KR101880211B1

KR101880211B1 - Curable composition

Info

Publication number: KR101880211B1
Application number: KR1020150190254A
Authority: KR
Inventors: 고민진
Original assignee: 주식회사 엘지화학
Priority date: 2015-12-30
Filing date: 2015-12-30
Publication date: 2018-07-20
Also published as: KR20170079551A

Abstract

The present application relates to curable compositions and uses thereof. The curable composition of the present application forms a cured product having excellent workability and moldability and excellent physical properties such as transparency, moisture resistance, mechanical properties, thermal shock resistance and crack resistance. Accordingly, the curable composition of the present application can be applied to various electronic components including optical semiconductor, for example, as an encapsulant or an adhesive, so that the electronic component can exhibit excellent reliability even when it operates for a long time under high temperature conditions , Wire open and the like can be prevented.

Description

{CURABLE COMPOSITION}

The present application relates to curable compositions and uses thereof.

ED (Light Emitting Diode) is a device that is 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 sealing materials known to date have insufficient transparency, moisture resistance, mechanical properties, thermal shock resistance and crack resistance, and therefore, it is not easy to stably ensure reliability.

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

The present application provides curable compositions and uses thereof.

Exemplary curable compositions include low molecular weight compounds having two or more alkenyl groups and having a given average unit. The curable composition may further comprise a compound having an alkenyl functional polyorganosiloxane and a silicon atom bonded hydrogen atom. The curable composition may be a composition that cures by reaction of an alkenyl group contained in the composition with a silicon atom-binding hydrogen atom, for example, a hydrosilylation reaction product.

The term & M unit in this specification, means a so-called monofunctional siloxane units in the case represented by the normal _{(R 3 SiO 1/2)} , and the term D unit is the case represented by the normal (R ₂ SiO _2/2) so-called transfer means a functional siloxane units, and the term T units represented by the normal (RSiO _3/2) with a so-called trifunctional means a functional siloxane units, and the term unit Q is normally (SiO _4/2) in the case represented by the Quot; siloxane unit " In the formula of each siloxane unit, R is a functional group bonded to silicon (Si), and may be, for example, hydrogen, an alkoxy group, an epoxy group or a monovalent hydrocarbon group.

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

As used herein, the term 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.

As used herein, the term alkyl group or alkoxy group may mean an alkyl group or an alkoxy 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 or alkoxy group may be linear, branched or cyclic. In addition, the alkyl or alkoxy group may be optionally substituted with one or more substituents.

As used herein, the term alkenyl or alkynyl group means an alkenyl group or 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 can do. The alkenyl or alkynyl group may be linear, branched or cyclic and may optionally be substituted with one or more substituents.

As used herein, the term aryl group means, unless otherwise specified, a compound comprising a benzene structure, a compound comprising a structure in which two or more benzenes are linked by a suitable linker, or two benzenes each having one or two carbon atoms Or may be a monovalent residue derived from a derivative of any one of the above-mentioned compounds. The range of the aryl group referred to in the present specification may include a so-called aralkyl group or an arylalkyl group as well as a functional group ordinarily referred to as an aryl group. The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group, dichlorophenyl, chlorophenyl, phenylethyl, phenylpropyl, benzyl, tolyl, xylyl group or naphthyl group.

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

The low molecular weight compound having two or more alkenyl groups contained in the curable composition may have, for example, an average unit represented by the following formula (1).

[Chemical Formula 1]

J _e Z _f SiO _{(4-ef) / 2}

(E + f) is in the range of 0.6 to 3.5, and e / (e + f (e + f) ) Is 0.01 to 0.7.

In the general formula (1), Z is a monovalent hydrocarbon group other than an alkenyl group, which is not particularly limited, but may be, for example, an alkyl group or an aryl group.

In formula (1), Z may be an alkoxy group, but it is preferable that the ratio is as small as possible. In one example, the ratio (AO / Si) of the number of moles (Si) of silicon atoms contained in the compound to the mole number (AO) of all alkoxy groups contained in the compound of Formula 1 is 0.4 or less, 0.35 or less, , 0.25 or less, 0.2 or less, 0.15 or less, 0.1 or less, 0.05 or less. The lower limit of the ratio (AO / Si) is not particularly limited and may be, for example, zero.

The compound of formula (1) may or may not contain an aryl group. For example, when the aryl group is included, the ratio (Ar / Si) of the number of moles (Ar) of the aryl group to the number of moles (Si) of the total silicon atoms of the compound of Formula (1) may be 1.5 or less or 1.2 or less. The ratio Ar / Si may be 0 or more, 0.05 or more, 0.1 or more, 0.15 or more, or 0.2 or more.

(E + f) in the formula (1) may be 0.7 or more, 0.8 or more, 0.9 or more, 1.0 or more, 1.5 or more, 1.7 or more, or 1.9 or more in other examples. In another example, (e + f) may be 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, 2.9 or less or 2.8 or less. In the formula (1), e / (e + f) may be 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, or about 0.23 or more. In the formula (1), e / (e + f) may be about 0.65 or less, about 0.6 or less, about 0.55 or less, or about 0.5 or less.

The compound of the formula (1) can improve the moisture resistance, mechanical properties, thermal shock resistance and crack resistance while maintaining excellent transparency of the composition or the cured product, and accordingly, the curable composition can be used as an encapsulating material for electronic parts When applied with an adhesive or the like, excellent reliability can be maintained even when the electronic component is operated for a long time at a high temperature, and defects such as wire open can be prevented in the process.

The compound of formula (I) may have a branched structure, a cyclic structure or a linear structure. In the case of having a branched structure, the compound of formula (1) may contain a T or Q unit, i.e., a unit of the following formula (3) or (4). The compound having such a structure can greatly improve its moisture resistance, mechanical properties, thermal shock resistance and crack resistance while maintaining excellent transparency of the composition or the cured product.

(3)

(RSiO _3/2)

[Chemical Formula 4]

(SiO _4/2)

In Formula (3), R is an epoxy group or a monovalent hydrocarbon group. In the formula (3), the monovalent hydrocarbon group is not particularly limited, but an alkyl group or an aryl group can be used.

The compound of formula (I) may comprise 1 to 5, 1 to 4, 1 to 3 or 1 to 2 of the above T or Q units.

In the case of a linear or cyclic structure, the compound of formula (1) may comprise a D unit, i.e. a unit of the following formula (5). The compound having such a structure can greatly improve its moisture resistance, mechanical properties, thermal shock resistance and crack resistance while maintaining excellent transparency of the composition or the cured product.

[Chemical Formula 5]

(R ₂ 2SiO _2/2)

In formula (2), R is an epoxy group or a monovalent hydrocarbon group. In the formula (2), the monovalent hydrocarbon group is not particularly limited, but an alkyl group or an aryl group may be used.

When the compound of Chemical Formula 1 has a cyclic structure, the D unit (Chemical Formula 5) may include 4 to 8 or 4 to 6 D units. When the compound of formula (1) is a linear structure, the compound of formula (1) may further include M units in addition to the D unit (formula (5)). In case of a linear structure, the compound of formula (1) may contain not more than 10, not more than 8, not more than 6, not more than 4, not more than 2, or one of the above-mentioned D unit (formula (5)).

The compound of formula (I) may contain 1 to 5 or 1 to 4 D units.

The compound of formula (1) may be a relatively low molecular weight compound, for example, having a weight average molecular weight of 1200 or less, 1000 or less, 800 or less, 700 or less, 600 or less or 550 or less. The weight average molecular weight of the compound of formula (1) may be 150 or more, 200 or more, 250 or more, or 300 or more. As used herein, the term weight average molecular weight may refer to a conversion value for standard polystyrene measured by GPC (Gel Permeation Chromatograph). Unless otherwise specified, the term molecular weight may mean weight average molecular weight. The compound having such a molecular weight can greatly improve its moisture resistance, mechanical properties, thermal shock resistance and crack resistance while maintaining excellent transparency of the composition or the cured product. The compound of the formula (1) is a compound having a relatively low molecular weight as described above, for example, three to ten silicon atoms (Si), three to nine, three to eight, three to seven, Three to six, or three to five.

The compound of formula (1) may have a viscosity at 25 ° C of 1000 mPa · s or less, thereby improving the moisture resistance, mechanical properties, thermal shock resistance and crack resistance of the cured product while maintaining the workability and moldability of the composition.

The compound of the formula (1) may be contained in the curable composition in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the alkenyl functional crosslinking type polyorganosiloxane described later. Unless otherwise specified, the unit weight portion in the present specification means the weight ratio between the components. In another embodiment, the proportion of the compound of Formula 1 is 0.5 part by weight or more, 1.0 part by weight or more, 1.5 parts by weight or more, 2.0 parts by weight or more, 2.5 parts by weight or more, 3.0 parts by weight or more, 3.5 parts by weight or more, . The proportion of the compound of Formula 1 may be about 15 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less in another example. When the proportion of the compound of the formula (1) is too high or low, when the curable composition is applied as an encapsulating material or an adhesive for electronic parts, it may cause defects such as wire open under thermal shock, So that the ratio can be adjusted within the above-mentioned range.

The curable composition may include an alkenyl functional bridging polyorganosiloxane as an additional component.

The term alkenyl functional polyorganosiloxane in the present application may mean a polyorganosiloxane containing at least one alkenyl group bonded to a silicon atom. The term crosslinked polyorganosiloxane may also refer to a polyorganosiloxane containing a T unit or Q unit as the siloxane unit.

In one example, the term crosslinked polyorganosiloxane as used herein includes T or Q units, wherein the sum of the total mole number (D + T + Q) of the total D, T and Q units contained in the polyorganosiloxane May denote a polyorganosiloxane having a ratio (D / (D + T + Q)) of the number of moles (D) in D units of not less than 0, less than 0.5, less than 0 to 0.4 or 0 to 0.3.

The alkenyl functional bridging polyorganosiloxane may comprise at least one T unit. The ratio of T units is not particularly limited, but may be 50 mol% or more based on the total mols of the total siloxane units (i.e., the total number of moles of M, D, T and / or Q units that can be contained in the polyorganosiloxane) 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, or 75 mol% or more. The upper limit of the molar ratio of T units is not particularly limited. For example, the molar ratio of T units may be 95 mol% or less, 90 mol% or 85 mol% or less. The alkenyl functional crosslinking polyorganosiloxane may include a T unit having an aryl group bonded to a silicon atom as a T unit. (T / (Q + Q)) of the total number of moles (T + Q) of the Q units contained in the alkenyl functional crosslinking type polyorganosiloxane, ) Is 0.5 or more, 0.7 or more, 0.9 or more, or 0.95 or more. Through the use of the crosslinking type polyorganosiloxane containing T unit or T unit having an aryl group in such a range, it is possible to secure the excellent reliability of an electronic part such as a photo semiconductor in which the curable composition is applied as an encapsulating material or an adhesive.

As the alkenyl functional crosslinking type polyorganosiloxane contained in the curable composition, for example, a polyorganosiloxane having an average unit represented by the following formula (2) can be exemplified.

(2)

P _a Q _b SiO _{(4-ab) / 2}

(A + b) is in the range of 1 to 2.2, and a / (a + b) is an integer of from 1 to 2.2, P is an alkenyl group, Q is a monovalent hydrocarbon group or alkoxy group excluding an epoxy group or an alkenyl group, ) Is in the range of 0.01 to 0.35.

In formula (2), Q may be an alkoxy group, but it is preferable that the ratio is as small as possible. In one example, the ratio (AO / Si) of the number of moles (Si) of silicon atoms contained in the compound to the mole number (AO) of all alkoxy groups contained in the compound of Formula 2 is 0.4 or less, , 0.25 or less, 0.2 or less, 0.15 or less, 0.1 or less, 0.05 or less. The lower limit of the ratio (AO / Si) is not particularly limited and may be, for example, zero.

(A + b) in formula (2) may be 2.0 or less, 1.8 or less, or 1.6 or less in another example. In the formula (2), a / (a + b) may be 0.05 or more or 0.1 or more in another example. The a / (a + b) may be 0.3 or less, 0.25 or less, or 0.2 or less in other examples.

One or two or more of Q in formula (2) may be an aryl group. For example, in the general formula (2), the ratio of the number of moles of the aryl group (Ar) to the number of moles (Si) of the total silicon atoms contained in the crosslinked polyorganosiloxane (Ar / Si) 0.3 to 1.0, 0.5 to 1.0, 0.7 to 1.0, or 0.75 to 1.0.

At least one of Q in formula (2) may be an epoxy group. For example, in the formula (2), the epoxy group of Q is such that the ratio (Ar / Si) of the number of moles (E) of the epoxy group to the number of moles (Si) of all silicon atoms contained in the polyorganosiloxane is 0.01 to 0.5 or 0.05 to 0.5 &Lt; / RTI >

The viscosity at 25 캜 of the alkenyl functional crosslinking type polyorganosiloxane can be within a range of, for example, 1,000 mPa s or more, 2,000 mPa s or more, and 5,000 mPa s or more. Within this range, the workability before molding, the formability, the mechanical properties after curing, the thermal shock resistance and the crack resistance can be properly maintained.

The alkenyl functional crosslinking polyorganosiloxane may have a weight average molecular weight of, for example, 1,000 or more, 1,500 or more, or 2,000 or more. The weight average molecular weight may be, for example, 50,000 or less, 40,000 or less, 30,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 6,000 or less, 4,000 or less or 3,500 or less. The molecular weight of the alkenyl-functional polyorganosiloxane can be controlled within the above range to effectively maintain the moldability or workability before curing, mechanical properties after curing, thermal shock resistance and crack resistance.

The curable composition may include the crosslinked polyorganosiloxane as a main component. That is, the curable composition may include about 55% or more, or about 60% or more, by weight of the crosslinked polyorganosiloxane. The ratio can be, for example, about 95% by weight or less, about 90% by weight or less, about 85% by weight or less, about 80% by weight or about 75% by weight or less.

The curable composition may optionally comprise an alkenyl functional linear polyorganosiloxane. The linear polyorganosiloxane is an optional component and is optionally not included in the curable composition.

The term linear polyorganosiloxane as used herein includes polyorganosiloxanes containing only M and D units as siloxane units or T or Q units as essential units of the crosslinking type polyorganosiloxane together with D units, (D / (D + T + Q)) of the D units relative to the total D, T and Q units is 0.7 or more but less than 1, which is a structure having a sufficiently long linear structure derived from the polyorganosiloxane.

The linear polyorganosiloxane is an optional component of the curable composition, and thus may or may not be included in the curable composition. When the linear polyorganosiloxane is included, the proportion of the linear polyorganosiloxane is 100 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less and 60 parts by weight or less based on 100 parts by weight of the crosslinked polyorganosiloxane Or 50 parts by weight or less. Accordingly, the proportion of the linear polyorganosiloxane is 0 to 100 parts by weight, 0 to 90 parts by weight, 0 to 80 parts by weight, 0 to 70 parts by weight, 0 to 60 parts by weight, relative to 100 parts by weight of the crosslinking type polyorganosiloxane Or 0 to 50 parts by weight. If the proportion of the linear polyorganosiloxane is excessively large, the heat-resistant impact resistance of the electronic component to which the curable composition is applied as the sealing material or the adhesive or the reliability at the time of the high temperature operation may be lowered.

The curable composition may further comprise a compound containing a hydrogen atom with a silicon atom bond. The compound may be, for example, one, two or more, two to ten, two to eight, two to six, two to four, two to three, or two One may be linear, partially crosslinked or crosslinked polyorganosiloxane.

For example, the compound may have an average unit represented by the following formula (6).

[Chemical Formula 6]

H _c R _d SiO _{(4-cd) / 2}

C and d are numbers within the range of 1 to 2.8, 1 to 2.6, 1 to 2.4, or 1 to 2.2, c / (c + d) 0.5. &Lt; / RTI >

The compound may be a curing agent capable of reacting with an alkenyl group of an alkenyl-functional compound such as the alkenyl-functional polyorganosiloxane to form a cured product by crosslinking the composition. For example, the hydrogen atom of the compound may undergo addition reaction with the alkenyl group to form a cured product.

In the average unit of formula (6), one or two or more of Q may be an aryl group. For example, the ratio (Ar / Si) of the number of moles (Ar) of the aryl group to the number of moles (Si) of the total silicon atoms contained in the compound of the average unit of the formula (6) is 0.25 or more, 0.25 To 1.0 or 0.3 to 1.0, the Q may be an aryl group.

Compounds having silicon atom bonded hydrogen atoms may be either solid or liquid. The compound has a viscosity at 25 占 폚 of 1,000 mPa 占 퐏 or less, 900 mPa 占 퐏 or less, 800 mPa 占 퐏 or less, 700 mPa 占 퐏 or less, 600 mPa 占 퐏 or less, 500 mPa 占 이하 or less, 400 mPa s or less, 300 mPa s or less, or 300 mPa s or less. By controlling the viscosity as described above, it is possible to maintain excellent workability of the composition, mechanical properties of the cured product, thermal shock resistance and crack resistance, and the like.

The compound having a silicon atom-bonded hydrogen atom may have a molecular weight of, for example, less than 1,000 or less than 800. The strength and the like of the cured product can be maintained in an appropriate range at the molecular weight in the above range. The lower limit of the molecular weight of the compound is not particularly limited, and may be 250, for example.

As the compound of the average unit of the formula (6), various kinds of compounds may be used as long as the above characteristics are satisfied. For example, as the above-mentioned compound, a compound represented by the following general formula (7) can be used.

(7)

Wherein at least one of R is an aryl group and n is an integer of 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 7, 5, 1 to 4, 1 to 3, or 1 to 2.

In formula (7), R may be, for example, an aryl group or an alkyl group, and may be an aryl group or an alkyl group within a range satisfying the ratio (Ar / Si) of the aryl group of the compound of the average unit of the formula (6).

The ratio, viscosity or molecular weight of the aryl group of the compound of formula (VII) may be within the above-mentioned range.

The content of the compound containing the hydrogen atom bonded to the silicon atom, for example, the compound of the average unit of the formula (6) or the compound of the formula (7) can be selected within a range that the mixture is cured to have the above- have. For example, the content of the compound is preferably such that the ratio of the number of moles (H) of the hydrogen atoms of the compound to the total molar number (Ak) of the alkenyl groups of the alkenyl functional polyorganosiloxane and the compound having three or more alkenyl groups Ak / H) is in the range of 0.9 to 3.0, 0.9 to 2.0 or 1 to 1.5.

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. Considering the catalytic efficiency and the like, a platinum-based catalyst can be used. Examples of such a catalyst 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 to.

The content of the hydrosilylation catalyst is not particularly limited as long as it is contained in the so-called catalytic amount, that is, the amount that can act as a catalyst. Typically, it can be used in an amount of 0.1 ppm to 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, and can improve the self-adhesiveness particularly to metals and organic resins.

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

If the adhesive property-imparting agent is included, for example, the adhesive property-imparting agent may be contained in a proportion of 0.1 to 20 parts by weight based on 100 parts by weight of the solid content of the curable composition, And can be changed appropriately. Unless otherwise specified, the unit weight portion in the present specification means the weight ratio of each component.

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.

As described above, the curable composition may be a composition of a type that cures by reaction of an alkenyl group contained in the composition with a silicon atom-binding hydrogen atom, for example, a hydrosilylation reaction product. In order to ensure proper physical properties, the curable composition may be prepared such that the ratio of the hydrogen atoms bonded to the silicon atoms remaining after the curing reaction is as low as possible, and alkenyl groups bonded to a small amount of silicon atoms remain.

For example, in the curable composition, the ratio (H / Si) of the number of moles of hydrogen atoms (H) bonded to silicon atoms to the number of moles of silicon atoms (Si) after the curing reaction is 0.05 or less, 0.04 or less, Or less or 0.01 or less, or substantially zero. (Ak / Si) of the number of moles (Ak) of the alkenyl group bonded to the silicon atom and the number of moles (Si) of the silicon atom after the curing reaction is 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, or 0.05 or more . &Lt; / RTI >

In order for the curable composition to have a hydrogen atom or an alkenyl group in the above-described state after curing, a method of controlling the proportion of the component having the hydrogen atom or the alkenyl group contained in the curable composition may be exemplified.

The present application may also be for a cured body formed by curing the curable composition as described above.

The ratio (H / Si) of the number of moles of hydrogen atoms (H) bonded to silicon atoms to the number of moles of silicon atoms (Si) in the cured body is 0.05 or less, 0.04 or less, 0.03 or less, 0.02 or less or 0.01 or less, Lt; / RTI >

(Ak / Si) of the number of moles (Ak) of the alkenyl group bonded to the silicon atom and the number of moles (Si) of the silicon atom in the cured product is 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, or 0.05 or more .

This application relates to semiconductor devices, for example, optical semiconductor devices. An exemplary semiconductor device may be one encapsulated by an encapsulant comprising a cured body of the curable composition.

The cured product can be obtained by, for example, hydrogenating a hydrogen atom of a compound containing an alkenyl group of a compound containing an alkenyl-functional polyorganosiloxane of the above composition and three or more alkenyl groups and a silicon atom- And the like. The conditions for curing the curable composition to form a cured body are not particularly limited and can be formed, for example, by holding the curable composition in a desired form at a temperature of about 60 캜 to 200 캜 for 10 minutes to 5 hours.

In the cured product of the present invention, it is preferable that the number of moles of the H functional group in the total Si atoms ([H] / [Si] is 0.05 mole or less,

In the cured product of the present invention, it is preferable that the mole number (Vi / Si) of the Vi functional group in the total Si atoms is 0.01 or more and 0.05 or more.

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 can be sealed with the cured body, and thus the sealing process can be carried out using the above-mentioned curable composition. The encapsulation of the light emitting diode can be performed only with the curable composition, and in some cases other encapsulant can be used in combination with the curable composition. In the case of using two kinds of sealing materials together, after sealing with the curable composition, the periphery thereof may be sealed with another sealing material, or may be first sealed with another sealing material, and then the periphery thereof may be sealed with the above-mentioned curable composition . Examples of other sealing materials include epoxy resins, silicone resins, acrylic resins, urea resins, imide resins, and glass.

Examples of the method of encapsulating the light emitting diode with the curable composition include a method of previously injecting the curable composition into a mold mold, immersing a lead frame or the like having the light emitting diode fixed thereon and curing the curable composition, A method in which a curable composition is injected into a mold inserted and cured. Examples of the method of injecting the curable composition include injection by a dispenser, transfer molding, injection molding, and the like. Examples of other sealing methods include a method in which a curable composition is dropped on a light emitting diode, applied by screen printing, screen printing, or a mask, and cured, or a cup in which a light emitting diode is disposed on the bottom, And curing, etc. may 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.

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.

It is possible to further improve the performance of the light emitting diode according to the 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.

BACKGROUND ART Optical semiconductors, for example, light emitting diodes are widely used as backlights for a liquid crystal display (LCD), lights, light sources such as various sensors, printers and copiers, instrument light sources for vehicles, Device, a light source of a planar light-emitting body, a display, a decoration, or various lights.

The curable composition of the present application can form a cured product having excellent physical properties such as transparency, moisture resistance, mechanical properties, thermal shock resistance and crack resistance, and has excellent workability and moldability in the process of forming the cured product. Accordingly, the curable composition of the present application can be applied to various electronic parts including optical semiconductor, for example, as an encapsulating material or an adhesive to provide an apparatus of excellent 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.

As used herein, unless otherwise specified, the symbols Vi, Ph, Me, and Ep represent a vinyl group, a phenyl group, a methyl group, and a 3-glycidoxypropyl group, respectively.

The evaluations of Examples and Comparative Examples were carried out in the following manner.

1. Wire open bad evaluation

Device reliability is evaluated using a 7030 LED package made of polyphthalamide (PPA). The curable composition was cured by performing the steps of dispensing the curable composition in a polyphthalamide cup, holding at 60 ° C for 1 hour, holding at 80 ° C for 1 hour, and holding at 150 ° C for 4 hours, , And a surface mount LED is manufactured. The produced LED is maintained at -50 占 폚 for 15 minutes and then at 130 占 폚 for 15 minutes, and the above cycle is repeated for one cycle. The above-mentioned 200 cycles are repeated for 20 LEDs, and the number of LED openings in which wire open has occurred relative to the total number (20) of LEDs is measured (the number of LED openings / Number of LEDs used in the evaluation).

2. High temperature operation long term reliability

The device characteristics are evaluated using an 8520 LED package made of polyphthalamide (PPA). The curable composition prepared in the polyphthalamide cup was dispensed, held at 60 占 폚 for 1 hour, held at 80 占 폚 for 1 hour, and held at 150 占 폚 for 4 hours, Cured to produce a surface mount LED. The manufactured LED was operated for 1500 hours while flowing a current of 30 mA while maintaining the LED at 150 ° C. The reliability of the LED was measured according to the following criteria by measuring the reduction rate of the luminance after the operation relative to the initial luminance before the operation.

A: When the luminance reduction rate is 7% or less

B: When the luminance reduction rate is more than 7% and less than 15%

C: When the luminance reduction rate exceeds 15%

3. Molecular weight evaluation method

The weight average molecular weight of the compounds used in Examples and Comparative Examples was measured by using a THF solvent in a GPC (Model: Waters e2695, column: PLGEL 5 μm mixed-C, PLGEL 5 μm mixed-D, PLGEL 3 μm mixed-E column) And compared with standard polystyrene.

Example 1

59.6 g of a polyorganosiloxane having an average molecular weight of about 2,300 and an average unit of the following formula A, 2 g of a polyorganosiloxane having an average unit represented by the following formula (B), a molecular weight of about 2,500, and an average unit represented by the following formula 2.5 g of the polyorganosiloxane having a molecular weight of about 414 and 20.5 g of the polyorganosiloxane of the following formula D were mixed and the catalyst (Platinum (0) -1,3-divinyl-1 , 1,3,3-tetramethyldisiloxane) was blended to prepare a curable composition.

(A)

(ViMe ₂ SiO _1/2 ) _0.21 (MePhSiO _2/2 ) _0.04 (PhSiO _3/2 ) _0.75

[Chemical Formula B]

(ViMe ₂ SiO _1/2 ) _0.15 (PhSiO _3/2 ) _0.54 (EpMeSiO _2/2 ) _0.31

&Lt; RTI ID = 0.0 &

(ViMe ₂ SiO _1/2 ) _0.75 (PhSiO _3/2 ) _0.25

[Chemical Formula D]

(HMe ₂ SiO _1/2 ) ₂ (Ph ₂ SiO _2/2 )

Example 2

59.6 g of a polyorganosiloxane having a molecular weight of about 2,300, an average unit of the following formula (E), 2 g of a polyorganosiloxane having an average unit of the formula (B) and a molecular weight of about 2,500, 2.5 g of a polyorganosiloxane having a weight average molecular weight of about 414, 10 g of a polyorganosiloxane having a molecular weight of about 6,990 with an average unit represented by the following formula (F), and 20.5 g of a polyorganosiloxane having the formula (D) (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was added in an amount so as to obtain a curable composition.

(E)

(ViMe ₂ SiO _1/2 ) _0.2 (PhSiO _3/2 ) _0.8

[Chemical Formula F]

(ViMe ₂ SiO _1/2 ) _0.05 (Me ₂ SiO _2/2 ) _0.53 (Ph ₂ SiO _2/2 ) _0.42

Example 3

A curable composition was prepared in the same manner as in Example 1, except that 2.5 g of a polyorganosiloxane having a molecular weight of about 440 was used instead of the compound having an average unit of the formula (C)

[Formula G]

(ViMe ₂ SiO _1/2 ) _0.8 (SiO _4/2 ) _0.2

Example 4

A curable composition was prepared in the same manner as in Example 1, except that 2.5 g of a polyorganosiloxane having a molecular weight of about 384 was used instead of the compound having an average unit of the formula (C)

[Formula H] <

(ViMe ₂ SiO _1/2 ) _0.67 (Ph ₂ SiO _2/2 ) _0.33

Example 5

A curable composition was prepared in the same manner as in Example 1, except that 2.5 g of a polyorganosiloxane having a molecular weight of about 322 was used instead of the compound having an average unit of the formula (C) and the average unit of the formula (I) was blended.

(I)

(ViMe ₂ SiO _1/2 ) _0.67 (MePhSiO _2/2 ) _0.33

Example 6

A curable composition was prepared in the same manner as in Example 1, except that 2.5 g of a polyorganosiloxane having a molecular weight of about 350 was used instead of the compound having an average unit represented by the formula (C).

[Chemical Formula J]

(ViMe ₂ SiO _1/2 ) _0.75 (MeSiO _3/2 ) _0.25

Example 7

A curable composition was prepared in the same manner as in Example 1, except that 2.5 g of a polyorganosiloxane having a molecular weight of about 525 was used instead of the compound having an average unit of the formula (C) .

[Chemical formula K]

(ViPhSiO _2/2)

Example 8

A curable composition was prepared in the same manner as in Example 1, except that 2.5 g of a polyorganosiloxane having a molecular weight of about 352 was used instead of the compound having an average unit of the formula C, Respectively.

[Chemical formula K]

₍₂ ViMeSiO _{/ 2)}

Comparative Example 1

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

Comparative Example 2

A curable composition was prepared in the same manner as in Example 1, except that the amount of the polyorganosiloxane in the average unit of the formula (C) was changed to 15 g.

Comparative Example 3

A curable composition was prepared in the same manner as in Example 3 except that the amount of the polyorganosiloxane in the average unit of the formula G was changed to 15 g.

Comparative Example 4

A curable composition was prepared in the same manner as in Example 1, except that a polyorganosiloxane having an average unit of the following formula (M) was used instead of the average unit of the polyorganosiloxane of the formula (A) and a molecular weight of about 2000 was used.

[Formula M]

(ViMe ₂ SiO _1/2 ) _0.13 (MePhSiO _2/2 ) _0.47 (PhSiO _3/2 ) _0.4

Comparative Example 5

Polyanosiloxane of Average Unit of Formula A Dye The curable composition was prepared in the same manner as in Example 1, except that the polyorganosiloxane having an average unit represented by the following formula (N) and having a molecular weight of about 5,500 was used.

[Chemical formula N]

(ViMe ₂ SiO _1/2 ) _0.21 (MePhSiO _2/2 ) _0.04 (PhSiO _3/2 ) _0.21 (SiO _4/2 ) _0.53

Comparative Example 6

A curable composition was prepared in the same manner as in Example 2, except that the amount of the polyorganosiloxane in the average unit of the formula (F) was changed to 65 g.

The results of measurement of physical properties for Examples and Comparative Examples are summarized in Table 1 below.

Wire open failure responsibility Example 1 2/22 A Example 2 0/22 A Example 3 1/22 A Example 4 2/22 A Example 5 3/22 A Example 6 4/22 A Example 7 4/22 A Example 8 4/22 A Comparative Example 1 22/22 A Comparative Example 2 10/22 C Comparative Example 3 8/22 C Comparative Example 4 6/22 C Comparative Example 5 22/22 B Comparative Example 6 6/22 C

Claims

An alkenyl functional bridging type polyorganosiloxane containing at least 70 mol% of trifunctional siloxane units based on the mole number of all siloxane units;
A compound having an average unit represented by the following formula (1) and having a weight average molecular weight of 1,200 or less, in an amount of 0.1 part by weight to 20 parts by weight based on 100 parts by weight of the alkenyl functional crosslinking type polyorganosiloxane;
An alkenyl functional linear polyorganosiloxane which is contained in a proportion of not more than 100 parts by weight based on 100 parts by weight of the alkenyl functional crosslinking polyorganosiloxane; And
A compound having a silicon atom-bonded hydrogen atom,
Wherein the compound having an average unit represented by the formula (1) is a linear or cyclic structure having a siloxane unit represented by the following formula (4) or a siloxane unit represented by the following formula (5)
[Chemical Formula 1]
J _e Z _f SiO _{(4-ef) / 2}
[Chemical Formula 4]
(SiO4 / ₂ )
[Chemical Formula 5]
(R ₂ SiO _2/2 )
(E + f) is in the range of 0.6 to 3.5, and e / (e + f (e + f) ) Is 0.01 to 0.7,
In formula (5), R is a monovalent hydrocarbon group.

The curable composition according to claim 1, wherein the alkenyl functional crosslinking type polyorganosiloxane has a weight average molecular weight of 1,000 or more.

The curable composition of claim 1, wherein the alkenyl functional bridging polyorganosiloxane has an average unit of the formula:
(2)
P _a Q _b SiO _{(4-ab) / 2}
(A + b) is in the range of from 1 to 2.2, and a / (a + b) is an integer of from 1 to 2. In the formula (2), P is an alkenyl group, Q is a monovalent hydrocarbon group other than an alkenyl group, an epoxy group or an alkoxy group, ) Is in the range of 0.01 to 0.35.

The curable composition according to claim 1, wherein the compound of the average unit of the formula (1) has a viscosity at 25 캜 of 1,000 mPa 이하 or less.

delete

The curable composition according to claim 1, wherein the average unit of the compound of the formula (1) is contained in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the alkenyl functional crosslinking type polyorganosiloxane.

The curable composition according to claim 1, wherein the average unit of the compound of Formula (1) is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the alkenyl functional crosslinking polyorganosiloxane.

The curable composition of claim 1, wherein the alkenyl functional linear polyorganosiloxane is included at a ratio of up to 50 parts by weight relative to 100 parts by weight of the alkenyl functional crosslinking polyorganosiloxane.

The curable composition according to claim 1, wherein the compound having a silicon atom-bonded hydrogen atom has an average unit represented by the following formula (6):
[Chemical Formula 6]
H _c R _d SiO _{(4-cd) / 2}
In formula (6), R is a monovalent hydrocarbon group, and c and d are numbers such that c + d is in the range of 1 to 2.8 and c / (c + d) is in the range of 0.01 to 0.5.

The curable composition according to claim 1, wherein the compound having a silicon atom-bonded hydrogen atom is a compound represented by the following formula (7):
(7)

R in Formula (7) is independently hydrogen, an epoxy group or a monovalent hydrocarbon group, at least one of R is an aryl group, and n is a number within a range of 1 to 10. [

The curable composition according to claim 1, wherein the ratio (H / Si) of the number of moles of hydrogen atoms (H) bonded to silicon atoms to the number of moles of silicon atoms (Si) after the curing reaction is 0.05 or less.

The curable composition according to claim 1, wherein the ratio (Ak / Si) of the number of moles (Ak) of the alkenyl group bonded to the silicon atom to the number of moles (Si) of the silicon atom after the curing reaction is 0.01 or more.

A semiconductor device encapsulated with an encapsulating material comprising a cured product of the curable composition of claim 1.

An optical semiconductor device encapsulated with an encapsulant comprising a cured product of the curable composition of claim 1.

A liquid crystal display device comprising the optical semiconductor element of claim 15.

15. A lighting comprising the optical semiconductor element of claim 15.