode, a method of forming a complementary coloring portion on the bottom portion, a method of providing a layer absorbing light having a shorter wavelength than the main emission peak on a light emitting diode A method in which a light emitting diode is encapsulated and then further molded with a hard material, a method in which a light emitting diode is inserted and fixed in a through hole, a method in which a light emitting diode is connected to a lead member or the like by flip chip connection or the like, And the like.

The optical semiconductor, for example, a light emitting diode can be used as a light source such as a backlight of a liquid crystal display (LCD), an illumination, various sensors, a printer, a copying machine, a vehicle instrument light source, A display device, a light source of a planar light-emitting body, a display, a decoration, or various lights.

In the present application, a polyorganosiloxane containing Q units is used as a bonding material or an encapsulating material to a semiconductor element such as an LED, for example, by using a component having a specific structure, and exhibits excellent crack resistance, It is possible to provide a device having excellent reliability without deterioration in luminance.

Hereinafter, the curable composition will be described in more detail by way of examples and comparative examples, but the scope of the curable composition is not limited by the following examples.

In the following, Vi, Ph, Me and Ep represent a vinyl group, a phenyl group, a methyl group and a 3-glycydoxypropyl group, respectively.

1. Evaluation of long-term reliability

The long-term reliability (long-term reliability at high temperatures) is evaluated using a 7020 LED package made of polyphthalamide (PPA). Specifically, the curable composition was dispensed in a polyphthalamide cup, held at 60 占 폚 for 1 hour, maintained at 80 占 폚 for 1 hour, and then held at 150 占 폚 for 4 hours to cure the surface mount LED . Thereafter, the produced LED was operated for 500 hours while flowing a current of 120 mA while maintaining the temperature at 85 캜. Next, the luminance reduction rate after the operation relative to the initial luminance is measured and evaluated as the following criteria.

<Evaluation Criteria>

A: When the luminance reduction rate is 5% or less

B: When the luminance reduction rate exceeds 5%

2. Heat resistance Impact

The number of LEDs that do not light up after holding the LEDs for 200 cycles is defined as the number of LEDs for evaluation, which is maintained for 15 minutes at -30 ° C for 15 minutes and then maintained at 100 ° C for 15 minutes. Respectively. Twenty LEDs were all manufactured with the same curing composition, and the number of tinted LEDs in the manufactured LEDs was evaluated and shown in the following Table 1 (number of LEDs not lit / number of LEDs evaluated).

Example  One

The following components prepared by a known method were mixed homogeneously (compounding amount: 12.3 g, chemical formula B: 1 g, chemical formula C: 7.7 g), and the content of Pt (0) was 2 ppm (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was added to the curing composition in an amount as described above.

(A)

_{(ViMe 2 SiO 1/2)} 0.06 (Me 3 SiO 1/2) 0.29 (Me 2 SiO 2/2) 0.05 (SiO 4/2) 0.6 (OMe) 0.06

[Chemical Formula B]

_{(HMe 2 SiO 1/2)} 0.05 (HMeSiO 2/2) 0.95

&Lt; RTI ID = 0.0 &

_{(ViMe 2 SiO 1/2)} 0.003 (Me 2 SiO 2/2) 0.997

Example  2

The following components were mixed in a known manner to prepare a mixture (the compounding amount: 12.3 g of the formula D, 1 g of the compound of the formula E, 7.7 g of the formula F), and the content of Pt (0) (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was added to the curing composition in an amount as described above.

[Chemical Formula D]

_{(ViMe 2 SiO 1/2)} 0.05 (Me 3 SiO 1/2) 0.23 (Me 2 SiO 2/2) 0.24 (SiO 4/2) 0.48 (OMe) 0.005

(E)

_{(HMe 2 SiO 1/2)} 0.05 (HMeSiO 2/2) 0.95

[Chemical Formula F]

_{(ViMe 2 SiO 1/2)} 0.003 (Me 2 SiO 2/2) 0.997

Comparative Example  One.

A curable composition was prepared in the same manner as in Example 1, except that the component of the average composition formula of the formula (G) was used in place of the component of the average composition formula of the formula (A).

[Formula G]

_{(ViMe 2 SiO 1/2)} 0.07 (Me 3 SiO 1/2) 0.33 (SiO 4/2) 0.60 (OMe) 0.15

Comparative Example  2.

A curable composition was prepared in the same manner as in Example 1, except that the component of the average composition formula of the formula (H) was used in place of the component of the average composition formula of the formula (A).

(E)

_{(ViMe 2 SiO 1/2)} 0.05 (Me 3 SiO 1/2) 0.22 (Me 2 SiO 2/2) 0.33 (SiO 4/2) 0.40

Comparative Example  3.

A curable composition was prepared in the same manner as in Example 1, except that the component of the average composition formula of the formula (I) was used instead of the component of the average composition formula of the formula (A).

(I)

_{(ViMe 2 SiO 1/2)} 0.06 (Me 3 SiO 1/2) 0.29 (Me 2 SiO 2/2) 0.02 (SiO 4/2) 0.6 (OMe) 0.06

The physical properties of the curable compositions of Examples and Comparative Examples were measured and reported in Table 1.

Long-term reliability Thermal shock resistance Example 1 A 2/20 Example 2 A 0/20 Comparative Example 1 B 18/20 Comparative Example 2 B 1/20 Comparative Example 3 B 10/20

Claims (16)

A polyorganosiloxane (A) having an average composition formula of the following formula (1) and having a ratio (Ak / Si) of the number of moles (Ak) of alkenyl groups to the number of moles (Si) of silicon atoms in a range of 0.01 to 0.4; And
A curable composition comprising a polyorganosiloxane (B) having a hydrogen atom bonded to a silicon atom:
[Chemical Formula 1]
(R ⁴ ₃ SiO _1/2 ) _e (R ⁵ ₂ SiO _2/2 ) _f (SiO _4/2 ) _g (OR) _x
In formula (1), R ⁴ and R ⁵ are substituent groups directly bonded to a silicon atom, each independently being an epoxy group or a monovalent hydrocarbon group, at least two or more of which are alkenyl groups, R is hydrogen or a monovalent hydrocarbon group, e, f and g are each a positive number, x is 0 or a positive number, f / (f + g) is in the range of 0.05 to 0.4 and e / g is in the range of 0.5 to 1.5. delete The method according to claim 1, wherein the ratio (Ak / T) of the number of moles (Ak) of the alkenyl group of R ⁴ to the total number of moles of the alkyl group and alkenyl group of R ⁴ (T = number of moles of alkyl group + number of moles of alkenyl group) 0.7 or less. The curable composition according to claim 1, wherein the ratio (Ar / Si) of the number of moles (Ar) of aryl groups to the number of moles (Si) of silicon atoms of the polyorganosiloxane (A) is 0.3 or less. The curable composition according to claim 1, further comprising a polyorganosiloxane (C) having an average composition formula of the following formula (2):
(2)
_{^{(R 1 3 SiO 1/2}} ) a (R 2 2 SiO 2/2) b
In the general formula (2), R ¹ and R ² are substituents directly bonded to a silicon atom, each independently represents an epoxy group or a monovalent hydrocarbon group, and R ¹ and R ² Is an alkenyl group, and a and b are positive numbers. The curable composition according to claim 5, wherein the ratio (Ak / Si) of the number of moles (Ak) of alkenyl groups to the number of moles (Si) of silicon atoms of the polyorganosiloxane (C) is in the range of 0.01 to 0.4. The curable composition according to claim 5, wherein the ratio (Ar / Si) of the number of moles (Ar) of aryl groups to the number of moles (Si) of silicon atoms of the polyorganosiloxane (C) is 0.3 or less. The curable composition according to claim 5, wherein the polyorganosiloxane (C) is contained in an amount of 200 parts by weight or less based on 100 parts by weight of the polyorganosiloxane (A). The curable composition according to claim 5, wherein the polyorganosiloxane (C) is contained in a proportion of 10 to 150 parts by weight based on 100 parts by weight of the polyorganosiloxane (A). The curable composition of claim 1, wherein the polyorganosiloxane (B) is a compound of formula
(3)

In Formula (3), R is independently hydrogen, an epoxy group or a monovalent hydrocarbon group, and n is a number of 1 to 10. The curable composition of claim 1, wherein the polyorganosiloxane (B) is a compound of formula (4):
[Chemical Formula 4]
R ₃ SiO (HRSiO) _r (R ₂ SiO) _s OSiR ₃
R in the formula (4) is independently hydrogen, an epoxy group or a monovalent hydrocarbon group, r is a number of 0 to 100, and s is a number of 0 to 100. The curable composition according to claim 1, wherein the ratio (H / Ak) of the number of moles (H) of the hydrogen atoms contained in the polyorganosiloxane (B) to the number of moles (Ak) of the alkenyl groups contained in the composition is in the range of 0.1 to 10 . A semiconductor device encapsulated with an encapsulating material comprising a cured product of the curable composition of claim 1. An optical semiconductor device encapsulated with an encapsulant comprising a cured product of the curable composition of claim 1. A liquid crystal display device comprising the optical semiconductor element of claim 14 in a backlight. 14. A lighting comprising the optical semiconductor element of claim 14.