KR20150035074A - Curable composition - Google Patents

Abstract

The present invention relates to a curable composition including: (A) polyorgano siloxane having an aryl group and two or more aliphatic unsaturated bonds; (B) polyorgano siloxane having two or more hydrogen atoms bound to the aryl group and a silicon atom; and metal particles. According to the present invention, the curable composition has excellent processability and reliability, and has excellent brightness and heat retrieving characteristics of an optical device. Also, the curable composition can be effectively used as a use for a die adhesive.

Description

{CURABLE COMPOSITION}

The present invention relates to a curable composition and its use.

Recently, light emitting diodes (LEDs) have been attracting attention as a new illumination that realizes energy saving. Such a light emitting diode can be combined with red, green and blue light emitting diodes to realize a high-quality full color image.

In addition, a technique of manufacturing a white light emitting diode by combining a blue light or an ultraviolet light emitting diode with a phosphor is known, and such a light emitting diode is in demand as a backlight of a liquid crystal display (LCD) or general illumination.

Conventionally, an epoxy resin having high adhesiveness and excellent durability as an adhesive resin for red, green, blue or ultraviolet light-emitting diode elements, specifically, an epoxy resin using an acid anhydride-based curing agent has been widely used. However, the epoxy resin has a problem in that the light transmittance to light in the blue to ultraviolet region is low, and furthermore, the light resistance is deteriorated due to deterioration due to light and coloring. In addition, recently, a high output LCD chip is used for a backlight of a liquid crystal display (LCD) or a general lighting, so that there is a problem that the die bond becomes yellow when used for a long time.

Accordingly, for the purpose of improving the above problems, there has been an example in which an epoxy having excellent heat resistance is used or a heat-resistant property is improved by using a silicone epoxy hybrid-modified resin. However, the epoxy resin or epoxy silicone modified hybrid resin adhesive still had a disadvantage that heat resistance was poor.

In recent years, there have been products in which heat resistance is solved by using a silicone resin which is excellent in heat resistance. However, since the refractive index of the used silicone resin is as low as about 1.4, there is a problem that the light extraction efficiency is low due to a large difference in refractive index from an alumina substrate used for manufacturing LED devices. In addition, the silicone resin has problems that the free volume of the resin is large and the heat dissipation property is deteriorated.

The present invention provides a curable composition and its use.

The present invention relates to (A) a polyorganosiloxane having an aryl group and two or more aliphatic unsaturated bonds;

(B) a polyorganosiloxane having two or more hydrogen atoms bonded to an aryl group and a silicon atom; And

The present invention relates to a curable composition comprising metal particles.

Hereinafter, the curable composition of the present invention will be described in more detail.

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 polyorganosiloxane comprising an aryl group and two or more aliphatic unsaturated bonds, and a polyorganosiloxane comprising an aryl group and two or more hydrogen atoms bonded to a silicon atom.

The term "M unit" herein formula (R ₃ SiO _1/2) so-called consistent mean-functional siloxane units that can be represented by a, and the term "D unit" is to be represented by the formula (R ₂ SiO _2/2) so-called transfer means a functional siloxane units, and the term "T unit", the formula (RSiO _3/2) means a so-called trifunctional siloxane units that can be represented by and, the term "Q unit" which can have formula (SiO _4/2 Quot;). ≪ / RTI > The R is a functional group bonded to silicon (Si), and may be, for example, a hydrogen atom, an alkoxy group, a hydroxy group, an epoxy group or a monovalent hydrocarbon group.

The curable composition according to the present invention may include an aryl group and a polyorganosiloxane having two or more aliphatic unsaturated bonds (hereinafter referred to as polyorganosiloxane (A)).

In the present invention, the polyorganosiloxane (A) may mean a crosslinked polyorganosiloxane or a network-like polyorganosiloxane essentially containing T or Q units, and may also be a linear polyol May mean a siloxane, a siloxane, or a siloxane. Specifically, the polyorganosiloxane (A) of the present invention may be a mixture of a crosslinked structure, a network-like structure, and a linear structure.

In one example, the polyorganosiloxane (A) may comprise, for example, a high-refraction polyorganosiloxane. As used herein, the term " high-refraction polyorganosiloxane " may refer to a polyorganosiloxane containing an aryl group in a molecule at a predetermined ratio or more. In the present specification, the ratio of the aryl group (Ar) to the total silicon atom (Si) of the above polyorganosiloxane (Ar / Si) can be appropriately controlled as the high refractive index polyorganosiloxane.

The term " aryl group " as used herein, unless otherwise specified, includes a benzene ring or a compound comprising a structure in which two or more benzene rings are connected to each other or are condensed or bonded while sharing one or two or more carbon atoms, or May refer to a monovalent residue derived from the derivative. In the present specification, an aryl group may mean a substituted or unsubstituted form with an alkyl group or a hydroxy 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, dichlorophenyl, chlorophenyl, phenylethyl, phenylpropyl, benzyl, tolyl, xylyl or naphthyl groups. have.

The polyorganosiloxane (A) may be, for example, a polyorganosiloxane having an average composition formula of the following formula (1).

 [Chemical Formula 1]

^{(R 4 R 5 R 6 SiO} 1/2) a (R 2 R 3 SiO 2/2) b (R 1 SiO 3/2) C (SiO 4/2) d

Wherein R ¹ to R ³ are each independently an alkoxy group, a hydroxy group, an epoxy group or a monovalent hydrocarbon group, R ⁴ To R ⁶ is a monovalent hydrocarbon group, each independently, R ¹ to R at least one of ^6, an aryl group, at least one of R ¹ to R ⁶ is an alkenyl group, a is 0 ≤ a ≤ 0.5, b is 0 <b? 0.8, c is 0 <c? 0.8, d is 0? D? 0.2, and a + b + c + d is 1.

The hydrocarbon group may be an alkyl group, an alkenyl group or an allyl group. Specifically, R ^{4 to} R ⁶ may be an alkyl group, an alkenyl group or an aryl group, and the respective substituents of R ¹ to R ⁶ may be the same or different from each other.

As used herein, the term &quot; polyorganosiloxane having a specific average composition formula &quot; means a mixture of two or more components as well as a polyorganosiloxane, which is a single component represented by the average composition formula thereof, But also a mixture of polyorganosiloxanes represented by a composition formula.

As used herein, &quot; alkoxy group &quot; may mean a monovalent moiety derived from a compound consisting of an alkyl group bonded with oxygen or a derivative of such a compound, unless otherwise specified. The alkoxy group may mean an alkoxy group having 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic and may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

As used herein, &quot; hydroxy group &quot; may mean a monovalent residue derived from a compound consisting of a bond of hydrogen and oxygen, unless otherwise specified.

As used herein, the term &quot; epoxy group &quot; may mean a monovalent moiety derived from a cyclic ether having three ring constituent atoms or a compound comprising such a cyclic ether, 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 &quot; monovalent hydrocarbon group &quot; 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.

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. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, Octyl, nonyl, decyl, and the like. Specifically, the alkyl group may mean methyl, and the alkyl group may be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, the term "alkenyl group" 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. The alkenyl group may be linear, branched or cyclic. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, an octenyl group or a decenyl group And so on. Specifically, the alkenyl group may mean a vinyl group or an allyl group, and the alkenyl group may be optionally 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.

Substituents which may be optionally substituted in the monovalent hydrocarbon group in this specification include halogen such as chlorine or fluorine; An epoxy group such as a glycidyl group, an epoxy alkyl group, a glycidoxyalkyl group or an alicyclic epoxy group; Acryloyl group; A methacryloyl group; Isocyanate group; A thiol group, a monovalent hydrocarbon group, and the like, but the present invention is not limited thereto.

As described above, the polyorganosiloxane (A) is a high-refractive-index polyorganosiloxane, whereby the molar ratio (Ar / Si) of the above-mentioned aryl groups can be appropriately controlled. When the polyorganosiloxane (A) is blended with the polyorganosiloxane (B) to be described later, the heat resistance of the cured product can be maintained to be excellent.

In addition, the compound of formula (I) may contain two or more alkenyl groups. 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 contained in the polyorganosiloxane of Formula (1) can be suitably controlled.

A, b, c and d represent molar ratios of the respective siloxane units, and when the sum is converted into 1, 0? A? 0.5, b is 0 < b? 0.8, and c is 0 < c? 0.8 and d is 0? D? 0.2.

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

The curable composition may include a polyorganosiloxane having two or more hydrogen atoms bonded to an aryl group and a silicon atom (hereinafter referred to as polyorganosiloxane (B)).

The molecular structure of the polyorganosiloxane (B) is not particularly limited, and any of those conventionally used as a crosslinking agent in the addition curing composition can be used.

In one example, the polyorganosiloxane (B) may be a polyorganosiloxane having an aryl group bonded to a silicon atom. In addition, the polyorganosiloxane (B) may be a solid or a liquid, and may have a linear structure, that is, a structure consisting of M and D units. In a linear structure, a hydrogen atom may be bonded to a silicon atom at the end of the linear structure. Such a polyorganosiloxane (B) may exhibit excellent reactivity with an aliphatic unsaturated bond contained in the polyorganosiloxane (A) and the like. Further, crack resistance of the cured product can be improved, and gas permeability can be maintained at a low level.

The polyorganosiloxane (B) may be a crosslinking agent that crosslinks the composition by reacting with aliphatic unsaturated bonds present in the polyorganosiloxane (A) or the like. For example, an aliphatic unsaturated bond such as an alkenyl group of the polyorganosiloxane (B) and an alkenyl group of the polyorganosiloxane (A) may be additionally reacted, and crosslinking and curing may proceed.

The hydrogen atom in the polyorganosiloxane (B) is preferably bonded to the silicon atom (Si) present at the end of the linear structure, and the hydrogen atom bonded to the silicon atom (Si) present in the repeating unit other than the terminal It may be appropriate to minimize the amount. The molar ratio (H / Si) of the hydrogen atom (H) to the silicon atom (Si) in the polyorganosiloxane (B) can be appropriately controlled in order to ensure appropriate reactivity.

In the polyorganosiloxane (B), for example, the molar ratio (Ar / Si) of the aryl group (Ar) bonded to the polyorganosiloxane (B) relative to the total silicon atoms (Si) can be suitably controlled.

The polyorganosiloxane (B) may be solid or liquid as described above.

The content of the polyorganosiloxane (B) in the present invention is included in the polyorganosiloxane (B) relative to the alkenyl group (Ak) contained in the total aliphatic unsaturated bond contained in the curable composition, for example, the polyorganosiloxane (A) (H / Ak) of the hydrogen atoms (H) bonded to the silicon atoms can be appropriately controlled.

As the polyorganosiloxane (B), various kinds of compounds can be used. For example, polyorganosiloxanes having an average composition formula selected from the group consisting of the following formulas (2) to (4) can be used.

(2)

_{^{(HR 11 R 10 SiO 1/}} 2) a (R 9 SiO 3/2) b (R 8 R 7 SiO 2/2) C

(A + b + c) of a, b and c is 1, a is 0.3 to 0.8, b is an integer of 1 to 3, and R is a monovalent hydrocarbon group and at least one of R is an aryl group. 0.2 to 0.7, and c is 0 to 0.5.

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 in the compound of Formula 2 may be, for example, about 0.2 to 1.0 or 0.3 to 1.0.

The ratio (Ar / Si) of the number of moles (Ar) of silicon atom-bonded aryl groups to the number of moles (Si) of the total silicon atoms may be, for example, about 0 to 0.8, 0.2 to 0.8 or 0 to 0.7.

(3)

In Formula 3, R is independently a monovalent hydrocarbon group, at least one of R is an aryl group, and n is a number of 1 to 10. In formula (2), n may be, for example, 1 to 8, 1 to 6, or 1 to 4.

[Chemical Formula 4]

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

In the formula (4), R is independently hydrogen, an epoxy group or a monovalent hydrocarbon group, r is a number of 5 to 100, and s may be a number of 0 to 100 or 5 to 100. In formula (4), the monovalent hydrocarbon group may be, for example, a monovalent hydrocarbon group other than an aryl group.

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 the compound of Formula 4 may be 0.2 to 1 or 0.3 to 1. The molar ratio (H / Si) can be controlled as described above to maintain excellent curability. The viscosity of the compound of Formula 4 at 25? May be 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. With the above viscosity, the processability of the composition and the hardness characteristics of the cured product can be kept excellent.

The ratio (Ar / Si) of the number of moles (Ar) of silicon atom-bonded aryl groups to the number of moles (Si) of the total silicon atoms of the compound of Formula 4 may be, for example, from 0 to 0.8 or from 0 to 0.7 have.

The curable composition according to the present invention may further contain, for example, a linear or partially crosslinked polyorganosiloxane (hereinafter referred to as a polyorganosiloxane (C)) as an aliphatic unsaturated bond-containing compound. The term &quot; linear polyorganosiloxane &quot; may refer to a polyorganosiloxane consisting of M units and D units, and the term &quot; partially crosslinked polyorganosiloxane &quot; means that the linear structure derived from the D unit is long enough, As a polyorganosiloxane in which Q units such as T units are partly introduced, for example, a ratio of D units (D / (D + T) to D units relative to all D, T and Q units contained in the polyorganosiloxane + Q) &lt; / RTI &gt; is greater than or equal to 0.7. The ratio (D / (D + T + Q)) may also be less than one.

The polyorganosiloxane (C) may be a low refractive polyorganosiloxane or a high refractive polyorganosiloxane, and it may be appropriate to use a low refractive polyorganosiloxane.

The polyorganosiloxane (C) may contain at least one aliphatic unsaturated bond, for example, an alkenyl group. For example, the polyorganosiloxane (C) has a molar ratio (Ak) of the functional group (Ak) including the aliphatic unsaturated bond to the total silicon atoms (Si) contained in the polyorganosiloxane (C), for example, / Si) is 0.001 to 0.3 or 0.001 to 0.2. By such control, the curability of the curable composition is maintained in an appropriate range, the unreacted components are prevented from leaking to the surface of the cured product after curing, and the excellent anti-creep property can be maintained

The polyorganosiloxane (C) may be a low refractive polyorganosiloxane or a high refractive polyorganosiloxane. For example, when a low refractive polyorganosiloxane is used as the polyorganosiloxane (C), the heat resistance and the like of the cured product can be kept excellent and compatibility with other components can be improved.

The polyorganosiloxane (C) may have an average composition formula of, for example, the following formula (5).

[Chemical Formula 5]

^{_{(R 3 14 SiO 1/2}} ) a (R 2 13 SiO 2/2) b (R 12 SiO 3/2) c (SiO 4/2) d

In formula (5), R ¹² to R ¹⁴ are each independently an epoxy group or a monovalent hydrocarbon group, and one or more of R ¹² to R ¹⁴ is an alkenyl group, and the sum (a + b + c + d) is 1, a is 0.001 to 0.2, b is 0.7 to 0.999, c is 0 to 0.3, and d may be 0 to 0.3. When the polyorganosiloxane (C) is a low refractive compound, the monovalent hydrocarbon group may be a monovalent hydrocarbon group other than an aryl group.

In the compound of formula (5), at least one of R ¹² to R ¹⁴ is an alkenyl group. For example, an alkenyl group may be present within a range satisfying the above-mentioned molar ratio (Ak / Si). For example, an alkenyl group may be present at the R ¹² position, although it is not particularly limited.

In the compound of formula (5), a, b, c and d represent molar ratios of respective siloxane units of the polyorganosiloxane (C). A is in the range of 0.001 to 0.2, b is in the range of 0.7 to 0.999, c is in the range of 0 to 0.3 or more than 0, and not more than 0.2, and d is 0, when the sum (a + b + c + d) To 0.3.

In the compound of formula (5), each siloxane unit may be present, for example, such that (c + d) / (a + b + c + d) ranges from 0 to 0.3. When the polyorganosiloxane (C) is partially crosslinked, b / (b + c + d) in formula (5) may be more than 0.7 and less than 1. In another example of the partially crosslinked form, b / (b + c + d) may be 0.7 to 0.97 or 0.65 to 0.97. By controlling the ratio of the siloxane unit in this manner, appropriate physical properties can be secured according to the application.

The polyorganosiloxane (C) may, for example, be contained in a ring-opening polymerization reaction of a mixture comprising a cyclic polyorganosiloxane. The reactant includes, for example, a cyclic compound having a weight average molecular weight (Mw) of 800 or less, 750 or less or 700 or less, for example, a cyclic polyorganosiloxane, the proportion being 7 wt% Or less or 3 wt% or less. The lower limit of the proportion of the cyclic compound may be, for example, 0% by weight or 1% by weight. It is possible to provide a cured product having excellent long-term reliability and crack resistance by controlling the ratio.

The polyorganosiloxane (C) or the reactant containing the same is preferably a polyorganosiloxane (C) or a reaction product containing the polyorganosiloxane (C), wherein the peak derived from the alkoxy group bonded to the silicon atom in the spectrum obtained by ¹ H NMR is an aliphatic unsaturated bond- May be 0.01 or less, 0.005 or less, or 0 based on the area of the peak derived from the same alkenyl group. Other properties may be maintained while exhibiting appropriate viscosity properties in the above range.

The polyorganosiloxane (C) or the reactant containing it may have an acid value of less than 0.02, less than 0.01, or 0, as determined by KOH titration. Other properties may be maintained while exhibiting appropriate viscosity properties in the above range.

The polyorganosiloxane (C) or reactants containing it may have a viscosity at 25 ° C of at least 500 cP, at least 1,000 cP, at least 2,000 cP, at least 5,000 cP. In this range, processability and hardness characteristics and the like can be appropriately maintained. For example, the viscosity is not more than 500,000 cP, not more than 400,000 cP, not more than 300,000 cP, not more than 200,000 cP, not more than 100,000 cP, not more than 80,000 cP, not more than 70,000 cP, or not more than 65,000 cP .

The polyorganosiloxane (C) or the reactants containing it may have a molecular weight of from 500 to 100,000 or from 1,500 to 50,000. Moldability, hardness and strength characteristics and the like can appropriately be maintained in this range.

The polymerization reactant comprising the polyorganosiloxane (C) may be, for example, a ring-opening polymerization reaction of a mixture comprising a cyclic polyorganosiloxane. When the polyorganosiloxane (C) is a partially crosslinked structure, the mixture may further include, for example, a polyorganosiloxane having a cage structure or a partial cage structure or containing T units. As the cyclic polyorganosiloxane compound, for example, a polyorganosiloxane having an average composition formula of the following formulas (6) to (8) can be used.

[Chemical Formula 6]

In the formula (6), R ^d and R ^e are each independently an epoxy group or a monovalent hydrocarbon group, and o may be 3 to 6.

(7)

[Chemical Formula 8]

In the general formulas (7) and (8), R ^f and R ^g are epoxy groups or alkyl groups, R ^h and R ⁱ are epoxy groups or monovalent hydrocarbon groups, p is a number of 3 to 6 and q is a number of 3 to 6.

The specific types of R ^d to R ⁱ , specific values of o, p and q, and the ratio of each component in the mixture in Formulas 6 to 8 can be determined by the structure of the desired polyorganosiloxane (C).

When the polyorganosiloxane (C) is a partially crosslinked structure, the mixture is a cage-structured polyorganosiloxane having, for example, a compound having an average composition formula of the following formula (9) or a partial cage structure As the polyorganosiloxane, a compound having an average composition formula of the following formula (10) may further be included.

[Chemical Formula 9]

[R ^j SiO _3/2]

[Chemical formula 10]

_{^{[R k R l 2 SiO 1}} /2] r [R m SiO 3/2] s

R ¹ , R ^k and R ^m are each independently an epoxy group or a monovalent hydrocarbon group, R ¹ is an epoxy group or an alkyl group having 1 to 4 carbon atoms, r is 1 to 3, s is 1 to 10 Lt; / RTI &gt;

In the general formulas (9) and (10), the specific kind of R ^j to R ^m , the specific values of r and s, and the ratio of each component in the mixture can be determined by the structure of the desired polyorganosiloxane (C).

When the cyclic polyorganosiloxane has a cage structure and / or a partial cage structure or is reacted with a polyorganosiloxane containing T units, the polyorganosiloxane having a desired partial crosslinking structure can be synthesized with a sufficient molecular weight. In addition, according to the above method, an object having excellent physical properties can be produced by minimizing a functional group such as an alkoxy group or a hydroxy group bonded to a silicon atom in a polyorganosiloxane or a polymerization reaction containing the same.

In one example, the mixture may further comprise a compound having an average composition formula of the formula (11).

(11)

(R ⁿ R ^o ₂ Si) ₂ O

In formula (11), R ⁿ and R ^o may be an epoxy group or a monovalent hydrocarbon group.

The specific kind of the monovalent hydrocarbon group in formula (11) or the blending ratio in the mixture may be determined according to the desired polyorganosiloxane (C).

The curable composition according to the present invention includes metal particles in addition to the above-mentioned polyorganosiloxanes (A) and (B). In the present invention, it is possible to improve the rigidity of the optical semiconductor element die bond agent by mixing metal particles with the curable composition, and to minimize the decrease in viscosity during the curing process. Further, the metal particles can improve the heat dissipation property, crack resistance, and the like.

In one example, the kind of the metal particles is not particularly limited, and metal oxide particles can be used. As the metal oxide particles, at least one selected from the group consisting of silica, alumina, aluminosilicate, aluminum nitride, zinc oxide, zirconium oxide and titanium oxide can be used. Specifically, alumina or aluminum nitride Ride can be used.

In the present invention, since the polyorganosiloxane (A) has high refractive index, the transparency of the die-bonding agent is lowered due to the refractive index difference of the silicon particles, and the brightness of the device may be lowered. Therefore, it is preferable that the metal particles have a small difference in refractive index from the silicon particles, specifically, less than 0.5, less than 0.2, and less than 0.1.

In one example, the metal particles may be surface treated metal particles to improve compatibility with the curable composition. The surface treatment of the metal particles is carried out using a surface treatment agent. The type of the surface treatment agent is not particularly limited, and an organosilicon compound can be used from the viewpoint of heat resistance.

The surface treatment method of the metal particles is not particularly limited, and a known method in this field can be used. For example, a wet process may be used in which the metal particles and the surface treatment agent are put in a solvent and stirred at 10 to 100 ° C for a certain period of time to react.

In one example, the size of the metal particles is not particularly limited, and may be, for example, 1 to 100 nm or 1 to 50 nm. If the average particle diameter is less than 1 nm, problems such as agglomeration of the metal particles may occur, and the plasticity may increase sharply and it may be difficult to disperse the metal particles uniformly in the die bonding material. On the other hand, if it is 100 nm or more, it is difficult to disperse and precipitate.

The metal particles of the present invention may be contained in an amount of 1 to 30 parts by weight or in an amount of 2 to 30 parts by weight based on 100 parts by weight of the curable composition. When the content of the metal particles is less than 1 part by weight, the improvement in the ruggedness and the reliability of the device is not significant. If the content is more than 30 parts by weight, problems may arise from the viewpoint of processability. Unless specifically stated otherwise herein, unit weight refers to the ratio of weight between components.

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

Examples of the catalyst that can be included in the mixture include a base catalyst. 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.

In one example, the reaction of the mixture can be carried out in the absence of solvent or 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, can be carried out, for example, by adding a catalyst and performing, for example, To 150? Or 30? RTI ID = 0.0 &gt; 130 C. &lt; / RTI &gt; In addition, the reaction time can be adjusted within a range of, for example, 1 hour to 3 days.

The curable composition may further comprise a hydrosilylation catalyst. The hydrosilylation catalyst may be used to promote the hydrogen silylation reaction. As the hydrosilylation catalyst, any of ordinary components known in this field 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 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 adhesive property-imparting agent include at least one selected from the group consisting of an alkenyl group such as a vinyl group, a (meth) acryloyloxy group, a hydrosilyl group (SiH group), an epoxy group, an alkoxy group, an alkoxysilyl group, a carbonyl group, 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 may contain, if desired, 2-methyl-3-butyne-2-ol, 2-phenyl- 3-hexene-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; 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.

In the present invention, the light transmittance at 450 nm of the specimen prepared by curing the above-mentioned curable composition to 1 mm thickness may be 80% or more, 85% or more, 90% or more, or 95% or more.

The present invention also relates to semiconductor devices, for example, optical semiconductor devices. An exemplary semiconductor element may be one in which the light emitting element is bonded by a die bonding agent including a cured body of the curable composition. Examples of such a semiconductor device 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 of laminating the semiconductor material on the substrate is not particularly limited, and for example, MOCVD, HDVPE, or liquid 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.

In the light emitting diode, the light emitting element can be bonded to the substrate by the above composition.

When curing of the composition is required, the curing method is not particularly limited. Or 200 ° C for 10 minutes to 5 hours, or may be subjected to a stepwise curing process through two or more steps at an appropriate temperature and time.

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.

The curable composition according to the present invention is excellent in processability and reliability, and is excellent in luminance and heat radiation characteristics of an optical device. The curable composition can be effectively used for die bond applications.

Hereinafter, the production method of the polarizing plate will be described in detail through examples and comparative examples, but the scope of the production method of the polarizing plate is not limited by the following examples.

Herein, Vi, Ph, Me and Ep in the present embodiment represent a vinyl group, a phenyl group, a methyl group and a 3-glycidoxypropyl group, respectively.

One. Light transmittance  Measure

The curable composition was coated on the organic substrate, held at 60 ° C for 30 minutes, and then held at 150 ° C for 1 hour to cure the plate to prepare a 1 mm thick plate-like specimen. The transmittance was measured at 450 nm using a UV-VIS spectrometer Respectively.

2. Dispersion Stability of Phosphor

The curable composition was placed in a 10 ml vial and allowed to stand at room temperature for 8 hours. The sedimentation state of the phosphor was visually observed to evaluate the dispersion stability of the phosphor as follows.

X: The phosphor is not uniformly dispersed but precipitated downward

O: The phosphor is kept dispersed evenly.

3. Evaluation of luminance characteristics of device

The device luminance characteristics were evaluated using a 6030 LED package made of polyphthalamide (PPA). Specifically, a curable composition containing a phosphor was dispersed in a polyphthalamide (PPA) cup and kept at 60 DEG C for 360 minutes, then held at 150 DEG C for 1 hour to cure the surface mount LED Respectively. Then, the luminance of the optical device was measured while flowing a current of 20 mA.

Example  One.

(Compound A: 80 g, Compound B: 20 g, Compound C: 200 g, Compound D: 70 g) prepared by mixing the compounds represented by the following Formulas A, B, C and D, ), 35 g of a catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) and 13 nm of alumina particles in an amount such that the content of Pt (0) To prepare a curable composition.

(A)

_{(ViMe 2 SiO 1/2)} 2 (ViMeSiO 2/2) 2 (PhMeSiO 2/2) 40

[Chemical Formula B]

_{(ViMe 2 SiO 1/2)} 2 (EpSiO 3/2) 3 (MePhSiO 2/2) 20

&Lt; RTI ID = 0.0 &

_{(ViMe 2 SiO 1/2)} 2 (Ph 2 SiO 2/2) 0.5 (PhSiO 3/2) 6

[Chemical Formula D]

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

Example  2.

(Compound E: 80 g, Compound F: 20 g, Compound G: 200 g, and Compound H: 70 g) were prepared by mixing the compounds of Formulas A, B and D and the compound of Formula E, (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) and 35 g of alumina particles of 13 nm in an amount such that the content of Pt (0) was 10 ppm.

30 g of alumina particles of 13 mm and 10 g of silica particles of 10 nm were further blended into the blended mixture to prepare a curable composition.

(E)

_{(ViMe 2 SiO 1/2)} 2 (CH 3 PhSiO 2/2) 0.5 (PhSiO 3/2) 6

Comparative Example  One.

A modified silicone die-bonding agent (Sanyo Lec DT-2058) was used as the curable composition.

Comparative Example  2.

(Compound A: 80 g, Compound B: 20 g, Compound C: 200 g, and Compound D: 70 g) obtained by mixing the compounds represented by Formulas A, B, C and D in Example 1 with a curing composition Respectively.

Comparative Example  3.

(Compounding amount: 185 g, compound J: 10 g, compound K: 135 g, compound L (compound I), and compound (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in an amount such that the content of Pt (0) was 10 ppm and 10 nm of silica fine particles 30 g.

To the blended mixture, 25 g of alumina particles of 13 mm and 10 g of silica particles of 10 nm were further blended to prepare a curable composition.

[Chemical Formula F]

_{(ViMe 2 SiO 1/2)} 5 (Me 3 SiO 1/2) 15 (Me 2 SiO 2/2) 2 (SiO 4/2) 20

[Formula G]

_{(ViMe 2 SiO 1/2)} 4 (Me 3 SiO 3/2) 6 (EpSiO 2/2) 2 (SiO 2/2) 4

[Formula H] &lt;

_{(ViMe 2 SiO 1/2)} 2 (CH 3 PhSiO 2/2) 0.5 (PhSiO 3/2) 6

(I)

_{(Me 3 SiO 1/2)} 2 (HMeSiO 2/2) 100

The curability of the curable compositions prepared in the above Examples and Comparative Examples is summarized in Tables 1 and 2 listed below.

Example 1 Comparative Example 1 Example 2 Comparative Example 2 Light transmittance 90% 79% Luminance 86 lm 80 lm

Example 2 Comparative Example 1 Comparative Example 2 Dispersion stability O X X

As can be seen from Tables 1 and 2, the cured composition of the embodiment of the present invention is excellent in the stability of the phosphor and the light transmittance of the cured product, and can improve the luminance characteristics of the manufactured phosphor.

Claims (12)

(A) a polyorganosiloxane having an aryl group and two or more aliphatic unsaturated bonds;
(B) a polyorganosiloxane having two or more hydrogen atoms bonded to an aryl group and a silicon atom; And
A curable composition comprising metal particles. The curable composition according to claim 1, wherein the polyorganosiloxane (a) has an average composition formula of the following formula (1):
[Chemical Formula 1]
^{(R 4 R 5 R 6 SiO} 1/2) a (R 2 R 3 SiO 2/2) b (R 1 SiO 3/2) C (SiO 4/2) d
Wherein R ¹ to R ³ are each independently an alkoxy group, a hydroxy group, an epoxy group or a monovalent hydrocarbon group, R ⁴ To R ⁶ are each independently a monovalent hydrocarbon group, R ¹ to R at least one of ^6, an aryl group, R ¹ to R ^6, at least one is an alkenyl group, a + b + c + d is 1. The curable composition of claim 1, wherein the polyorganosiloxane (B) is a compound of formula (2):
(2)
_{^{(HR 11 R 10 SiO 1/}} 2) a (R 9 SiO 3/2) b (R 8 R 7 SiO 2/2) C
Wherein R ⁷ to R ¹¹ are each independently a monovalent hydrocarbon group, at least one of R ⁷ to R ¹¹ is an aryl group, and a + b + c is 1. The curable composition of claim 1, wherein the metal particles are metal oxide particles. The curable composition according to claim 1, wherein the average particle diameter of the metal particles is 1 to 100 nm. The curable composition according to claim 1, wherein the content of the metal particles is 1 to 20 parts by weight based on 100 parts by weight of the curable composition. The curable composition of claim 1, further comprising a curing catalyst. The curable composition according to claim 1, wherein the cured composition has a light transmittance at 450 nm of not less than 80%. A semiconductor device comprising a light-emitting element bonded with a die bond agent comprising the curable composition according to claim 1. A photo-semiconductor device comprising a light-emitting element bonded with a die bond material comprising the curable composition according to claim 1. 11. A liquid crystal display device comprising the optical semiconductor element of claim 10. 11. A lighting comprising the optical semiconductor element of claim 10.