KR20140015034A - Poly(organosiloxane) - Google Patents

Abstract

The present invention relates to poly(organosiloxane) and a use thereof. The poly(organosiloxane) of the present invention, for instance, can be used as an improver of adhesive properties. The poly(organosiloxane) of the present invention, for instance, shows excellent adhesive properties against various materials containing organic materials, etc., and can be used for producing a composition with excellent optical properties and reliability or a hardened material thereof. The composition or the hardened material thereof, for instance, can be used as an encapsulating agent of an optical semiconductor device.

Description

Polyorganosiloxane {POLY (ORGANOSILOXANE)}

This application relates to a polyorganosiloxane and its use.

High brightness products using GaN-based compound semiconductors such as GaN, GaAlN, InGaN and InAlGaN have been obtained as LEDs (Light Emitting Diodes), for example, blue or ultraviolet LEDs having an emission wavelength of about 250 nm to 550 nm. The technique of combining red and green LEDs with blue LEDs also enables the formation of high quality full color images. For example, a technique of manufacturing a white LED by combining a blue LED or an ultraviolet LED with a phosphor is known. Such LEDs are in widespread use as a light source for a display device such as an LCD (Liquid Crystal Display) or an illumination device.

As the LED encapsulating material, an epoxy resin having high adhesiveness and excellent mechanical durability is widely used, but the epoxy resin has a low transmittance to light in the blue to ultraviolet region and is poor in light resistance. Accordingly, for example, Patent Documents 1 to 3 propose a technique for improving the above.

Silicone materials are known as materials having excellent resistance to light in the low wavelength region. Silicone resins lack heat resistance and appear sticky on the surface after curing. In order for the silicone resin to be effectively applied as an LED encapsulation material, it is necessary to secure properties such as high refractive index, crack resistance, surface hardness, adhesive force, and thermal shock resistance.

Silicone resins do not exhibit sufficient adhesion to substrates made of metals or organic materials. Accordingly, when a thermal shock is applied after the sealing of the device or the adhesion of the device using the silicone resin or maintained at a high temperature, peeling is frequently caused, resulting in a problem of low reliability.

Patent Document 1: JP-A-11-274571 Patent Document 2: JP-A-2001-196151 Patent Document 3: Japanese Patent Application Laid-Open No. 2002-226551

The present application provides polyorganosiloxanes and uses thereof.

Exemplary polyorganosiloxane may have an average composition formula of the following formula (1).

[Formula 1]

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

In formula (1), R ¹ is an epoxy group or a monovalent hydrocarbon group, at least one of R ¹ is an alkenyl group, at least one of R ¹ is an epoxy group, a is 0 or a positive number, b is a positive number, c Is a positive number, d is 0 or a positive number, the sum of a, b and c is 1, b / (b + c) is 0.4 to 0.97, and R is an alkyl group or a hydrogen atom.

The mole number (Si) of the total silicon atoms of the polyorganosiloxane and the ratio ((OH + OR) / Si) of the total mole number (OH + OR) of the total hydroxy group and the alkoxy group included in the polyorganosiloxane may be 0.01 or less. .

In the present specification, the polyorganosiloxane is represented by a predetermined average composition formula, which means that the polyorganosiloxane is a single component represented by the average composition formula, as well as a mixture of two or more components and an average of the composition of the components in the mixture. If taken, it may also include the case represented by the average composition formula.

On the other hand, the term "M unit" in the present specification, a (R ₃ SiO _1/2) is so-called consistent mean-functional siloxane units, and the term "D unit" is (R ₂ SiO _2/2) in the case represented by the means a so-called di-functional siloxane units in the case represented, and the term "T unit" means a so-called trifunctional siloxane unit with the case shown by (RSiO _3/2), and the term "Q unit" is (SiO _{4 / 2} ) may mean so-called tetrafunctional siloxane units. In the above, R is a functional group bonded to the silicon atom (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 mean a monovalent residue derived from a compound containing an aliphatic hydrocarbon ring structure and including 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, unless otherwise specified, the term "monohydric hydrocarbon group" may refer to a compound consisting of carbon and hydrogen or a monovalent moiety derived from a derivative of such a compound. For example, the monovalent hydrocarbon group may contain from 1 to 25 carbon atoms. As the monovalent hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group or an aryl group can be exemplified.

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 be optionally substituted with one or more substituents.

In the present specification, the term "alkynyl group" 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 be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, the term "aryl group" may mean a monovalent moiety derived from a compound or a derivative thereof including a structure in which a benzene ring or a structure in which two or more benzene rings are condensed or bonded. The range of the aryl group may include a so-called aralkyl group or an arylalkyl group as well as a functional group ordinarily called 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 phenyl group, dichlorophenyl, chlorophenyl, phenylethyl group, phenylpropyl group, benzyl group, tolyl group, xylyl group or naphthyl group.

Examples of the substituent that may be optionally substituted with an epoxy group or a monovalent hydrocarbon group include epoxy groups such as halogen, glycidyl group, epoxyalkyl group, glycidoxyalkyl group or alicyclic epoxy group such as chlorine or fluorine, acryloyl group and methacryl A royl group, an isocyanate group, a thiol group, or a monovalent hydrocarbon group may be exemplified, but is not limited thereto.

In the average formula of Formula 1, a, b and c represent the molar ratios of the M, D and T units of the polyorganosiloxane, respectively, and the sum (a + b + c) is 1. Wherein a is 0 or a positive number, for example 0.01 to 0.15, b is a positive number, for example 0.65 to 0.97, c is a positive number, for example 0.03 to 0.60. In the polyorganosiloxane, the ratio of D units to total D and T units, that is, b / (b + c) may be 0.4 to 0.97 or 0.4 to 0.95. By adjusting the ratio of the D and T units of the polyorganosiloxane as described above, for example, the polyorganosiloxane may be blended into a composition used as an encapsulant or an adhesive to exhibit appropriate physical properties.

In Formula (1), d represents the amount of a hydroxyl group or an alkoxy group contained in the polyorganosiloxane. In Formula 1, d is 0 or a positive number, for example, the number of moles (Si) of the total silicon atoms of the polyorganosiloxane and the total number of moles of the total hydroxy and alkoxy groups included in the polyorganosiloxane (OH + OR). The ratio of ((OH + OR) / Si) can be determined in a range of 0.01 or less. The lower limit of the ratio ((OH + OR) / Si) may be, for example, zero. When the ratio of the hydroxy group or the alkoxy group included in the polyorganosiloxane is adjusted as described above, for example, the polyorganosiloxane may be blended into the encapsulant or the adhesive composition to exhibit appropriate physical properties.

The polyorganosiloxane includes at least one aliphatic unsaturated bond or a functional group containing the same, for example, an alkenyl group. Therefore, at least one of R ¹ in Formula 1 may be, for example, an alkenyl group. For example, the number of moles (Ak) of an aliphatic unsaturated bond or a functional group including the aliphatic unsaturated bond with respect to the number of moles (Si) of all silicon atoms contained in the polyorganosiloxane, for example, the ratio of the number of moles of alkenyl groups (Ak / Si) It may be at least 0.005 or at least 0.01. The ratio (Ak / Si) may further be 0.4 or less or 0.3 or less. By adjusting the ratio (Ak / Si) to 0.005 or more or 0.01 or more, the reactivity in the composition in which the polyorganosiloxane is blended can be properly maintained, and unreacted components can be prevented from leaking to the surface of the cured product. have. In addition, by adjusting the ratio (Ak / Si) to 0.4 or less or 0.3, it is possible to maintain excellent crack resistance of the cured product in which the polyorganosiloxane is blended.

The polyorganosiloxane may include at least one epoxy group bonded to a silicon atom, and in this case, at least one of R ¹ in Formula 1 may be an epoxy group. For example, the ratio (Ep / Si) of the number of moles (Si) of all silicon atoms contained in the polyorganosiloxane and the number of moles (Ep) of the epoxy groups bonded to all the silicon atoms contained in the polyorganosiloxane is, for example, , 0.05 to 0.4. Within this range, for example, the adhesiveness of the encapsulant or adhesive in which the polyorganosiloxane is blended can be kept excellent.

The polyorganosiloxane may include one or more aryl groups, for example, one or more aryl groups bonded to silicon atoms, in which case at least one of R ¹ in Formula 1 may be an aryl group. For example, the ratio of the number of moles (Si) of all the silicon atoms contained in the polyorganosiloxane to the number of moles (Ar) of the aryl groups bonded to all the silicon atoms contained in the polyorganosiloxane (Ar / Si) is 0.3 or more or 0.35 or more. The composition in which the polyorganosiloxane is blended within the above range has excellent processability and workability, and may be cured to exhibit excellent moisture resistance, light dispersibility, light transmittance and hardness characteristics.

In one example, the polyorganosiloxane may have a viscosity at 25 ° C. of 100 cP to 500000 cP or 100 cP to 100,000 cP. Within this range, the processability and hardness characteristics of the composition to which the polyorganosiloxane is applied can be properly maintained.

In one example, the polyorganosiloxane may have a weight average molecular weight (Mw) of about 1,000 to 100,000 or about 1,500 to 30,000. The term "weight average molecular weight" means a conversion value with respect to standard polystyrene measured by Gel Permeation Chromatograph (GPC). Unless otherwise specified herein, the term molecular weight may mean a weight average molecular weight. Within this range, the moldability and hardness and strength characteristics of the composition to which the polyorganosiloxane is applied may be properly maintained.

Polyorganosiloxanes can be prepared, for example, by ring-opening polymerization of cyclic siloxane compounds. For example, the polyorganosiloxane may be a ring-opening polymerization reactant of a mixture containing a cyclic polyorganosiloxane or a component included in the reactant. In this way, the polyorganosiloxane is prepared by a ring-opening polymerization reaction, in particular, a ring-opening polymerization reaction of a predetermined raw material described later, and the length of the linear structure of the polyorganosiloxane can be easily adjusted to the desired range, and the hydroxyl group in the polyorganosiloxane and / Or the ratio of an alkoxy group etc. can be adjusted.

For example, the polyorganosiloxane may be a ring-opening polymerization reactant of a mixture including a cyclic compound of Formula 2 below.

(2)

In Formula 2, R ^a and R ^b are each independently an epoxy group or a monovalent hydrocarbon group, and o is 3 to 6.

Specific types of R ^a and R ^b in the formula (2), for example, can be adjusted in consideration of the structure of the desired polyorganosiloxane.

The mixture applied to the ring-opening polymerization reaction is a polyorganosiloxane of a cage structure, for example, includes a compound or a T unit having an average composition formula of the following formula (3), or as a polyorganosiloxane of a partial cage structure It may further include a compound having an average composition formula of.

(3)

[R ^c SiO _3/2]

[Chemical Formula 4]

_{^{[R d R f 2 SiO 1}} /2] p [R c SiO 3/2] q

In Formulas 3 and 4, R ^c to R ^f are each independently an epoxy group or a monovalent hydrocarbon group, p is 1 to 3, and q is 1 to 10. When the polyorganosiloxane of the average compositional formula of Formula 4 has a partial cage structure, p may be 1 to 2, and q may be 3 to 10.

In the formulas (3) and (4), the specific type of R ^c to R ^f , the specific values of p and q, and the ratio of each component in the mixture may be determined by the structure of the desired polyorganosiloxane.

A cyclic polyorganosiloxane, for example, a compound of formula (2) is reacted with a polyorganosiloxane having a cage structure and / or a partial cage structure or with the polyorganosiloxane containing T units, thereby producing a polyorganosiloxane having a desired structure. It can synthesize | combine with sufficient molecular weight. In addition, according to the above method, it is possible to prepare a target having excellent physical properties by minimizing a functional group such as an alkoxy group or a hydroxyl group bonded to a silicon atom in the polyorganosiloxane or a polymerization reaction including the same.

In one example, the mixture applied to the ring-opening polymerization reaction may further include a compound represented by the following Formula 5.

[Chemical Formula 5]

(R ^d R ^f ₂ Si) ₂ O

In formula (5), R ^d and R ^f are an epoxy group or a monovalent hydrocarbon group.

In the formula (5), the specific type of epoxy group or monovalent hydrocarbon group or the blending ratio in the mixture may be determined according to the desired polyorganosiloxane.

The reaction of each component in the mixture can be carried out in the presence of a suitable catalyst. Thus, the mixture may further comprise a catalyst.

As a catalyst, a base catalyst can be used, for example. Suitable base catalysts include metal hydroxides such as KOH, NaOH or CsOH; Metal silanolates or tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide, which contain an alkali metal compound and a siloxane, and the like, Quaternary ammonium compounds, and the like, but the present invention is not limited thereto.

The proportion of the catalyst in the mixture may be appropriately selected in consideration of the desired reactivity and the like, for example, 0.01 to 30 parts by weight or 0.03 to 5 parts by weight relative to 100 parts by weight of the total weight of the reactants in the mixture Can be included. Unless specifically stated otherwise herein, unit weight refers to the ratio of weight between components.

In one example, the reaction of the mixture can be carried out in the presence of a suitable solvent. As the solvent, any kind can be used as long as the reactants in the mixture, that is, the disiloxane or the polysiloxane, etc., and the catalyst can be properly mixed and the reactivity is not adversely affected. Examples of the solvent include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, 2,2,4-trimethylpentane, cyclohexane or methylcyclohexane; Aromatic solvents such as benzene, toluene, xylene, trimethylbenzene, ethylbenzene or methylethylbenzene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, Ketone solvents such as methylcyclohexanone and acetylacetone; Propyl ether, isopropyl ether, diglyme, dioxine, dimethyl dioxin, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diethyl ether, Ether type solvents such as propylene glycol monomethyl ether and propylene glycol dimethyl ether; Ester solvents such as diethyl carbonate, methyl acetate, ethyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate or ethylene glycol diacetate; Amide solvents such as N-methylpyrrolidone, formamide, N-methylformamide, N-ethylformamide, N, N-dimethylacetamide or N, N-diethylacetamide can be exemplified. But is not limited to.

The reaction of the mixture, for example the ring-opening polymerization reaction, can be carried out, for example, with the addition of a catalyst, for example at a reaction temperature in the range of 0 ° C to 150 ° C or 30 ° C to 130 ° C. In addition, the reaction time can be adjusted within a range of, for example, 1 hour to 3 days.

The present application also relates to a curable composition comprising the polyorganosiloxane. The curable composition may be used, for example, as an encapsulant for an optical semiconductor or an adhesive composition including an LED.

The curable composition may include components that allow it to be cured by hydrosilylation, for example by reaction of an aliphatic unsaturated bond with a hydrogen atom.

For example, the curable composition may be polyorganosiloxane (hereinafter, polyorganosiloxane (A)) having an average composition formula of the following formula (6); And a compound of Formula 7 (hereinafter, Compound (C)) together with the polyorganosiloxane. For example, the polyorganosiloxane may be included in an amount of 0.01 parts by weight to 50 parts by weight based on 100 parts by weight of the polyorganosiloxane (A) in the curable composition.

[Chemical Formula 6]

_{^{(R 2 3 SiO 1/2}} ) a (R 2 2 SiO 2/2) b (R 2 SiO 3/2) c (SiO 4/2) d

[Formula 7]

R ³ _h H _i SiO _{(4-hi) / 2}

R ² in Formulas 6 and 7 is a monovalent hydrocarbon group, at least one of R ² is an alkenyl group, the sum of a, b, c and d is 1, a is 0 to 0.5, b is 0 to 0.8 and c is 0 to 0.8, d is 0 to 0.5, (a + b) / (a + b + c + d) is 0.2 to 0.7, and R ³ is a monovalent hydrocarbon group having no aliphatic unsaturated bonds. For example, it is an alkyl group or an aryl group, h is 1-2.2, i is 0.01-1, and the sum of h and i (h + i) is 1-3.

In the average composition formula (6), a, b, c and d represent the molar ratio of the siloxane units contained in the polyorganosiloxane (A). When the sum (a + b + c + d) is converted to 1, a is 0 to 0.5, b is 0 to 0.8, c is 0 to 0.8, d is 0 to 0.5, and (a + b ) / (a + b + c + d) may be 0.2 to 0.7. By adjusting the ratio of the siloxane units in this way it is possible to ensure suitable physical properties according to the application.

The polyorganosiloxane (A) contains at least one aliphatic unsaturated bond or a functional group including the same, for example, an alkenyl group. Accordingly, at least one of R ² in Formula 6 may be an alkenyl group. For example, an aliphatic unsaturated bond with respect to the number-of-moles (Si) of all the silicon atoms contained in polyorganosiloxane (A), or the number-of-moles (Ak) of the functional group containing it, for example, the ratio of the number-of-moles of an alkenyl group (Ak / Si) may be at least 0.01 or at least 0.05. The ratio (Ak / Si) may further be 0.4 or less or 0.35 or less. By adjusting the ratio (Ak / Si) to 0.01 or more or 0.05 or more, the reactivity can be properly maintained, and the phenomenon that the unreacted component is bleeded to the surface of the cured product can be prevented. In addition, by adjusting the ratio (Ak / Si) to 0.4 or less or 0.35 or less, it is possible to maintain excellent crack resistance of the cured product.

The polyorganosiloxane (A) may contain one or more aryl groups, for example, an aryl group bonded to a silicon atom. In this case, at least one of R ² in Formula 6 may be an aryl group. In the case of containing an aryl group, for example, the number of moles of all silicon atoms (Si) included in the polyorganosiloxane (A) and the number of moles of aryl groups bonded to all the silicon atoms contained in the polyorganosiloxane (A) ( The ratio (Ar / Si) of Ar) may be 0.3 to 1.5 or 0.3 to 1.2. Thereby, the composition has excellent workability and workability, and can be cured to exhibit excellent moisture resistance, light dispersibility, light transmittance and hardness characteristics, and the like.

In one example, the polyorganosiloxane (A) may have a viscosity at 25 ° C. of at least 2,000 cP, at least 3,000 cP, at least 4,000 cP, at least 5,000 cP, at least 7,000 cP, at least 9,000 cP, or at least 9,500 cP. Within this range, the processability of the curable composition and the hardness characteristics after curing can be properly maintained. The upper limit of the viscosity is not particularly limited, but for example, the viscosity may be 100,000 cP or less, 90,000 cP or less, 80,000 cP or less, 70,000 cP or less, or 65,000 cP or less.

The molecular weight of the polyorganosiloxane (A) may be, for example, about 800 to 50,000 or about 800 to 30,000. Within this range, the moldability of the curable composition and the hardness and strength characteristics after curing can be properly maintained.

The polyorganosiloxane (A) may be prepared by applying a conventional method known in the art of producing polyorganosiloxane or through a ring-opening polymerization reaction for producing the polyorganosiloxane.

The curable composition may further include, for example, a polyorganosiloxane having an average composition formula of the following Formula 8. The polyorganosiloxane (hereinafter, polyorganosiloxane (B)) of the average composition formula of Formula 8 may be, for example, a crosslinked polyorganosiloxane. The term "crosslinked polyorganosiloxane" may mean a polyorganosiloxane that necessarily includes a T unit or a Q unit as the siloxane unit.

[Formula 8]

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

R ⁴ in formula (8) is each independently an epoxy group or a monovalent hydrocarbon group, at least one of R ⁴ is an alkenyl group, the sum of e, f, g and h is 1, e is 0 or a positive number, f Is 0 or positive number, g is 0 or positive number, h is 0 or positive number, (e + f) / (e + f + g + h) is 0.2 to 0.7, f / ( f + g + h) is 0.4 or less, and g / (g + h) is 0.8 or more.

At least one or two or more of R ⁴ in Formula 8 may be an alkenyl group. In one example, the ratio (Ak / Si) of the number of moles (Ak) of the alkenyl group to the number of moles (Si) of the total silicon atoms included in the polyorganosiloxane (B) may be 0.05 or more or 0.15 or more. The ratio (Ak / Si) may also be 0.4 or less, 0.35 or less or 0.3 or less. By controlling the molar ratio (Ak / Si) to 0.05 or more or 0.15 or more, the reactivity can be properly maintained, and the phenomenon that the unreacted component is bleeded out onto the surface of the cured product can be prevented. In addition, by adjusting the molar ratio (Ak / Si) to 0.4 or less, 0.35 or less, or 0.3 or less, the hardness characteristics, crack resistance, thermal shock resistance, and the like of the cured product can be maintained excellent.

The polyorganosiloxane (B) may include at least one aryl group or may not include an aryl group. For example, it may be possible to control the relationship between the refractive index between the components through the control of the inclusion and / or the ratio of the aryl group. In the case of including an aryl group, at least one of R ⁴ in Formula 8 may be an aryl group. In the above case, for example, the ratio (Ar / Si) of the number of moles (Ar) of the aryl group to the number of moles (Si) of all the silicon atoms of the polyorganosiloxane (B) is 0.35 to 1.2 or 0.5 to 0.5. May be 1.1. The refractive index, gas permeability, water permeability, thermal shock resistance, crack resistance and hardness characteristics of the cured product were adjusted by adjusting the molar ratio (Ar / Si) as described above, adjusting the relationship of the refractive index with the polyorganosiloxane (A) to the desired range. And the viscosity of the composition can also be appropriately maintained.

In the average compositional formula of formula (4), e, f, g and h represent the molar ratio of each siloxane unit, and when the sum is 1, e is 0 or a positive number such as 0 to 0.5 or 0.05 to 0.5 f is 0 or a positive number, for example 0 to 0.5 or 0 to 0.3, g is 0 or a positive number, for example 0 to 0.95, 0.2 to 0.95 or 0.2 to 0.85, and h is 0 Or a positive number, for example 0 to 0.3 or 0 to 0.2. In addition, in the average composition formula (8) of the polyorganosiloxane (B), (e + f) / (e + f + g + h) is 0.2 to 0.7, and f / (f + g + h) is 0.4 or less. , g / (g + h) may be at least 0.8. By adjusting the ratio of M, D, T, and Q units within this range, the composition exhibits excellent processability and workability, and may be cured to provide a composition having excellent physical properties such as hardness, crack resistance, and thermal shock resistance.

The polyorganosiloxane (B) may have a viscosity of 5,000 cP or more, 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.

In addition, the polyorganosiloxane (B) may have a molecular weight of, for example, 800 to 100,000 or 1,000 to 100,000. By controlling the molecular weight to 800 or more, the moldability before curing and the strength after curing can be effectively maintained, and the molecular weight can be adjusted to 100,000 or less to maintain the viscosity and the like at an appropriate level.

The polyorganosiloxane (B) can be produced, for example, by applying a known method for producing a polyorganosiloxane, or by applying the ring-opening polymerization method described above.

The polyorganosiloxane (B) may be included, for example, in an amount of 50 parts by weight to 700 parts by weight or 50 parts by weight to 500 parts by weight relative to 100 parts by weight of polyorganosiloxane (A).

The compound of the formula (7) is a silicon compound (compound (C)) containing a hydrogen atom bonded to the silicon atom, the formula (7), for example, the silicon compound (C) may be an average composition formula. The silicon compound (C) may have one or more or two or more hydrogen atoms bonded to silicon atoms.

Silicon compound (C) can act as a crosslinking agent which reacts with the aliphatic unsaturated bond containing functional group of polyorganosiloxane, and crosslinks a composition. For example, the hydrogen atom of the silicon compound (C) may react with an aliphatic unsaturated bond such as an alkenyl group of the polyorganosiloxane (A) and / or the polyorganosiloxane (B) to crosslink and cure.

In one example, the ratio (H / Si) of the number of moles (H) of hydrogen atoms bonded to the silicon atoms to the number of moles (Si) of the total silicon atoms of the silicon compound (C) of Formula 7 may be 0.2 or more or 0.3 or more. . The ratio (H / Si) may also be 0.8 or less or 0.75 or less. The molar ratio (H / Si) is adjusted to 0.2 or more or 0.3 to maintain excellent curability of the composition, and to 0.8 or less or 0.75 or less, thereby maintaining excellent crack resistance and thermal shock resistance. .

The silicon compound (C) may comprise at least one aryl group, in which case at least one of R ³ in Formula 7 may be an aryl group. In the case of containing an aryl group, for example, the ratio (Ar / Si) of the number of moles (Ar) of the aryl group to the number of moles (Si) of all the silicon atoms contained in the silicon compound (C) is 0.3 to 1.5 or 0.3 To 1.2. By adjusting the molar ratio (Ar / Si) as described above, the refractive index and the hardness of the cured product can be maximized while controlling the relationship between the refractive index with the polyorganosiloxane (A), and the viscosity and crack resistance can be properly maintained. .

The silicon compound (C) may have a viscosity of 0.1 cP to 100,000 cP, 0.1 cP to 10,000 cP, 0.1 cP to 1,000 cP or 0.1 cP to 300 cP at 25 캜. If it has the said viscosity, the processability of the composition, the hardness of hardened | cured material, etc. can be maintained outstanding.

In addition, the silicon compound (C) may have a molecular weight of, for example, less than 2,000, less than 1,000 or less than 800. When the molecular weight of a silicon compound (C) is 1,000 or more, there exists a possibility that the intensity | strength of hardened | cured material may fall. The lower limit of the molecular weight of the silicon compound (C) is not particularly limited, and may be 250, for example. The molecular weight of the silicon compound (C) may be a weight average molecular weight or may mean a conventional molecular weight of the compound.

The method for producing the silicon compound (C) is not particularly limited, and can be produced, for example, by applying a method commonly known in the preparation of polyorganosiloxane, or by applying a method according to polyorganosiloxane (A). have.

The silicon compound (C) is, for example, the polyorganosiloxane (A), the polyorganosiloxane (A) contained in the polyorganosiloxane (A) and an adhesion imparting agent, or the polyorganosiloxane (A), or a polio contained as an adhesion imparting agent. Hydrogen atom couple | bonded with the silicon atom contained in the silicon compound (C) with respect to the mole number (Ak) of the total aliphatic unsaturated bond contained in the organosiloxane and the said polyorganosiloxane (B), or the functional group containing it, for example, an alkenyl group It can be included in the curable composition so that the ratio (H / Ak) of the number of moles (H) of 0.5 or more or 0.7 or more. Silicon compound (C) can also be included in curable composition so that the said ratio (H / Ak) may be 2.0 or less or 1.5 or less. Thereby, it is possible to provide a composition which exhibits excellent workability and workability prior to curing, cures to exhibit excellent crack resistance, hardness characteristics, heat shock resistance and adhesiveness, and does not cause turbidity or surface stickiness under severe conditions. have.

The curable composition may further comprise a hydrosilylation catalyst. Hydrosilylation catalysts can be used to accelerate the hydrogensilylation 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, the amount that can act as a catalyst. Typically, it can be used in an amount of 0.1 ppm to 500 ppm or 0.2 ppm to 100 ppm based on the atomic weight of platinum, palladium or rhodium.

The curable composition may also contain a separate adhesion imparting agent in addition to the polyorganosiloxane in view of further improvement of the adhesion to various substrates. The tackifier is a component capable of improving self adhesiveness, and in particular, can improve self adhesiveness to metals and organic resins.

As an adhesive imparting agent, 1 or more types chosen from the group which consists of alkenyl groups, such as a vinyl group, a (meth) acryloyloxy group, a hydrosilyl group (SiH group), an epoxy group, an alkoxy group, an alkoxy silyl group, a carbonyl group, and a phenyl group Or silanes having two or more functional groups; Or organic silicon compounds such as cyclic or linear siloxanes having 2 to 30 or 4 to 20 silicon atoms, and the like, but are not limited thereto. In the present application, one kind or two or more kinds of the above-mentioned adhesion imparting agents may be further mixed and used.

When the adhesive property-imparting agent is included in the composition, for example, the total weight of the other compounds contained in the curable composition, for example, the above-mentioned polyorganosiloxane (A), the polyorganosiloxane (B) and / May be contained in an amount of 0.1 part by weight to 20 parts by weight based on 100 parts by weight of the resin. However, the content may be appropriately changed in consideration of the desired adhesiveness improving effect and the like.

The curable composition may contain, if necessary, 2-methyl-3-butyne-2-ol, 2-phenyl-3-1- 3-hexen-1-yne, 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; 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 curable composition may also include particles, such as inorganic particles. The particles may satisfy the following Equation 1.

[Equation 1]

| P-Q | ≤ 0.1

In Equation 1, P is the refractive index of the curable composition or the cured product thereof except for the particles, and Q is the refractive index of the particles. The refractive index may be, for example, a refractive index for light having a wavelength of 450 nm. The absolute value of the difference between P and Q may be 0.08 or less, 0.07 or less, or 0.05 or less in another example.

The particles can, for example, prevent sedimentation of phosphors that can be blended into the curable composition, improve heat resistance, heat dissipation crack resistance, and the like, thereby improving overall reliability. In addition, the particles can maintain the transparency of the composition or cured product while performing the above functions, for example, to improve the luminance of the device.

As the particles, as long as the formula 1 is satisfied, for example, all kinds of particles that are used as fillers in the industry may be used. In one example, as the particles, particles having a refractive index (Q) of 1.40 or more, 1.45 or more, 1.48 or more, 1.50 or more, or 1.55 or more may be used.

Examples of the particles include silica (SiO ₂ ), organo silica, alumina, alumino silica, titanium, zirconia, cerium oxide, hafnium oxide, niobium pentoxide, tantalum pentoxide, indium oxide, tin oxide, and indium tin oxide. , Zinc oxide, silicon, zinc sulfate, calcium carbonate, barium sulfate, aluminosilicate or magnesium oxide may be used, which may be in the form of porous or hollow particles.

The average particle diameter of the particles may be, for example, 1 nm to 50 μm or 2 nm to 10 μm. With an average particle diameter of 1 nm or more, the particles can be uniformly dispersed in the composition or the cured product thereof, and also set to 50 µm or less, so that the dispersion of the particles can be effectively performed and the sedimentation of the particles can be prevented.

The particles may be included in the composition in an amount of 0.1 to 30 parts by weight or 0.2 to 10 parts by weight based on 100 parts by weight of the total weight of the polyorganosiloxane (A) or the polyorganosiloxane (B) and the silicon compound (C). . If the content of the particles is 0.1 parts by weight or more, excellent sedimentation suppression of the phosphor or the effect of improving the reliability of the device can be secured, and if it is 30 parts by weight or less, excellent processability can be maintained.

The curable composition may further comprise a phosphor. The kind of phosphor that can be used is not particularly limited, and for example, a conventional kind of phosphor applied to an LED package to implement white light may be used.

The present application also relates to a semiconductor device, for example, an optical semiconductor device. Exemplary semiconductor devices may be encapsulated by an encapsulant comprising a cured product of the curable composition. Examples of the semiconductor element encapsulated with the encapsulant include a diode, a transistor, a thyristor, a photocoupler, a CCD, a solid state image pickup element, an integrated IC, a hybrid IC, an LSI, a VLSI, a light emitting diode (LED), and the like. In one example, the semiconductor element may be a light emitting diode.

As a light emitting diode, the light emitting diode etc. which were formed by laminating | stacking a semiconductor material on a board | substrate can be illustrated, for example. 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.

Further, at the time of 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 composition. The encapsulation of the light emitting diode may be performed only with the composition, and in some cases, another encapsulant may 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.

As a method of encapsulating a light emitting diode with a curable composition, for example, the composition is pre-injected into a mold form die, a lead frame having a light emitting diode fixed thereto is immersed therein, and a method of curing the composition and a light emitting diode is inserted. The method of injecting and curing the composition in one form can be 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.

If necessary, the curable composition may be used as a die-bonding material for fixing the light emitting diode to a lead terminal or a package, a passivation film or a package substrate on the light emitting diode.

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, may be, for example, a backlight of a liquid crystal display (LCD), an illumination, various sensors, a light source such as a printer, a copier, a vehicle instrument light source, a signal lamp, an indicator light, It can be effectively applied to a display device, a light source of an area light emitting body, a display, a decoration or various lights.

The polyorganosiloxane of the present application can be used, for example, as an adhesion improving agent. The polyorganosiloxane of the present application can be used to form a composition or a cured product thereof that exhibits excellent adhesion to various materials including organic materials and the like, and has excellent optical properties and reliability. The composition or the cured product thereof may be used, for example, as an encapsulant for an optical semiconductor device.

Hereinafter, the polyorganosiloxane, the curable composition, and the like will be described in more detail with reference to Examples and Comparative Examples, but the range of the polyorganosiloxane and the like is not limited by the following examples. In the examples, Vi represents a vinyl group, Ph represents a phenyl group, Me represents a methyl group, and Ep represents a 3-glycidoxypropyl group.

1. Evaluation of device characteristics

Device properties are evaluated using a 6030 LED package made of polyphthalamide (PPA). The curable composition is dispensed into a polyphthalamide cup, held at 70 ° C. for 30 minutes, and then maintained at 150 ° C. for 1 hour to cure to produce a surface mounted LED.

Thereafter, the thermal shock test and the long-term reliability test are performed according to the following method.

(One) Thermal shock  Test

The LED was kept at -40 ° C for 30 minutes and again at 100 ° C for 30 minutes as one cycle, and the above was repeated 10 times, i.e., 10 cycles, and maintained at room temperature, and the thermal shock resistance was investigated by examining the peeling state. Evaluate. At the time of evaluation, the above-mentioned tests were carried out for each of 10 LEDs made from the same curable composition, and the number of LEDs that were peeled off is shown in Table 1 below.

(2) Long-term reliability test

The LEDs are operated for 200 hours with a current of 30 mA maintained at 85 ° C and 85% relative humidity. Next, the rate of decrease of the latter luminance after the above operation relative to the initial luminance before the operation is measured and evaluated according to the following criteria.

<Evaluation Criteria>

○: The luminance reduction ratio to the initial luminance is 10% or less

X: The luminance reduction ratio with respect to the initial luminance exceeds 10%

2. On polyorganosiloxane  About ^One H- NMR  Measure

¹ H-NMR analysis of polyorganosiloxane was performed under the following conditions.

< ¹ H-NMR analysis content>

Measuring instrument: Varian Unity Inova 500 MHz NMR

Solvent used: acetone-d6

Measuring conditions:

Pulse sequence: s2pul

Sweep width: 8012.8hz

Acquisition time: 2.045 sec

Delay time: 2 sec

Pulse width: 45 degree pulse (8.10 μsec)

Number of scan: 16

Synthetic example  One.

Divinyltetramethyldisiloxane 15.7 in a mixture of 60 g of octamethylcyclotetrasiloxane, 106.96 g of octaphenylcyclotetrasiloxane and 44.96 g of Ep-POSS g and 0.73 mL of tetramethylammonium hydroxide (TMAH; tetramethylammonium hydroxide) were combined. Thereafter, the mixture was reacted at a temperature of 115 ° C. for about 20 hours. After the reaction was completed, the low molecular weight material was removed from the reactant to obtain a polysiloxane (A) in the form of a transparent oil having an average compositional formula of the formula (A). The viscosity at 25 degrees C of the said polysiloxane (A) was 28,300 cP, and the molecular weight (Mw) was about 4,500. In addition, on the spectrum measured by <^1> H-NMR with respect to polysiloxane (A), the peak derived from an alkoxy group or a hydroxyl group (silanol) was not observed.

(A)

_{[ViMe 2 SiO 1/2]} 0.05 [Me 2 SiO 2/2] 0.49 [Ph 2 SiO 2/2] 0.31 [EpSiO 3/2] 0.15

Synthetic example  2.

Change the amount of Ep-POSS (octaglycidyldimethylsilyl POSS, EP0435, Hybrid Plastics) to 22.48 g, change the amount of divinyl tetramethyldisiloxane to 12.54 g, and change the amount of tetramethylammonium hydroxide (TMAH) 0.65 Except for changing to mL, the reaction was carried out in the same manner as in Synthesis Example 1 to obtain a polysiloxane (B) having an average composition formula of the formula (B). The viscosity at 25 degrees C of polysiloxane (B) was 19,500 cP, and the molecular weight (Mw) was about 6,100. Moreover, the peak derived from an alkoxy group or a hydroxyl group (silanol) was not observed on the spectrum measured by <^1> H-NMR with respect to polysiloxane (B).

[Formula B]

_{[ViMe 2 SiO 1/2]} 0.05 [Me 2 SiO 2/2] 0.50 [Ph 2 SiO 2/2] 0.34 [EpSiO 3/2] 0.11

Synthetic example  3.

Except for not using octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane, instead using 183.71 g of tetramethyltetraphenylcyclotetrasiloxane and changing the amount of divinyltetramethyldisiloxane to 12.10 g The reaction was carried out in the same manner as in Synthesis example 1 to obtain a polysiloxane (C) having an average composition formula of the formula (C). The viscosity at 25 degrees C of polysiloxane (C) was 17,400 cP, and the molecular weight (Mw) was about 4,400. In addition, on the spectrum measured by <^1> H-NMR with respect to polysiloxane (C), the peak derived from an alkoxy group or a hydroxyl group (silanol) was not observed.

&Lt; RTI ID = 0.0 &

_{[ViMe 2 SiO 1/2]} 0.05 [PhMeSiO 2/2] 0.84 [EpSiO 3/2] 0.11

Synthetic example  4.

Change the amount of Ep-POSS (octaglycidyldimethylsilyl POSS, EP0435, Hybrid Plastics) to 124.87 g, change the amount of divinyl tetramethyldisiloxane to 41.75 g, and change the amount of tetramethylammonium hydroxide (TMAH) to 1.06 Except for changing to mL, the reaction was carried out in the same manner as in Synthesis Example 1 to obtain a polysiloxane (D) having an average composition formula of the formula (D). The viscosity at 25 degrees C of polysiloxane (D) was 3,780 cP, and molecular weight (Mw) was about 4,300. In addition, the peak derived from an alkoxy group or a hydroxyl group (silanol) was not observed on the spectrum measured by <^1> H-NMR with respect to polysiloxane (D).

[Chemical Formula D]

_{[ViMe 2 SiO 1/2]} 0.14 [Me 2 SiO 2/2] 0.32 [Ph 2 SiO 2/2] 0.24 [EpSiO 3/2] 0.30

compare Synthetic example  One.

The reaction was carried out in the same manner as in Synthesis Example 1, except that 63.54 g of (3-glycidoxypropyl) trimethoxy silane was used without using Ep-POSS. The polyorganosiloxane produced from the obtained reactant was not able to be separated because its molecular weight was similar to that of the low molecular cyclic compound included in the reactant. Moreover, the ratio ((OR + OH) / Si) with respect to the silicon atom of the alkoxy group (methoxy group) and the hydroxy group was 0.16 as a result of the measurement of <^1> H-NMR.

compare Synthetic example  2.

To a solution of 97.27 g of dimethoxydimethyl silane, 131.81 g of dimethoxydiphenyl silane, and 12.54 g of divinyltetramethyldisiloxane in 130 g of toluene were added, 106.0 g of water and 8.6 mL of nitric acid were added. The reaction was carried out for hours. After the reaction, the solution was cooled to room temperature, washed with water until neutral, and then 31.77 g of (3-glycidoxypropyl) trimethoxy silane and 0.2 g of KOH were added to proceed with dehydration condensation. After the reaction, the reaction was neutralized with AcOH, washed with water to neutrality, and then the solvent was removed by distillation under reduced pressure. The polyorganosiloxane produced from the obtained reactant was in the form of an oil without transparency, contained a large amount of cyclic low molecular weight compound, and the molecular weight of the obtained polyorganosiloxane was similar to that of the low molecular cyclic compound included in the reaction, and thus could not be separated. . Further, yiyeotda ¹ H-NMR measurement results, an alkoxy group (a methoxy group) and the ratio ((OR + OH) / Si) of silicon atoms than the hydroxy group is 0.015.

Example  One

100 g of polyorganosiloxane of Formula E, 200 g of polyorganosiloxane of Formula F, 50 g of polyorganosiloxane of Formula G, and 5 g of polyorganosiloxane having an average composition formula of Formula A prepared in Synthesis Example 1 After mixing, the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was mixed so that the content of Pt (0) was 5 ppm, and uniformly mixed to prepare a curable composition. .

(E)

_{(ViMe 2 SiO 1/2)} 2 (Me 2 SiO 2/2) 20 (Ph 2 SiO 2/2) 10

[Chemical Formula F]

_{(ViMe 2 SiO 1/2)} 2 (Ph 2 SiO 2/2) 8

[Formula G]

_{(HMe 2 SiO 1/2)} 2 (HMeSiO 2/2) 0.5 (Ph 2 SiO 2/2) 1.5

Example 2.

A curable composition was prepared in the same manner as in Example 1, except that 20 g of the polyorganosiloxane having the average composition formula of Formula B was mixed instead of the polyorganosiloxane of the formula A of Formula A.

Example 3.

A curable composition was prepared in the same manner as in Example 1, except that 20 g of the polyorganosiloxane having the average composition formula of Formula C was mixed instead of the polyorganosiloxane having the formula composition of Formula A.

Example 4.

A curable composition was prepared in the same manner as in Example 1, except that 20 g of the polyorganosiloxane having the average composition formula of Formula D was mixed instead of the polyorganosiloxane having the formula composition of Formula A.

Comparative Example  One.

A curable composition was prepared in the same manner as in Example 1, except that the polyorganosiloxane of the average composition formula of Formula A was not used.

Comparative Example  2

Curable compositions were prepared in the same manner as in Example 2, except that the polyorganosiloxane of the average composition formula of Formula B was not used.

Comparative Example  3

A curable composition was prepared in the same manner as in Example 1, except that the polyorganosiloxane of the average composition formula of Formula A was not used, and instead the reactant obtained in Comparative Synthesis Example 1 was used.

Comparative Example  4

A curable composition was prepared in the same manner as in Example 1, except that the polyorganosiloxane of the average composition formula of Formula A was not used, and instead the reactant obtained in Comparative Synthesis Example 2 was used.

Thermal shock test Heat resistance Example 1 0/10 ○ Example 2 0/10 ○ Example 3 0/10 ○ Example 4 0/10 ○ Comparative Example 1 10/10 × Comparative Example 2 10/10 × Comparative Example 3 5/10 × Comparative Example 4 6/10 ×

Claims (16)

A polyorganosiloxane having an average composition formula of the following formula (1), wherein the ratio (OH + OR) / Si of the number of moles (Si) of all silicon atoms and the total number of moles (OH + OR) of all the hydroxy and alkoxy groups is 0.01 or less:
[Chemical Formula 1]
_{^{(R 1 3 SiO 1/2}} ) a (R 1 2 SiO 2/2) b (R 1 SiO 3/2) c (OR) d
In Formula 1, R ¹ is an epoxy group or a monovalent hydrocarbon group, at least one of R ¹ is an alkenyl group, at least one of R ¹ is an epoxy group, a is 0 or a positive number, b is a positive number, c is a positive number, d is 0 or a positive number, the sum of a, b, and c is 1, b / (b + c) is 0.4 to 0.97, and R is an alkyl group or a hydrogen atom. The polyorganosiloxane according to claim 1, wherein the ratio (Ak / Si) of the number of moles (Ak) of the alkenyl group to the number of moles (Si) of all the silicon atoms is 0.005 to 0.4. The polyorganosiloxane according to claim 1, wherein the ratio (Ep / Si) of the number of moles (Si) of all the silicon atoms and the number of moles (Ep) of the epoxy group bonded to all the silicon atoms is 0.05 to 0.4. The polyorganosiloxane of claim 1 comprising at least one aryl group bonded to a silicon atom. The polyorganosiloxane according to claim 4, wherein the ratio (Ar / Si) of the number of moles (Si) of all the silicon atoms and the number of moles (Ar) of the aryl groups bonded to all the silicon atoms is 0.3 or more. The polyorganosiloxane according to claim 1, wherein the weight average molecular weight is 1,000 to 100,000. The polyorganosiloxane of claim 1 which is a ring-opening polymerization reaction of a mixture comprising a compound of formula:
(2)

In Formula 2, R ^a and R ^b are each independently an epoxy group or a monovalent hydrocarbon group, and o is 3 to 6. The polyorganosiloxane of claim 7, wherein the mixture further comprises a polyorganosiloxane having an average composition formula of Formula 3 or:
(3)
[R ^c SiO _3/2]
[Chemical Formula 4]
_{^{[R d R f 2 SiO 1}} /2] p [R c SiO 3/2] q
In Formulas 3 and 4, R ^c to R ^f are each independently an epoxy group or a monovalent hydrocarbon group, p is 1 to 3, and q is 1 to 10. The polyorganosiloxane of claim 7, wherein the mixture further comprises a compound represented by Formula 5:
[Chemical Formula 5]
(R ^d R ^f ₂ Si) ₂ O
In Formula 5, R ^d and R ^f are an epoxy group or a monovalent hydrocarbon group. Curable composition containing the polyorganosiloxane of Claim 1. 11. The method of claim 10, Polyorganosiloxane having an average composition formula of the formula (6); And a compound of Formula 7 further comprising:
[Chemical Formula 6]
_{^{(R 2 3 SiO 1/2}} ) a (R 2 2 SiO 2/2) b (R 2 SiO 3/2) c (SiO 4/2) d
(7)
R ³ _h H _i SiO _{(4-hi) / 2}
In Formulas 6 and 7, R ² is a monovalent hydrocarbon group, at least one of R ² is an alkenyl group, the sum of a, b, c and d is 1, a is 0 to 0.5, and b is 0 to 0.8 C is 0 to 0.8, d is 0 to 0.5, (a + b) / (a + b + c + d) is 0.2 to 0.7, and R ³ is a monovalent hydrocarbon having no aliphatic unsaturated bond. Group, for example, an alkyl group or an aryl group, h is 1 to 2.2, i is 0.01 to 1, and the sum of h and i (h + i) is 1 to 3. The curable composition of claim 11, wherein the polyorganosiloxane having an average composition formula of Formula 1 is included in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of polyorganosiloxane having an average composition formula of Formula 2. 12. The curable composition of claim 11, further comprising a polyorganosiloxane of an average composition formula of Formula 8:
[Chemical Formula 8]
_{^{(R 4 3 SiO 1/2}} ) e (R 4 2 SiO 2/2) f (R 4 SiO 3/2) g (SiO 4/2) h
R ⁴ in formula (8) is each independently an epoxy group or a monovalent hydrocarbon group, at least one of R ⁴ is an alkenyl group, the sum of e, f, g and h is 1, e is 0 or a positive number, f Is 0 or positive number, g is 0 or positive number, h is 0 or positive number, (e + f) / (e + f + g + h) is 0.2 to 0.7, f / ( f + g + h) is 0.4 or less, and g / (g + h) is 0.8 or more. An optical semiconductor encapsulated with the curable composition of claim 10. A liquid crystal display comprising the optical semiconductor of claim 14 in a backlight unit. A lighting device comprising the optical semiconductor of claim 14.