KR101591185B1 - Curable composition - Google Patents

Abstract

The present application relates to curable compositions and uses thereof. An exemplary curable composition can provide a cured product that is excellent in workability, workability, adhesiveness, etc. and does not cause cloudiness or stickiness on the surface. The curable composition can also provide a cured product having excellent transparency, moisture resistance, mechanical properties and crack resistance, and thus can be applied to various electronic components, for example, to exhibit excellent long-term reliability.

Description

{CURABLE COMPOSITION}

The present application relates to curable compositions and uses thereof.

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

As an LED encapsulant, epoxy resin having high adhesiveness and excellent durability is widely used. However, the epoxy resin has a low transmittance to light in the range of blue to ultraviolet rays, and has a problem in that heat resistance and light resistance are inferior. Accordingly, for example, Patent Documents 1 to 3 propose a technique for improving the above problems. However, the encapsulant disclosed in the above document has insufficient heat resistance and light resistance.

A silicone resin is known as a material having excellent light resistance and high temperature heat resistance in a low wavelength region.

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 curable compositions and uses thereof.

Exemplary curable compositions may include components that enable them to be cured by hydrosilylation, for example, by reaction of aliphatic unsaturated bonds with hydrogen atoms. For example, the curable composition may comprise a polyorganosiloxane comprising an aliphatic unsaturated bond.

The term "M unit" in the present specification, expressions in the industry (R ₃ SiO _1/2) means the so-called monofunctional siloxane units in the case represented by and, the term "D unit" is expression in the industry (R ₂ SiO _{2 / 2)} so-called transfer means a functional siloxane units in the case represented by and, the term "T unit" means "means a so-called trifunctional siloxane unit in the case of the formula (RSiO _3/2) in the industry, and the term Q unit "may refer to so-called Tetrafunctional siloxane units in the case of the formula ₍₄ SiO _{/ 2).} The R is a functional group bonded to silicon (Si), and may be, for example, a hydrogen atom, an epoxy group or a monovalent hydrocarbon group.

As the polyorganosiloxane containing an aliphatic unsaturated bond, for example, a linear or partially crosslinked polyorganosiloxane (hereinafter referred to as polyorganosiloxane (A)) may be used. The term "linear structure" may mean a structure of a polyorganosiloxane composed of M units and D units, and the term "partially crosslinked structure" means a structure having a sufficiently long linear structure derived from a D unit and a T or Q unit, For example, it may mean the structure of a polyorganosiloxane in which T units are partially introduced. In one example, the polyorganosiloxane of the partially crosslinked structure is a polyorganosiloxane having a ratio of D units (D / (D + T + Q)) relative to the total D, T and Q units contained in the polyorganosiloxane of 0.7 or more It can mean.

The polyorganosiloxane (A) may contain at least one functional group containing an aliphatic unsaturated bond, for example, an alkenyl group. For example, the polyorganosiloxane (A) has a molar ratio of the functional group (Ak) containing the aliphatic unsaturated bond to all the silicon atoms (Si) contained in the polyorganosiloxane (A), for example, an alkenyl group Ak / Si) is 0.001 to 0.3 or 0.002 to 0.25, based on the total amount of the aliphatic unsaturated bond. By controlling the molar ratio (Ak / Si) to 0.001 or 0.002 or more, it is possible to maintain the reactivity appropriately and prevent the unreacted component from leaking to the surface of the cured product. Further, by adjusting the molar ratio (Ak / Si) to 0.3 or 0.25 or less, the crack resistance of the cured product can be kept excellent.

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

[Chemical Formula 1]

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

In formula (1), R ¹ to R ³ are each independently an epoxy group or a monovalent hydrocarbon group, and one or more of R ¹ to R ³ is an alkenyl group, and the sum (a + b + c + d) is 1, a is 0.00005 to 0.3, b is 0.7 to 0.9995, c is 0 to 0.2, and d is 0 to 0.2.

The expression of the polyorganosiloxane in the present specification as a specific average compositional formula means that when the polyorganosiloxane is a single component represented by the average composition formula thereof, it is a mixture of two or more components and averages the composition of the components in the mixture , And the case where the average composition formula is shown.

The term " epoxy group ", unless otherwise specified, may mean a monovalent moiety derived from a cyclic ether having three ring constituting atoms or a compound comprising such a cyclic ether. 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.

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

The term "alkyl group", unless otherwise specified, 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. 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", unless otherwise specified, 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 and may optionally be substituted with one or more substituents.

The term "alkynyl group", unless otherwise specified, 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. The alkynyl group may be linear, branched or cyclic and may optionally be substituted with one or more substituents.

The term "aryl group", unless otherwise specified, may mean a monovalent residue derived from a compound or derivative containing 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 a phenyl group, dichlorophenyl, chlorophenyl, phenylethyl, phenylpropyl, benzyl, tolyl, xylyl group or naphthyl group.

Examples of the substituent which may optionally be substituted with an epoxy group or monovalent hydrocarbon group include halogen such as chlorine or fluorine, epoxy group such as glycidyl group, epoxy alkyl group, glycidoxyalkyl group or alicyclic epoxy group, acryloyl group, methacryloyl group An isocyanate group, a thiol group, or a monovalent hydrocarbon group, but the present invention is not limited thereto.

In formula (1), at least one of R ¹ to R ³ is an alkenyl group, and 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 position of R < ³ > although not particularly limited.

A, b, c and d represent molar ratios of the respective siloxane units of the polyorganosiloxane (A). A is in the range of 0.00005 to 0.3, b is in the range of 0.7 to 0.9995, c is in the range of 0 to 0.2 or more than 0 and not more than 0.2, and d is 0 to 0.2.

Each siloxane unit in formula (1) may be present, for example, such that (c + d) / (a + b + c + d) is from 0 to 0.2. Further, when the polyorganosiloxane (A) is a partially crosslinked type, b / (b + c + d) may be more than 0.7 and less than 1. If it is a partially crosslinked structure, 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.

In the curable composition, the polyorganosiloxane (A) may be included in the ring-opening polymerization reaction of a mixture containing, for example, 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 resistance to cracking by controlling the ratio. The term " weight average molecular weight " may refer to a conversion value for standard polystyrene measured by Gel Permeation Chromatograph (GPC). Unless otherwise specified, the term " molecular weight " can mean weight average molecular weight.

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

The polyorganosiloxane (A) 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 (A) or the polymerization reaction product containing it may have a viscosity of at least 5 cp, at least 50 cp, at least 500 cP, at least 1,000 cP at 25 ° C. 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 (A) or the polymerization reactant containing it may have a molecular weight of 500 to 50,000 or 1,500 to 30,000. Moldability, hardness and strength characteristics and the like can appropriately be maintained in this range.

The polymerization reactant comprising the polyorganosiloxane (A) may be, for example, a ring-opening polymerization reaction of a mixture comprising a cyclic polyorganosiloxane. When the polyorganosiloxane (A) 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 compound represented by the following formula (3) can be used.

(3)

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

The cyclic polyorganosiloxane may also include a compound of the following formula (4) and a compound of the following formula (5).

[Chemical Formula 4]

[Chemical Formula 5]

In the formulas (4) and (5), 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.

In the formulas (3) to (5), the specific types of R ^f to R ⁱ , the specific values of o, p and q, and the ratio of each component in the mixture can be determined by the structure of the desired polyorganosiloxane (A) .

When the polyorganosiloxane (A) 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 (6) or a partial cage structure, As the polyorganosiloxane, a compound having an average composition formula of the following formula (7).

[Chemical Formula 6]

[R ^j SiO _3/2]

(7)

^{_{[R k R l 2 SiO 1}} /2] p [R m SiO 3/2] q

Wherein 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, p is 1 to 3, q is an integer of 1 to 10, to be.

In the formulas (6) and (7), the specific kind of R ^j to R ^m , the specific values of p and q, and the ratio of each component in the mixture can be determined by the structure of the desired polyorganosiloxane (A).

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 represented by the following formula (8).

[Chemical Formula 8]

(R ⁿ R ^o ₂ Si) ₂ O

In the general formula (8), R ⁿ and R ^o are an epoxy group or a monovalent hydrocarbon group.

The specific kind of the monovalent hydrocarbon group in formula (8) or the blending ratio in the mixture may be determined according to the desired polyorganosiloxane (A).

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.

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. 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 absence of a 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 reaction, can be carried out, for example, by adding and carrying out 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 curable composition may further include a crosslinkable polyorganosiloxane (hereinafter, referred to as polyorganosiloxane (B)). The term " cross-linked polyorganosiloxane " may refer to a polyorganosiloxane essentially comprising T or Q units. For example, the crosslinking polyorganosiloxane may essentially comprise a Q unit.

The crosslinkable polyorganosiloxane may have an average composition formula of, for example, the following formula (2).

(2)

^{_{(R 4 SiO 1/2)}} e (R 5 SiO 2/2) f (R 6 SiO 3/2) g (SiO 4/2) h (OR) x

Wherein R ⁴ to R ⁶ are each independently an epoxy group or a monovalent hydrocarbon group, at least one of R ⁴ to R ⁶ is an alkenyl group, R is hydrogen or a monovalent hydrocarbon group, e, f, g and h is from 0 to 0.3, h is from 0.2 to 0.8, x is 0 or a positive (= 0) H / (g + h) is 0.7 or more, and x / (g + h) is 0.2 or less or 0.15 or less.

In formula (2), at least one of R ⁴ to R ⁶ may be an alkenyl group. In one example, the alkenyl group has a ratio (Ak / R) of the molar number (Ak) of the alkenyl group to the molar number (R) of the functional group bonded to the total silicon atoms (Si) included in the polyorganosiloxane (B) 0.01 to 0.7 or 0.01 to 0.5. By adjusting the molar ratio (Ak / R) to 0.01 or more, it is possible to maintain the reactivity appropriately and prevent the unreacted component from leaking out to the surface of the cured product. Further, by controlling the molar ratio (Ak / R) to 0.7 or less or 0.5 or less, the hardness, crack resistance and thermal shock resistance of the cured product can be kept excellent.

E, f, g and h represent molar ratios of the respective siloxane units. When the sum is converted into 1, e is 0.2 to 0.8, f is 0 to 0.3, g is 0 to 0.3 And h is 0.2 to 0.8. (E + f) / (e + f + g + h) can be adjusted to be 0.2 to 0.7 in order to maximize the strength, crack resistance and thermal shock resistance of the cured product. In the formula (2), h (h + g) can be adjusted to be 0.7 or more. The upper limit of h / (h + g) is not particularly limited, and may be, for example, 1.0

In Formula (2), x represents the amount of a condensing functional group, for example, a hydroxyl group or an alkoxy group contained in the polyorganosiloxane. In formula (2), x is 0 or a positive number. For example, the number of moles (Si) of the total silicon atoms belonging to the T unit and the Q unit of the polyorganosiloxane (B) (OR / Si = x / (h + g)) of the number of moles (OR) of the all-axis synthetic functional groups is 0.2 or less, 0.15 or less or 0.12 or less. The peaks T2 and Q3 derived from a condensing functional group such as a hydroxyl group or an alkoxy group in the above-mentioned spectrum, relative to the area (A) of the peak derived from the silicon atom of T3 and Q4 units in the Si NMR spectrum of the polyorganosiloxane (B) The ratio of the Q2 area (B) (100 x B / A) may be 20% or less or 15% or less. Through this, it is possible to maintain the compatibility of each component of the curable composition, to form a cured product having excellent transparency after curing, and to maintain excellent moisture resistance of the cured product, and the cured product is, for example, When applied to an element or the like, long-term reliability of the element can be secured.

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.

Further, the polyorganosiloxane (B) may have a molecular weight of 800 to 20,000 or 800 to 10,000, for example. By controlling the molecular weight to 800 or more, the moldability before curing and the strength after curing can be effectively maintained, and the viscosity and the like can be maintained at an appropriate level by controlling the molecular weight to 20,000 or 10,000 or less.

The polyorganosiloxane (B) containing the condensing functional group in the above ratio can be obtained, for example, by carrying out a hydrolysis and condensation reaction under appropriate conditions under acid catalyst and / or by performing an additional condensation reaction after synthesis of the polyorganosiloxane (B) . ≪ / RTI >

The polyorganosiloxane (B) is, for example, 30 parts by weight to 1000 parts by weight, 30 parts by weight to 900 parts by weight, 30 parts by weight to 800 parts by weight, 30 parts by weight to 700 parts by weight, 30 parts by weight to 600 parts by weight, 30 parts by weight to 500 parts by weight, 30 parts by weight to 400 parts by weight, 30 parts by weight to 300 parts by weight, 30 parts by weight to 200 parts by weight, 30 parts by weight to 100 parts by weight , 30 parts by weight to 90 parts by weight, 30 parts by weight to 80 parts by weight or 30 parts by weight to 70 parts by weight or 30 parts by weight to 60 parts by weight. Unless otherwise specified, the unit weight portion in the present specification means the weight ratio between the respective components. When the proportion of the polyorganosiloxane (B) is 30 parts by weight or more, sufficient mechanical properties can be ensured after curing, and 100 parts by weight or less of the polyorganosiloxane (B) can maintain excellent crack resistance and the like.

The curable composition may further include a silicon compound (silicon compound (C)) containing a hydrogen atom bonded to a silicon atom. The silicon compound (C) may have one or more hydrogen atoms or two or more hydrogen atoms.

The silicon compound (C) can act as a crosslinking agent for crosslinking the composition by reacting with an aliphatic unsaturated bond-containing functional group. For example, the hydrogen atom of the silicon compound (C) and the alkenyl group of the polyorganosiloxane (A) or the polyorganosiloxane (B) may undergo addition reaction to proceed crosslinking and curing.

As the silicon compound (C), various kinds may be used as far as they contain hydrogen atoms (Si-H) bonded to silicon atoms in the molecule. The silicon compound (C) may be, for example, a linear, branched, cyclic or crosslinked polyorganosiloxane. The silicon compound (C) may be a compound having 2 to 1000 silicon atoms, preferably 3 to 300 silicon atoms.

As the silicon compound (C), for example, a compound represented by the following formula (9) can be used.

[Chemical Formula 9]

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

R in the formula (9) is independently hydrogen, an epoxy group or a monovalent hydrocarbon group, r is a number in the range of 0 to 100, and s is a number in the range of 0 to 100. However, r and s are not 0 at the same time.

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

The 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. With such a viscosity, the workability of the composition and the hardness characteristics of the cured product can be kept excellent.

The silicon compound (C) may have a molecular weight of, for example, less than 2,000, less than 1,000 or less than 800. If the molecular weight is 1,000 or more, the strength of the cured product may be lowered. The lower limit of the molecular weight is not particularly limited, and may be 250, for example. In the case of the compound (C), the molecular weight may be a weight average molecular weight or may mean a conventional molecular weight of a compound.

The method for producing the compound (C) is not particularly limited, and for example, it can be prepared by applying a conventionally known method to the production of a polyorganosiloxane, or by applying a method similar to the polyorganosiloxane (A) .

The content of the silicon compound (C) is not particularly limited so long as the content of the aliphatic unsaturated bond-containing functional group contained in the curable composition, for example, the functional group containing a lipophilic unsaturated bond such as an alkenyl group contained in the polyorganosiloxane (A) and / (H / Ak) of the hydrogen atoms (H) bonded to the silicon atoms contained in the compound (C) to the total amount of the organopolysiloxane (A-Ak) is from 0.5 to 3.0 or from 0.7 to 2. By blending at such a molar ratio (H / Ak), excellent workability and workability are exhibited before curing, and the cured product exhibits excellent crack resistance, hardness characteristics, thermal shock resistance and adhesiveness and exhibits opacity and surface stickiness in harsh conditions Lt; RTI ID = 0.0 >

The curable composition may further contain a functional group having an aliphatic unsaturated bond, for example, a polyorganosiloxane (hereinafter referred to as a polyorganosiloxane (D)) containing an alkenyl group and an epoxy group.

The polyorganosiloxane (D) can be used, for example, as an adhesion-imparting agent for improving the adhesion.

As one example, the polyorganosiloxane (D) can be represented by an average composition formula of the following formula (10).

[Chemical formula 10]

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

In formula (14), R ¹⁴ is each independently an epoxy group or a monovalent hydrocarbon group, at least one of R ¹⁴ is an alkenyl group, at least one of R ¹⁴ is an epoxy group, and (a + b + c + d) B is 0 to 0.5, c is 0 to 0.8, and d is 0 to 0.2, wherein (c + d) / (a + b + c + d) is 0.2 to 0.7 , and c / (d + d) is 0.8 or more.

At least one or two or more of R < ¹⁴ > in formula (10) may be an alkenyl group. In one example, the alkenyl group is an alkenyl group in an amount such that the molar ratio (Ak / Si) of the alkenyl group (Ak) to the total silicon atoms (Si) contained in the polyorganosiloxane (D) is 0.05 to 0.35 or 0.05 to 0.3 Can exist. It is possible to provide a cured product which exhibits excellent reactivity with other compounds at such a molar ratio (Ak / Si), forms covalent bonds with the silicone resin after curing, exhibits excellent bonding strength, and has excellent physical properties such as impact resistance.

At least one of R < ¹⁴ > in formula (10) may also be an epoxy group. As a result, the strength and scratch resistance of the cured product can be appropriately maintained, and excellent adhesiveness can be exhibited. The epoxy group may be present in such an amount that the molar ratio (Ep / Si) of the epoxy group (Ep) to the total silicon atoms (Si) contained in the polyorganosiloxane (D) is 0.1 or more or 0.2 or more. In such a molar ratio (Ep / Si), the cross-linking structure of the cured product can be appropriately maintained, and properties such as heat resistance and adhesiveness can be kept excellent. The upper limit of the mole ratio (Ep / Si) is not particularly limited, and may be, for example, 1.0.

A, b, c and d are molar ratios of the respective siloxane units, a is 0 to 0.7, b is 0 to 0.5, and c is 0 to 0.8 And d may be from 0 to 0.2. In the above, c and d may not be 0 at the same time. (C + d) / (a + b + c + d) is 0.3 to 0.7, and c / c + d) can be adjusted to a range of 0.8 or more. The upper limit of c / (c + d) is not particularly limited, and may be 1.0, for example.

The polyorganosiloxane (D) may have a viscosity of 100 cP or more, or 100000 cP or more at 25 占 폚, so that the workability before curing and the hardness characteristics after curing can be appropriately maintained.

The polyorganosiloxane (D) may have a molecular weight of, for example, 1,000 or more or 1,500 or more. By controlling the molecular weight to 1,000 or 1,500 or more, it is possible to provide a cured product having excellent workability and workability before curing and excellent in crack resistance, thermal shock resistance and adhesive property to a substrate. The upper limit of the molecular weight is not particularly limited, and may be, for example, 20,000.

The polyorganosiloxane (D) can be applied, for example, to a commonly known process for producing a polyorganosiloxane, or to a process similar to the production of the polyorganosiloxane (A).

The polyorganosiloxane (D) can be obtained, for example, by adding the other components contained in the curable composition such as the polyorganosiloxane (A), the polyorganosiloxane (B) and / or the silicon compound (C) May be included in the composition in a proportion of 0.2 to 10 parts by weight, or 0.5 to 5 parts by weight, based on the weight of the composition. Adhesion and transparency can be kept excellent within such a range.

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 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. Usually, it may be used in an amount of 0.1 ppm to 200 ppm, preferably 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, either alone or in combination with the polyorganosiloxane (D), from the viewpoint of further improvement in adhesiveness to various substrates. The adhesive property-imparting agent can improve the self-adhesiveness to metal and organic resin as a component capable of improving the self-adhesiveness of the composition or the cured product.

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

When the adhesive property-imparting agent is included in the composition, 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; filler; A phosphor; Silver, a metal powder such as copper or aluminum, or a conductivity imparting agent such as various carbon materials; A coloring agent such as a pigment or a dye, and the like.

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

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

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

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

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

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

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

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

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

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

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

An exemplary curable composition can provide a cured product that is excellent in workability, workability, adhesiveness, etc. and does not cause cloudiness or stickiness on the surface. The curable composition can also provide a cured product having excellent transparency, moisture resistance, mechanical properties and crack resistance, and thus can be applied to various electronic components, for example, to exhibit excellent long-term reliability.

Hereinafter, the curable composition will be described in more detail by way of examples and comparative examples, but the scope of the curable composition is not limited by the following examples. In the following, OR represents an alkoxy group, the symbol Vi represents a vinyl group, the symbol Me represents a methyl group, and the symbol Ep represents a 3-glycidoxypropyl group.

One. NMR  analysis

The amount of alkoxy group (OR) in the polyorganosiloxane was evaluated by NMR analysis. Specifically, the amount of the alkoxy group (OR) is calculated from the ratio of the T unit of the polyorganosiloxane and the integral value of the peak derived from the silicon atom of the Q unit through ²⁹ Si NMR (Bruker 300 MHz SSNMR / 4 mm MAS probe) Respectively.

2. Light transmittance  Measure

The light transmittances of the curable materials of Examples and Comparative Examples were evaluated in the following manner. The curable composition is injected between two sheets of glass at intervals of about 1 mm and held at 150 占 폚 for 1 hour to cure, thereby preparing a plate-like specimen having a thickness of 1 mm. Thereafter, the light transmittance in the thickness direction of the specimen was measured at a wavelength of 450 nm using a UV-VIS spectrometer at room temperature, and evaluated according to the following criteria

≪ Light transmittance evaluation standard &

A: When the light transmittance is 98% or more

B: When the light transmittance is 95% or more and less than 98%

C: When the light transmittance is less than 95%

3. Evaluation of device characteristics

The device characteristics are evaluated using a 7030 LED package made of polyphthalamide (PPA). Specifically, the curable composition is dispensed in a polyphthalamide cup, maintained at 70 占 폚 for 30 minutes, and then held at 150 占 폚 for 4 hours to cure the surface-mounted LED. Thereafter, the test is carried out according to the following method.

(One) Thermal shock  Test

The LED was maintained at -40 占 폚 for 30 minutes and then maintained at 85 占 폚 for 30 minutes. The LED was repeated 200 times, that is, 200 times, and maintained at room temperature. The peeled state was examined to evaluate the thermal shock resistance do. At the time of evaluation, 20 LEDs made from the same curable composition were subjected to the same tests as above, and the number of peeled LEDs is shown in Table 1 (number of peeled LEDs / number of total LEDs (20)).

(2) Long-term reliability test

The LED is operated for 500 hours while maintaining a current of 85 mA and a relative humidity of 85% and a current of 30 mA. Next, the luminance reduction rate after the operation relative to the initial luminance is measured and evaluated as the following criteria.

<Evaluation Criteria>

A: When the luminance reduction ratio with respect to the initial luminance is 8% or less

B: When the luminance reduction ratio with respect to the initial luminance is 10% or less

C: When the reduction rate of the luminance relative to the initial luminance exceeds 10%

4. Evaluation of surface stickiness

The curable compositions of the examples and comparative examples were poured into a mold and held at 150 DEG C for about 1 hour to cure, and then the surface was hand-contacted to evaluate the surface stickiness characteristics according to the following criteria.

<Evaluation Criteria>

A: I do not feel sticky on the surface

B: I feel sticky on the surface.

Manufacturing example  One: Of the polyorganosiloxane (B)  Produce

The crosslinked polyorganosiloxane having an alkenyl group (except for the component having an epoxy group) used in Examples and Comparative Examples was prepared by reacting monomers such as divinyltetramethyldisiloxane and tetramethoxysilane with methanesulfonic acid, water and isopropyl alcohol , KOH was added to the reaction mixture to concentrate the reaction mixture to 90 wt%, and the resulting mixture was subjected to a Dean-Stark reaction at 70 ° C for 10 hours, followed by neutralization and washing to adjust the proportion of condensation functional groups .

Example  One.

(C): 110 g of the compound of the formula (A), 60 g of the compound of the formula (B), 10 g of the compound of the formula (C), and the mixture of the compounds of the formulas A to D were mixed to prepare a curable composition which can be cured by the hydrosilylation reaction. (D): 4 g. Then, a catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was added in an amount such that the content of Pt (0) , And uniformly mixed to prepare a curable composition.

(A)

_{(ViMe 2 SiO 1/2)} 2 (Me 2 SiO 2/2) 800

[Chemical Formula B]

_{(ViMe 2 SiO 1/2)} (Me 3 SiO 1/2) 4 (SiO 4/2) 10 (OR) 1.4

&Lt; RTI ID = 0.0 &

_{(Me 3 SiO 1/2)} 2 (HMeSiO 2/2) 30

[Chemical Formula D]

_{(ViMe 2 SiO 1/2)} 2 (EpSiO 3/2) 2 (Me 2 SiO 2/2) 10

Example  2.

Compound of Formula B A curable composition was prepared in the same manner as in Example 1 except that the compound of Formula E was used.

(E)

_{(ViMe 2 SiO 1/2)} (Me 3 SiO 1/2) 4 (SiO 4/2) 10 (OR)

Example  3.

A curable composition was prepared in the same manner as in Example 1, except that the compound of the formula (F) was used instead of the compound of the formula (B).

[Chemical Formula F]

_{(ViMe 2 SiO 1/2)} (Me 3 SiO 1/2) 4 (SiO 4/2) 10 (OR) 0.8

Comparative Example  One.

The curable composition was prepared in the same manner as in Example 1, except that the compound of the formula (G) was used in place of the compound of the formula (B).

[Formula G]

_{(ViMe 2 SiO 1/2)} (Me 3 SiO 1/2) 4 (SiO 4/2) 10 (OR) 2.2

Comparative Example  2.

Same as Example 2 except that the content of the compound of the formula A was 110 g, the content of the compound of the formula E was 20 g, the content of the compound of the formula C was 6 g and the content of the compound of the formula D was 4 g Lt; / RTI &gt; curable composition.

Comparative Example  3.

Same as Example 2 except that the content of the compound of the formula A was 50 g, the content of the compound of the formula E was 550 g, the content of the compound of the formula C was 16 g and the content of the compound of the formula D was 4 g Lt; / RTI &gt; curable composition.

Comparative Example  4.

A curable composition was prepared in the same manner as in Example 1 except that 60 g of the compound of the formula (H) was compounded with 110 g of the compound of the formula (A), 14 g of the compound of the formula (C) and 4 g of the compound of the formula (D) .

[Formula H] &lt;

_{(ViMe 2 SiO 1/2)} 4 (Me 3 SiO 1/2) (SiO 4/2) 10 (OR) 3

The physical properties measured for Examples and Comparative Examples are summarized in Table 1 below.

Light transmittance Surface stickiness Thermal Shock Characteristics Long-term reliability Example 1 A A 0/20 A Example 2 A A 0/20 A Example 3 A A 0/20 A Comparative Example 1 C A 0/20 C Comparative Example 2 A C 3/20 A Comparative Example 3 A A 15/20 C Comparative Example 4 A A 14/20 C

Claims (15)

(A) a linear or partially crosslinked polyorganosiloxane having an average composition formula of the following formula (1) and containing an aliphatic unsaturated bond; And (B) a polyorganosiloxane having an average composition formula of the following formula (2)
Wherein the polyorganosiloxane (B) is contained in a proportion of 30 parts by weight to 1000 parts by weight based on 100 parts by weight of the polyorganosiloxane (A)
[Chemical Formula 1]
(R ³ SiO _1/2 ) _a (R ² SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c (SiO _4/2 ) _d
Wherein R ¹ to R ³ are each independently an epoxy group or a monovalent hydrocarbon group, one or more of R ¹ to R ³ is an alkenyl group, and the sum of a, b, c and d (a + b c is 0 to 0.2, and d is 0 to 0.2; and &lt; RTI ID = 0.0 &gt;
(2)
(R ⁴ SiO _1/2 ) _e (R ⁵ SiO _2/2 ) _f (R ⁶ SiO _3/2 ) _g (SiO _4/2 ) _h (OR) _x
Wherein R ⁴ to R ⁶ are each independently an epoxy group or a monovalent hydrocarbon group, at least one of R ⁴ to R ⁶ is an alkenyl group, R is hydrogen or a monovalent hydrocarbon group, e, f, g and h is from 0 to 0.3, h is from 0.2 to 0.8, x is 0 or a positive (= 0) H / (g + h) is 0.7 or more, and x / (g + h) is 0.2 or less. The curable composition according to claim 1, wherein the ratio (Ak / Si) of the number of moles (Ak) of aliphatic unsaturated bonds to the number of moles (Si) of the total silicon atoms contained in the polyorganosiloxane (A) is 0.001 to 0.3. delete The curable composition according to claim 1, wherein (c + d) / (a + b + c + d) in the average composition formula of Formula 1 is 0 to 0.2. The curable composition according to claim 1, wherein the polyorganosiloxane (A) has a viscosity of 5 cP or more at 25 캜. The curable composition according to claim 1, wherein the polyorganosiloxane (B) has a viscosity of 5,000 cP or more at 25 캜. The curable composition according to claim 1, further comprising (C) a silicon compound containing a hydrogen atom bonded to a silicon atom. The curable composition according to claim 7, wherein the silicon compound (C)
[Chemical Formula 9]
R ₃ SiO (HRSiO) _r (R ₂ SiO) _s OSiR ₃
R in the formula (9) is independently hydrogen, an epoxy group or a monovalent hydrocarbon group, r is a number within a range of 0 to 100, and s is a number within a range of 0 to 100. The curable composition according to claim 7, wherein the ratio (H / Si) of the number of moles (H) of silicon atom-bonded hydrogen atoms to the number of moles (Si) of all silicon atoms contained in the silicon compound (C) is 0.2 to 0.99. 8. The curable composition according to claim 7, wherein the silicon compound (C) has a viscosity at 25 DEG C of from 0.1 cP to 100,000 cP. The method according to claim 7, wherein the mole number (H) of hydrogen atoms bonded to the silicon atom contained in the silicon compound (C) with respect to the mole number (Ak) of the lipophilic unsaturated bond contained in the polyorganosiloxane (A) ) (H / Ak) of from 0.5 to 3.0. A semiconductor device encapsulated with an encapsulant comprising a cured product of the curable composition of claim 1. An optical semiconductor device encapsulated with an encapsulant comprising a cured product of the curable composition of claim 1. 14. A liquid crystal display device comprising the optical semiconductor element of claim 13 in a backlight. 14. A lighting comprising the optical semiconductor element of claim 13.