WO2015115812A1

WO2015115812A1 - Cured product

Info

Publication number: WO2015115812A1
Application number: PCT/KR2015/000931
Authority: WO
Inventors: 고민진; 김경미; 정재호; 최범규; 김민균
Original assignee: 주식회사 엘지화학
Priority date: 2014-01-28
Filing date: 2015-01-28
Publication date: 2015-08-06

Abstract

The present application relates to a cured product and use thereof. A cured product, when applied to an optical semiconductor such as an LED, etc., can for example provide a device which, even when used for a long time, has minimal decrease in luminance and excellent crack resistance and thus has excellent long-term reliability. A cured product has excellent processability, workability, adhesiveness and the like, and does not induce stickiness on a surface, turbidity, and the like. Moreover, a cured product has excellent high-temperature heat resistance, gas barrier properties and the like. A cured product, for example, can be applied as a sealant or an adhesive material for a semiconductor device.

Description

Cured product

This application relates to a cured product and its use.

Light emitting diodes (LEDs) are devices that are utilized in various fields such as light sources and lighting of display devices.

As the LED encapsulant, an epoxy resin having high adhesiveness and excellent mechanical durability is widely used. However, the epoxy resin has a problem in that the transmittance of light in the blue to ultraviolet region is low, and the heat resistance and light resistance are inferior. Accordingly, for example, Patent Documents 1 to 3 propose techniques for improving the above problems. However, the sealing material known to date is insufficient in gas barrier property, adhesiveness, etc., and lacks heat resistance, heat shock resistance, and crack resistance.

[Preceding technical literature]

[Patent Documents]

Patent Document 1: Japanese Patent Application Laid-Open No. 11-274571

Patent Document 2: Japanese Patent Laid-Open No. 2001-196151

Patent Document 3: Japanese Patent Laid-Open No. 2002-226551

The present application provides a cured product and its use.

The cured product of the present application is a reactant of a mixture (curable composition) containing an aliphatic unsaturated bond functional polyorganosiloxane and a compound (crosslinking agent) containing a hydrogen atom bonded to a silicon atom, for example, hydrogen silica of the mixture. It may be a hydrosilylation reaction product.

This cured product is, for example, in the case represented by the normal (R ₃ SiO _1/2) a (, unit M or less) so-called monofunctional siloxane units represented by the case, usually (R ₂ SiO _2/2) So-called bifunctional siloxane units (hereinafter referred to as D units), usually referred to as (RSiO _3/2 ), so-called trifunctional siloxane units (hereinafter referred to as T units) and usually referred to as (SiO _4/2 ) It may comprise one or more siloxane units selected from so-called tetrafunctional siloxane units (hereinafter referred to as Q units). 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.

The cured product may include one or more units represented by the following Formula (1).

[Formula 1]

(R ₂ SiO _1/2 A _1/2 )

In formula (1), each R is independently hydrogen, an epoxy group, an alkoxy group, or a monovalent hydrocarbon group, and A is an alkylene group having 1 to 4 carbon atoms.

As used herein, unless otherwise specified, the term epoxy group may mean a cyclic ether having three ring constituent atoms or a monovalent moiety derived from a compound containing the cyclic ether. Examples of the epoxy group include glycidyl group, epoxyalkyl group, glycidoxyalkyl group or alicyclic epoxy group. In the above, the alicyclic epoxy group may mean a monovalent moiety derived from a compound containing an aliphatic hydrocarbon ring structure, wherein the two carbon atoms forming the aliphatic hydrocarbon ring also include an epoxy group. As the alicyclic epoxy group, an alicyclic epoxy group having 6 to 12 carbon atoms can be exemplified, for example, a 3,4-epoxycyclohexylethyl group or the like can be exemplified.

As used herein, unless otherwise specified, the term monovalent hydrocarbon group may refer to a compound consisting of carbon and hydrogen or a monovalent moiety derived from a derivative of such a compound. For example, the monovalent hydrocarbon group may contain 1 to 25 carbon atoms. As a monovalent hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group, etc. can be illustrated.

As used herein, unless otherwise specified, 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. The alkyl group or alkoxy group may be linear, branched or cyclic. In addition, the alkyl group or alkoxy group may be optionally substituted with one or more substituents.

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

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

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

In the present specification, substituents that may be optionally substituted with an epoxy group, an alkoxy group or a monovalent hydrocarbon group include an epoxy group such as halogen, glycidyl group, epoxyalkyl group, glycidoxyalkyl group or alicyclic epoxy group such as chlorine or fluorine, and acryl. A royl group, a methacryloyl group, an isocyanate group, a thiol group, or a monovalent hydrocarbon group may be exemplified, but is not limited thereto.

The unit of Chemical Formula 1 may be formed by a reaction between an aliphatic unsaturated bond and a hydrogen atom bonded to a silicon atom in the process of forming a cured product. Thus, the ratio (C / Si) is a kind of material of the cured product, The ratio and / or reaction conditions can be selected and adjusted. By adjusting the ratio (C / Si) in the range as described above, it is possible to form a cured body suitable for the intended use, in particular it may be possible to provide a cured body excellent in heat resistance, crack resistance and thermal shock resistance. A specific method of controlling the ratio (C / Si) in the formation of the cured product will be described later.

In Formula 1, A may be, in another example, an alkylene group having 1 to 3 carbon atoms, 1 to 2 carbon atoms, or 2 carbon atoms.

The unit of Formula (1) is a unit of the structure in which at least 2 silicon atoms (Si) contained in a hardening body are connected by the alkylene group represented by A.

In the cured product, the ratio (C / Si) of the number of moles of carbon atoms (C) and the number of moles of silicon (Si) of all silicon atoms in the formula (1) may be in the range of 0.15 to 0.55. The ratio (C / Si) may be 0.2 or more in another example. In another example, the ratio (C / Si) may be, for example, 0.5 or less, 0.45 or less, or 0.4 or less.

The ratio may be obtained by performing NMR analysis, for example, ²⁹ Si-NMR analysis on the cured product. NMR analysis is performed using a phenomenon in which a material containing an atomic nucleus ( ²⁹ Si) having nuclear magnetic resonance and a magnetic moment absorbs electromagnetic waves of a specific frequency in a magnetic field. The absorption depends on the kind of atomic nucleus, and even on the same atomic nucleus, depending on the chemical environment surrounding the atom (ex. The kind of atoms bonded to the atom). Therefore, the said ratio can be measured through the specific absorption spectrum which shows according to the kind of atomic nucleus or its chemical environment. Since a hardened | cured material is solid at normal temperature normally, in this case, a high temperature NMR or a solid-state NMR system can be applied.

The cured product may include an aryl group, for example, an aryl group bonded to a silicon atom. The aryl group may be included, for example, such that the ratio (Ar / Si) of the number of moles (Si) of the total silicon atoms of the cured product and the number of moles (Ar) of the aryl group is within a range of 0.2 to 1.2 or 0.4 to 1.0. . In this range, when applied to an optical semiconductor device such as an LED, such as an aryl group, excellent light extraction efficiency can be ensured, and a cured body in which gas permeation characteristics and the like can be efficiently controlled can be provided. The ratio (Ar / Si) can be adjusted by controlling the number of moles of aryl groups and silicon atoms present in the polyorganosiloxane or crosslinking agent forming the cured product. The ratio can also be measured by the NMR method described above.

The cured body may include one or more siloxane units selected from M, D, T, and Q units, as described above. In one example, the cured body is represented by at least one T unit, for example, represented by Formula 2 below. It may include units.

[Formula 2]

(RSiO _3/2 )

R in formula (2) is hydrogen, an epoxy group, an alkoxy group or a monovalent hydrocarbon group.

The unit of formula (2), for example, the ratio (T / Si) of the number of moles (T) of the T unit and the number of moles (Si) of the total silicon atoms of the cured body is within the range of about 0.3 to about 0.6 or about 0.35 to 0.5 It may be included to belong. If T unit is included in this range, the hardened | cured material which is excellent in the characteristic calculated | required by the intended use, such as mechanical strength or gas permeation characteristic, for example can be provided. The said ratio (T / Si) can be adjusted through adjustment of the ratio of the said T unit and silicon atom contained in the polyorganosiloxane and crosslinking agent which form hardened | cured material. The ratio can also be measured by the NMR method described above.

The cured product may include one or more T units including silicon atoms bonded to aryl groups. For example, the T unit including the silicon atoms bonded to the aryl group has a ratio (T / Si) of the number of moles (T) of the T units and the number of moles (Si) of all the silicon atoms of the cured product to about 0.19 to about 0.6 Or in the range of about 0.3 to about 0.6. When the T unit is included in this range, for example, when applied to an optical semiconductor element such as an LED, an appropriate light extraction efficiency can be secured, and a cured body that can also efficiently control gas permeation characteristics can be provided. The said ratio (T / Si) can be adjusted through adjustment of the ratio of the said T unit and silicon atom contained in the polyorganosiloxane and crosslinking agent which form hardened | cured material. The ratio can also be measured by the NMR method described above.

The cured product may include one or more D units in the siloxane units. For example, in the D unit, the ratio (D / Si) of the number of moles (D) of the D units and the number of moles (Si) of all silicon atoms of the cured body is about 0.6 or less, 0.55 or less, 0.5 or less, 0.45 or less, or 0.4 or less The scope of can be included so that I can be. In other examples, the ratio (D / Si) may be greater than 0, 0.01 or more, 0.05 or more, 0.1 or more, or 0.15 or more. When the D unit is included in this range, for example, physical properties such as crack resistance, heat resistance, and thermal shock resistance are improved. The ratio (D / Si) can be adjusted by controlling the ratio of the D unit and silicon atoms included in the polyorganosiloxane and the crosslinking agent forming the cured product. The ratio can also be measured by the NMR method described above.

The cured product may include one or more epoxy groups, for example epoxy groups bonded to silicon atoms. An epoxy group can be contained in the range which the ratio (E / Si) of the number-of-moles (Si) of all the silicon atoms of a hardened | cured body, and the number-of-moles (E) of the said epoxy group are in the range of 0.0001-0.15, for example. The ratio (E / Si) may be 0.001 or more in another example. In another example, the ratio (E / Si) may be, for example, about 0.1 or less or about 0.05 or less. By including an epoxy group in this range, it can be provided with a cured body exhibiting excellent adhesion and can be efficiently applied to various applications. The ratio can be controlled by controlling the ratio of the epoxy group and silicon atoms contained in the polyorganosiloxane and the crosslinking agent, which forms a cured product.

The cured product may include one or more alkenyl groups bonded to silicon atoms. Typically, the cured product formed through the reaction between an aliphatic unsaturated bond such as an alkenyl group and a hydrogen atom bonded to a silicon atom is formed such that the aliphatic unsaturated bond, which is the reactive functional group, and the hydrogen atom bonded to the silicon atom are exhausted. Alkenyl groups may be present. The alkenyl group is, for example, about 0.15 or less, while the ratio (Ak / Si) of the number of moles (Ak) of the total alkenyl groups of the cured product and the number of moles (Si) of the total silicon atoms of the cured product exceeds 0, or 0.001 or more. Or about 0.1 or less. This has the advantage of improving the physical properties such as crack resistance, heat resistance and thermal shock resistance. The ratio (Ak / Si) is adjusted so that the ratio of the alkenyl group which is an aliphatic unsaturated bond in the mixture forming the cured body is higher than the ratio of hydrogen atoms bonded to the silicon atoms reacting with it, or This can be achieved by adjusting the alkenyl group to remain. The said ratio can also be measured by the NMR method mentioned above.

The alkenyl group may be included, for example, in M units. For example, the cured product may include units of the following Chemical Formula 3 as M units.

[Formula 3]

(R ¹ R ² ₂ SiO _1/2 )

In Formula 3, R ¹ may be an alkenyl group, and R ² may be a monovalent hydrocarbon group, for example, an alkyl group.

The unit of Formula 3 is an M unit including at least one alkenyl group, and this unit is, for example, a ratio of the number of moles (V) of the M units to the number of moles (Si) of all silicon atoms of the cured product (V / Si). ) May be greater than 0, or greater than 0.001 and within the range of about 0.15 or less or about 0.1 or less. Through this, a hardened body of appropriate physical properties can be obtained.

The cured product can be obtained by reacting a mixture containing an aliphatic unsaturated bond functional polyorganosiloxane and a compound (crosslinking agent) containing a hydrogen atom bonded to a silicon atom, for example, hydrogen siliconization reaction. In the reaction process, an alkylene group is generated by the reaction of the aliphatic unsaturated bond with the hydrogen atom, and the unit of Chemical Formula 1 may be generated.

Therefore, the unit of Formula 1 and the ratio (C / Si) are basically controlled by controlling the ratio between the aliphatic unsaturated bonds contained in the polyorganosiloxane and the hydrogen atoms present in the crosslinking agent and the catalyst promoting the reaction between them. May be controlled.

However, the present inventors are difficult to control the ratio only by controlling only the ratio between the aliphatic unsaturated bonds contained in the polyorganosiloxane and the hydrogen atoms present in the crosslinking agent and the catalyst promoting the reaction therebetween. It was confirmed that the environment of the reaction should also be considered. For example, optical semiconductors such as LEDs, which are the main uses of the cured bodies, include various housing materials such as polyphthalamide (PPA), polycyclohexylene-dimethylene terephthalates (PCT), epoxy molding compound (EMC), and white silicone, Depending on the application, any one of the above housing materials is selected and used. The hardening process in which the hardened body is formed is usually performed in a state in which a curable composition, that is, a mixture containing the polyorganosiloxane and a crosslinking agent is injected into the housing material, and according to the housing material, a lot of outgassing occurs during the hardening process. And out-gassing inhibits hardening to inhibit the reaction of the aliphatic unsaturated bonds and hydrogen atoms, thereby making it difficult to achieve the desired ratio (C / Si).

Therefore, in order to achieve the ratio (C / Si), a housing having a low outgassing is selected, or a prebaking process is performed on a housing in which outgassing occurs, and then injection and curing of the curable composition are performed. It may be advantageous to proceed.

In addition to the above, there are various factors related to the curing of the curable composition, and in consideration of such factors, the curing reaction needs to proceed so that the ratio (C / Si, etc.) can be achieved.

As an aliphatic unsaturated bond functional polyorganosiloxane which forms the said hardened body, the polyorganosiloxane which has an average unit of following General formula (4) can be used, for example.

[Formula 4]

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

In Formula 4, P is an alkenyl group, Q is an epoxy group alkoxy group or monovalent hydrocarbon group, and a and b are numbers such that a + b is 1 to 2.2 and a / (a + b) is 0.001 to 0.5. .

In the present specification, the polyorganosiloxane having a specific average unit means that the polyorganosiloxane is not only a single component having the average unit but also a mixture of two or more components and taking the average of the composition of the mixture. It may also be included in the case displayed in the average unit.

In one example, the polyorganosiloxane having an average unit of Formula 4 may include at least one of linear polyorganosiloxane, partially cross-linked polyorganosiloxane, or cross-linked polyorganosiloxane.

As used herein, the term linear polyorganosiloxane may mean a polyorganosiloxane including only M and D units as siloxane units, and the term partially crosslinked polyorganosiloxane includes T or Q units together with D units. A polyorganosiloxane having a sufficiently long linear structure derived from D units, having a ratio of D units (D / (D + T + Q)) to total D, T and Q units of 0.7 or more and less than 1 Can be. As used herein, the term crosslinked polyorganosiloxane essentially includes T or Q units, and may mean a polyorganosiloxane having a ratio (D / (D + T + Q)) of 0 or more and less than 0.7.

In Formula 4, a + b may be at least 1.1, at least 1.2, at least 1.3, or at least 1.4. Also, in Formula 4, a + b may be 2.1 or less, 2.0 or less, or 1.9 or less.

In Formula 4, a / (a + b) may be at least 0.005, at least 0.01, at least 0.03, or at least 0.06 in another example. Also, in Formula 4, a / (a + b) may be 0.4 or less, 0.3 or less, 0.25 or less, 0.2 or less, or 0.15 or less in another example.

In Formula 4, one or two or more of Q may be an aryl group. For example, in the formula (4), the aryl group of Q has a ratio (Ar / Si) of the number of moles (Ar) of the aryl group to the number of moles (Si) of all the silicon atoms contained in the polyorganosiloxane of 0.3 to 1.0 or 0.5 to 0.5. May be present in an amount such that 1.0.

At least one of Q in Formula 4 may be an epoxy group. For example, the epoxy group of Q in the formula (4), the ratio (E / Si) of the number of moles (E) of the epoxy group to the number of moles (Si) of the total silicon atoms contained in the polyorganosiloxane is about 0.2 or less, about 0.15 or less , About 0.1 or less, about 0.05 or less, or about 0.03 or less.

The polyorganosiloxane of the average unit of formula (4) is, for example, the weight average molecular weight (Mw) in the range of about 1000 to 10,000, about 1500 to about 8,000, about 1500 to 6000, about 1500 to 4000 or about 1500 to 3000 Can have As used herein, the term weight average molecular weight may refer to a conversion value for standard polystyrene measured by gel permeation chromatography (GPC). Unless otherwise specified, the term molecular weight may mean weight average molecular weight. The molecular weight of the polyorganosiloxane of the average unit of the formula (4) can be adjusted within the above range to effectively maintain moldability or workability before curing or strength after curing.

The compound containing the hydrogen atom bonded to the silicon atom contained in the mixture may be, for example, a linear, partially crosslinked or crosslinked polyorganosiloxane having one or two or more hydrogen atoms.

For example, the compound may have an average unit of Formula 5 below.

[Formula 5]

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

In Formula 5, Q is an epoxy group, an alkoxy group or a monovalent hydrocarbon group, c and d are numbers such that c + d is 1 to 2.8 and c / (c + d) is 0.001 to 0.34.

In Formula 5 c + d may be in the range of 1.5 to 2.8, about 2 to 2.8 or about 2.3 to 2.8 in another example. Also, in Formula 5, c / (c + d) may be in the range of about 0.005 to 0.34, about 0.01 to 0.34, about 0.05 to 0.34, about 0.1 to 0.34, or about 0.15 to 0.34.

Such a compound may be a curing agent capable of reacting with the aliphatic unsaturated bonds of the aliphatic unsaturated bond functional polyorganosiloxane described above to crosslink the mixture to form a cured product. For example, the hydrogen atom of the compound may react with the aliphatic unsaturated bond of the aliphatic unsaturated bond functional polyorganosiloxane to form a cured product.

One or two or more of Q in the average unit of formula (5) 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 all silicon atoms contained in the compound of the average unit of the formula (5) is, for example, 0.25 or more, 0.3 In the above, Q may be an aryl group in a range which may be in a range of about 0.3 to 1.0 or about 0.5 to 1.0.

Compounds of average units of formula (5) may be solid or liquid. If the compound is a liquid, the viscosity at 25 ° C. may fall within the range of 300 mPa · s or less or 300 mPa · s or less. By controlling the viscosity as described above, the processability of the mixture and the hardness characteristics of the cured product can be maintained excellently. The compound may, for example, have a molecular weight of less than 1,000 or less than 800. By adjusting the molecular weight in the above range, the strength and the like of the cured product can be maintained in an appropriate range. The lower limit of the molecular weight of the compound is not particularly limited, and may be, for example, 250.

As the compound of the average unit of Formula 5, all kinds of compounds may be used as long as the above properties are satisfied. For example, the compound of formula 6 may be used as the compound.

[Formula 6]

In formula (6), each R is independently hydrogen, an epoxy group, or a monovalent hydrocarbon group, and n is a number in the range of 1 to 10. In Formula 6, R may be, for example, an aryl group or an alkyl group, and may be an aryl group and an alkyl group within a range satisfying the ratio (Ar / Si) of the aryl group of the compound of the average unit of Formula 5 described above.

N in Formula 6 may be, for example, 1 to 8, 1 to 6, 1 to 4, 1 to 3 or 1 to 2.

The proportion, viscosity or molecular weight of the aryl group of the compound of formula 6 may be within the above range.

The compound containing a hydrogen atom bonded to the silicon atom, for example, the content of the compound of the average unit of formula (5) or the compound of formula (6) may be selected within the range such that the mixture is cured to have the above characteristics have. For example, the content of the compound is a ratio of the number of moles (H) of hydrogen atoms of the compound (H / Ak) to the number of moles (Ak) of aliphatic unsaturated bonds of the aliphatic unsaturated bond functional polyorganosiloxane is 0.5 to 3.0, 0.7 to 2 or 1.05 to 1.3 can be selected.

The mixture may further comprise a hydrosilylation catalyst. Hydrosilylation catalysts can be used to accelerate the hydrogensilylation reaction. As the hydrosilylation catalyst, any conventional component known in the art can be used. Examples of such a catalyst include platinum, palladium or rhodium-based catalysts. In consideration of catalyst efficiency, a platinum-based catalyst may be used, and examples of such catalysts include chloroplatinic acid, platinum tetrachloride, olefin complexes of platinum, alkenyl siloxane complexes of platinum or carbonyl complexes of platinum, and the like. It is not limited.

The content of the hydrosilylation catalyst is not particularly limited as long as it is contained in a so-called catalytic amount, that is, an amount that can act as a catalyst. Typically, it may 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 mixture may also further include an tackifier in view of further improvement of adhesion to various substrates. The tackifier is a component capable of improving self adhesiveness, and in particular, can improve self adhesiveness to metals and organic resins.

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

When the adhesion imparting agent is included, for example, it may be included in a ratio of 0.1 parts by weight to 20 parts by weight with respect to 100 parts by weight of the solid content of the mixture, the content may be appropriately changed in consideration of the desired adhesive improvement effect.

The mixture is, if necessary, 2-methyl-3-butyn-2-ol, 2-phenyl-3-1-butyn-2ol, 3-methyl-3-penten-1-yne, 3,5-dimethyl- Reaction inhibitors such as 3-hexene-1-yne, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane or ethynylcyclohexane; Inorganic fillers such as silica, alumina, zirconia or titania; Carbon functional silanes having an epoxy group and / or an alkoxysilyl group, partial hydrolysis condensates or siloxane compounds thereof; Thixotropy-imparting agents, such as fumed silica which can be used together with polyether etc .; filler; Phosphor; Conductivity imparting agents such as metal powders such as silver, copper or aluminum, and various carbon materials; Additives, such as a color tone adjuster, such as a pigment or dye, may further contain a kind or two or more types.

Conditions for curing the mixture to form a cured body are set such that the final cured body includes the above-described configuration. For example, the cured product may be formed by maintaining the mixture at a temperature of about 60 ° C. to 200 ° C. for 10 minutes to 5 hours.

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

As a light emitting diode, the light emitting diode etc. which were formed by laminating | stacking a semiconductor material on a board | substrate can be illustrated, for example. Examples of the semiconductor material may include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, or SiC, but are not limited thereto. In addition, as the substrate, sapphire, spinel, SiC, Si, ZnO, or GaN single crystal may be exemplified.

At the time of manufacture of a light emitting diode, a buffer layer may be formed between a board | substrate and a semiconductor material as needed. As the buffer layer, GaN or AlN may be used. The method of laminating the semiconductor material on the substrate is not particularly limited, and for example, the MOCVD method, the HDVPE method, or the liquid phase growth method can be used. In addition, the structure of the light emitting diode may be, for example, a monojunction having a MIS junction, a PN junction, a PIN junction, a heterojunction, a double heterojunction, or the like. In addition, the light emitting diode may be formed in a single or multiple quantum well structure.

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

The light emitting diode may be encapsulated with the cured body, and thus the encapsulation process may be performed using the above-mentioned mixture. Encapsulation of the light emitting diode may be carried out only with the mixture, and in some cases, other encapsulation materials may be used in combination with the mixture. When using 2 types of sealing materials together, after sealing using the said mixture, you may seal with the other sealing material, you may seal with the other sealing material first, and then seal the surrounding with the said mixture. As another sealing material, an epoxy resin, a silicone resin, an acrylic resin, a urea resin, an imide resin, glass, etc. are mentioned.

As a method of encapsulating a light emitting diode in a mixture, for example, the mixture is pre-injected into a mold form die, a lead frame in which the light emitting diode is fixed is immersed therein, the method of curing the mixture, and a light emitting diode inserted therein. A method of pouring the mixture in the formwork and curing can be used. As a method of injecting a mixture, injection by a dispenser, transfer molding, injection molding, etc. can be illustrated. In addition, as another encapsulation method, the mixture is dropped onto a light emitting diode, applied by stencil printing, screen printing or a mask, and cured, the mixture is injected by a dispenser or the like into a cup having a light emitting diode disposed at the bottom thereof, Curing method and the like can be used.

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

The shape of the sealing material is not particularly limited, and can be formed, for example, in the form of a shell lens, a plate or a thin film.

According to the conventionally known method, further performance improvement of a light emitting diode can be aimed at. As a method for improving the performance, for example, a method of providing a light reflection layer or a light collecting layer on the back surface of a light emitting diode, a method of forming a complementary coloring part at the bottom, and providing a layer on the light emitting diode that absorbs light having a wavelength shorter than the main emission peak Method of encapsulating the light emitting diode and then molding it with a hard material, inserting and fixing the light emitting diode into the through hole, and connecting the light emitting diode to a lead member by flip chip connection or the like to extract light from the substrate direction. The method etc. are mentioned.

An optical semiconductor, for example, a light emitting diode is, for example, a backlight of a liquid crystal display (LCD), a light source, a light source of various sensors, a printer, a copier, a vehicle instrument light source, a signal lamp, an indicator light, a display, and the like. It can be effectively applied to a device, a light source of a planar light emitting body, a display, a decoration or various lights.

Exemplary cured bodies, for example, when applied to an optical semiconductor such as an LED, can provide a device having a low luminance degradation, excellent crack resistance, and excellent long-term reliability even when the device is used for a long time. Hardened | cured material is excellent in workability, workability, adhesiveness, etc., and does not produce cloudiness, stickiness on the surface, etc. Moreover, the hardened | cured material is excellent in high temperature heat resistance, gas barrier property, etc. The cured product can be applied to, for example, an encapsulant or an adhesive material of a semiconductor element.

Hereinafter, the mixture will be described in more detail with reference to Examples and Comparative Examples, but the scope of the mixture is not limited by the following Examples.

Hereinafter, the symbols Vi, Ph, Me and Ep represent a vinyl group, a phenyl group, a methyl group and a 3-glycidoxypropyl group, respectively.

Physical properties of the cured product prepared in Examples and Comparative Examples were evaluated in the following manner.

1. 몰비율 평가 방식1. Mole ratio evaluation method

The ratio (C / Si) of the number of moles (C) of silicon atoms connected to the ethylene group and the number of moles of carbon atoms (Si) of all the silicon atoms (C / Si) connected by the ethylene group present in the cured product is known in the known ²⁹ Si NMR method Measured accordingly. ²⁹ reference compound during the measurement of the Si NMR using a TMS (Tetramethylsilane dilute in CDCl ₃₎ was dissolved in CDCl ₃ and chemical shifts were measured (chemical shift).

2. 고온 장기 신뢰성2. High temperature long term reliability

Device properties are evaluated using LED packages made of polyphthalamide (PPA) or polycyclohexylphthalamide (PCT). Specifically, a mixture prepared in a PPA or PCT cup is dispensed and cured under the conditions given in each example or comparative example to produce a surface mount LED. Subsequently, the manufactured LED was operated for 1000 hours while maintaining a current of 50 mA while keeping the manufactured LED at 85 ° C., and then the reduction rate of the luminance after the operation compared to the initial luminance before the operation was measured to evaluate the reliability according to the following criteria.

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

B: When the luminance reduction rate is more than 5% but less than 10%

C: When luminance reduction exceeds 10%

3. 내열 충격성3. Thermal shock resistance

After holding the LED package for 15 minutes at -40 ° C for 15 minutes and again at 100 ° C for 1 cycle, after 200 cycles, the number of unlighted packages compared to the total number of 20 evaluated packages was evaluated to evaluate thermal shock resistance. It was.

실시예 1.Example 1.

119.5 g of an aliphatic unsaturated bond functional polyorganosiloxane in a solid state having an average unit of the formula (A) having a weight average molecular weight of about 2300 and 29.2 g of the compound of the formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining a catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in an amount such that the catalyst was used. Subsequently, the prepared mixture was kept at 140 ° C. for 1 hour to prepare a cured product. Curing of the cured product was performed by dispensing the mixture into a PPA cup. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Was found to be about 0.3. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.65, and the ratio of silicon atoms to the number of moles (T) of all T units in the cured product The number of moles (Si) was about 0.51, the ratio of moles (Si) of silicon atoms to the number of moles (D) of the total D units was about 0.19, and the silicon atoms to the number of moles (V) of all vinyl groups in the cured product. The ratio (V / Si) of the number of moles (Si) of was 0.

[Formula A]

(ViMe ₂ SiO _1/2 ) _0.19 (Me ₂ SiO _2/2 ) _0.14 (Ph ₂ SiO _2/2 ) _0.07 (PhSiO _3/2 ) _0.60

[Formula B]

(HMe ₂ SiO _1/2 ) ₂ (Ph ₂ SiO _2/2 )

실시예 2. Example 2.

124.2 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (C) having a weight average molecular weight of about 2300 and 29.2 g of the compound of Formula B are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Was found to be about 0.3. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.70, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles (Si) of was about 0.53, the ratio of moles (Si) of silicon atoms (D / Si) to the number of moles (D) of all D units was about 0.17, and the number of moles (V) of all vinyl groups in the cured product. The ratio (V / Si) of the number-of-moles (Si) of silicon atoms was zero.

[Formula C]

(ViMe ₂ SiO _1/2 ) _0.19 (MeEpSiO _2/2 ) _0.01 (MePhSiO _2/2 ) _0.20 (PhSiO _3/2 ) _0.60

실시예 3. Example 3.

122.1 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (D) having a weight average molecular weight of about 2500 and 29.2 g of the compound of the formula (B), wherein the content of Pt (0) is 2 ppm The catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was combined to prepare a mixture. Subsequently, after dispensing the mixture in a PPA cup as in Example 1, the mixture was maintained at 140 ° C. for 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Was found to be about 0.3. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.67, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles of Si was about 0.49, the ratio of moles of silicon atoms (D / Si) to the number of moles (D) of the total D units was about 0.19, and the silicon to the number of moles (V) of all the vinyl groups in the cured product. The ratio (V / Si) of the number of moles of atoms (Si) was zero.

[Formula D]

(ViMe ₂ SiO _1/2 ) _0.19 (MeEpSiO _2/2 ) _0.01 (MePhSiO _2/2 ) _0.20 (PhSiO _3/2 ) _0.57 (SiO _4/2 ) _0.03

실시예 4. Example 4.

121.9 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (E) having a weight average molecular weight of about 2600 and 18.5 g of the compound of the above formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, the prepared mixture was dispensed into a PCT cup, and the cured product was prepared by maintaining the temperature at 140 ° C. for about 1 hour. As the PCT cup in which the mixture was dispensed, a PCT cup prebaked at 160 ° C. for about 30 minutes before dispensing the mixture was used. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Was found to be about 0.2. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.79, and the ratio of silicon atoms to the number of moles (T) of all T units in the cured product The number of moles (Si) was about 0.46, the ratio of moles (Si) of silicon atoms (D / Si) to the number of moles (D) of all D units was about 0.30, and the number of moles (V) of all vinyl groups in the cured product. The ratio (V / Si) of the number-of-moles (Si) of silicon atoms was zero.

[Formula E]

(ViMe ₂ SiO _1/2 ) _0.12 (Me ₂ SiO _2/2 ) _0.18 (Ph ₂ SiO _2/2 ) _0.1 (PhSiO _3/2 ) _0.60

실시예 5. Example 5.

120.3 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (F) having a weight average molecular weight of about 2300 and 43.1 g of the compound of the above formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.4. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.72, and the ratio of silicon atoms to the number of moles (T) of all T units in the cured product The number of moles (Si) was about 0.46, the ratio of the number of moles (Si) of silicon atoms (D / Si) to the number of moles (D) of the total D units was about 0.20, and the silicon to the number of moles (V) of all vinyl groups in the cured product. The ratio (V / Si) of the number of moles of atoms (Si) was zero.

Formula F]

(ViMe ₂ SiO _1/2 ) _0.28 (MeEpSiO _2/2 ) _0.01 (MePhSiO _2/2 ) _0.11 (PhSiO _3/2 ) _0.60

실시예 6. Example 6.

123.9 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (G) having a weight average molecular weight of about 2300 and 23.4 g of the compound of the formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Was found to be about 0.2. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured body was about 0.71, and the silicon atoms to the number of moles (T) of all T units in the cured body. The number of moles (Si) of was about 0.45, the ratio of moles (Si) of silicon atoms (D / Si) to the number of moles (D) of all D units was about 0.26, and the number of moles (V) of all vinyl groups in the cured product. The ratio (V / Si) of the number-of-moles (Si) of silicon atoms was zero.

[Formula G]

(ViMe ₂ SiO _1/2 ) _0.12 (Me ₂ SiO _2/2 ) _0.16 (MeViSiO _2/2 ) _0.04 (Ph ₂ SiO _2/2 ) _0.08 (PhSiO _3/2 ) _0.60

실시예 7. Example 7.

121.9 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (H) having a weight average molecular weight of about 2300 and 36.6 g of the compound of the above formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Was found to be about 0.3. Further, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.62, and the ratio of silicon atoms to the number of moles (T) of all T units in the cured product The number of moles (Si) was about 0.40, the ratio of the number of moles (Si) of silicon atoms (D / Si) to the number of moles (D) of the total D units was about 0.20, and the silicon to the number of moles (V) of all vinyl groups in the cured product. The ratio (V / Si) of the number of moles of atoms (Si) was zero.

[Formula H]

(ViMe ₂ SiO _1/2 ) _0.21 (Me ₂ SiO _2/2 ) _0.10 (MeViSiO _2/2 ) _0.04 (Ph ₂ SiO _2/2 ) _0.05 (PhSiO _3/2 ) _0.60

실시예 8.Example 8.

118.7 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (I) having a weight average molecular weight of about 2100 and 52.7 g of the compound of the above formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.4. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.57, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles (Si) of was about 0.34, and the ratio (D / Si) of the number of moles of silicon atoms (D) to the number of moles (D) of the total D units was about 0.17 and the number of moles (V) of the total vinyl groups in the cured product. The ratio (V / Si) of the number-of-moles (Si) of silicon atoms was zero.

[Formula I]

(ViMe ₂ SiO _1/2 ) _0.32 (Me ₂ SiO _2/2 ) _0.06 (MeViSiO _2/2 ) _0.04 (Ph ₂ SiO _2/2 ) _0.03 (PhSiO _3/2 ) _0.55

실시예 9.Example 9.

117.3 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (J) having a weight average molecular weight of about 2100 and 60.0 g of the compound of the above formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.45. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.57, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles (Si) of was about 0.32, and the ratio (D / Si) of the number of moles of silicon atoms (D) to the number of moles (D) of the total D units was about 0.17 and the number of moles (V) of the total vinyl groups in the cured product. The ratio (V / Si) of the number-of-moles (Si) of silicon atoms was zero.

[Formula J]

(ViMe ₂ SiO _1/2 ) _0.37 (Me ₂ SiO _2/2 ) _0.04 (MeViSiO _2/2 ) _0.04 (Ph ₂ SiO _2/2 ) _0.02 (PhSiO _3/2 ) _0.53

실시예 10. Example 10.

119.9 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (M) having a weight average molecular weight of about 2300 and 23.4 g of the compound of the above formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup as in Example 1, the mixture was maintained at 140 ° C. for 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Was found to be about 0.2. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.67, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles of Si was about 0.44, the ratio of moles of silicon atoms (D / Si) to the number of moles (D) of the total D units was about 0.25, and the number of moles (V) of the total vinyl groups in the cured product. The ratio (V / Si) of the number-of-moles (Si) of silicon atoms was zero.

[Formula M]

(ViMe ₂ SiO _1/2 ) _0.12 (Me ₂ SiO _2/2 ) _0.18 (Ph ₂ SiO _2/2 ) _0.10 (PhSiO _3/2 ) _0.56 (ViSiO _3/2 ) _0.04

실시예 11. Example 11.

119.1 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (N) having a weight average molecular weight of about 2300 and 36.6 g of the compound of the above formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Was found to be about 0.3. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.63, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles (Si) of was about 0.40, the ratio (D / Si) of the number of moles of silicon atoms (D) to the number of moles (D) of the total D units was about 0.20, and the number of moles of all vinyl groups (V) in the cured product. The ratio (V / Si) of the number-of-moles (Si) of the silicon atoms was 0.

[Formula N]

(ViMe ₂ SiO _1/2 ) _0.21 (Me ₂ SiO _2/2 ) _0.11 (Ph ₂ SiO _2/2 ) _0.08 (PhSiO _3/2 ) _0.56 (ViSiO _3/2 ) _0.04

실시예 12. Example 12.

114.7 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (O) having a weight average molecular weight of about 2300 and 52.7 g of the compound of the above formula (B), wherein the content of Pt (0) is 2 ppm The catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was combined to prepare a mixture. Subsequently, after dispensing the mixture in a PPA cup as in Example 1, the mixture was maintained at 140 ° C. for 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.4. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.58, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles (Si) of was about 0.35, the ratio (D / Si) of the number of moles of silicon atoms (D) to the number of moles (D) of the total D units was about 0.18, and the number of moles of all vinyl groups (V) in the cured product. The ratio (V / Si) of the number-of-moles (Si) of the silicon atoms was 0.

[Formula O]

(ViMe ₂ SiO _1/2 ) _0.32 (Me ₂ SiO _2/2 ) _0.08 (Ph ₂ SiO _2/2 ) _0.05 (PhSiO _3/2 ) _0.51 (ViSiO _3/2 ) _0.04

실시예 13. Example 13.

113.3 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (P) having a weight average molecular weight of about 2200 and 60.0 g of the compound of the formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.45. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.58, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles (Si) of was about 0.33, the ratio (D / Si) of the number of moles of silicon atoms (D) to the number of moles (D) of the total D units was about 0.17, and the number of moles of all vinyl groups (V) in the cured product. The ratio (V / Si) of the number-of-moles (Si) of the silicon atoms was 0.

[Formula P]

(ViMe ₂ SiO _1/2 ) _0.37 (Me ₂ SiO _2/2 ) _0.06 (Ph ₂ SiO _2/2 ) _0.04 (PhSiO _3/2 ) _0.49 (ViSiO _3/2 ) _0.04

비교예 1 Comparative Example 1

120.9 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (T) having a weight average molecular weight of about 2300 and 10.8 g of the compound of Formula B are blended, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.13. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.80, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles (Si) of was about 0.56, the ratio (D / Si) of the number of moles of silicon atoms (D) to the number of moles (D) of the total D units was about 0.34, and the number of moles of all vinyl groups (V) in the cured product. The ratio (V / Si) of the number-of-moles (Si) of the silicon atoms was 0.

[Formula S]

(ViMe ₂ SiO _1/2 ) _0.07 (Me ₂ SiO _2/2 ) _0.23 (Ph ₂ SiO _2/2 ) _0.10 (PhSiO _3/2 ) _0.60

비교예 2 Comparative Example 2

109.4 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (U) having a weight average molecular weight of about 2000 and 76.9 g of the compound of the above formula (B) are combined, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.58. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.58, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles (Si) of was about 0.26, the ratio (D / Si) of the number of moles of silicon atoms (D) to the number of moles (D) of the total D units was about 0.21, and the number of moles of all vinyl groups (V) in the cured product. The ratio (V / Si) of the number-of-moles (Si) of the silicon atoms was 0.

[Formula U]

(ViMe ₂ SiO _1/2 ) _0.50 (Me ₂ SiO _2/2 ) _0.07 (Ph ₂ SiO _2/2 ) _0.03 (PhSiO _3/2 ) _0.40

비교예 3 Comparative Example 3

126.8 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (K) having a weight average molecular weight of about 2300, and 10.2 g of the compound of the formula (B), wherein the content of Pt (0) is 2 ppm The catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was combined to prepare a mixture. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.1. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.80, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles (Si) of was about 0.56, the ratio (D / Si) of the number of moles of silicon atoms (D) to about the number of moles (D) of the total D units was about 0.32, and the number of moles of all vinyl groups (V) in the cured product. The ratio (V / Si) of the number-of-moles (Si) of the silicon atoms was 0.

[Formula K]

(ViMe ₂ SiO _1/2 ) _0.03 (Me ₂ SiO _2/2 ) _0.19 (MeViSiO _2/2 ) _0.04 (Ph ₂ SiO _2/2 ) _0.10 (PhSiO _3/2 ) _0.64

비교예 4 Comparative Example 4

107.3 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (L) having a weight average molecular weight of about 2300 and 102.5 g of the compound of Formula (B) are blended, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.65. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.48, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles of Si was about 0.14, the ratio of moles of silicon atoms (D / Si) to the number of moles (D) of the total D units was about 0.20, and the number of moles (V) of the total vinyl groups in the cured product. The ratio (V / Si) of the number-of-moles (Si) of silicon atoms was zero.

[Formula K]

(ViMe ₂ SiO _1/2 ) _0.06 (Me ₂ SiO _2/2 ) _0.02 (MeViSiO _2/2 ) _0.04 (Ph ₂ SiO _2/2 ) _0.01 (PhSiO _3/2 ) _0.27

비교예 5 Comparative Example 5

129.6 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (R) having a weight average molecular weight of about 2300 and 10.2 g of the compound of Formula B are blended, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.1. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.83, and the silicon atoms to the number of moles (T) of all T units in the cured product The number of moles (Si) of was about 0.57, the ratio (D / Si) of the number of moles of silicon atoms (D) to the number of moles (D) of the total D units was about 0.32, and the number of moles (V) of all vinyl groups in the cured product. The ratio (V / Si) of the number-of-moles (Si) of the silicon atoms was 0.

[Formula R]

(ViMe ₂ SiO _1/2 ) _0.03 (Me ₂ SiO _2/2 ) _0.19 (Ph ₂ SiO _2/2 ) _0.14 (PhSiO _3/2 ) _0.60 (ViSiO _3/2 ) _0.04

비교예 6 Comparative Example 6

107.6 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the formula (S) having a weight average molecular weight of about 2300 and 102.5 g of the compound of the formula (B) are blended, and the content of Pt (0) is 2 ppm. A mixture was prepared by combining the catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in amounts. Subsequently, after dispensing the mixture in a PPA cup in the same manner as in Example 1, the mixture was maintained at 140 ° C. for about 1 hour to prepare a cured product. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.65. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.48, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles (Si) of was about 0.15, the ratio (D / Si) of the number of moles of silicon atoms (D) to the number of moles (D) of the total D units was about 0.20, and the number of moles of all vinyl groups (V) in the cured product. The ratio (V / Si) of the number-of-moles (Si) of the silicon atoms was 0.

[Formula R]

(ViMe ₂ SiO _1/2 ) _0.66 (Me ₂ SiO _2/2 ) _0.04 (Ph ₂ SiO _2/2 ) _0.03 (PhSiO _3/2 ) _0.23 (ViSiO _3/2 ) _0.04

비교예 7 Comparative Example 7

A cured product was prepared in the same manner as in Example 4, except that the PCT cup without prebaking was used as the PCT cup to which the mixture was dispensed. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Was found to be about 0.08. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.79, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles of Si was about 0.52, the ratio of moles of silicon atoms (D / Si) to the number of moles (D) of the total D units was about 0.30, and the number of moles (V) of all the vinyl groups in the cured product. The ratio (V / Si) of the number-of-moles (Si) of silicon atoms was zero.

비교예 8 Comparative Example 8

Same as Example 4 except that a mixture containing a catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in an amount of 0.2 ppm of Pt (0) was used. The cured product was produced in a manner. As a result of analysis of the prepared cured product, the cured product contains silicon atoms connected by an ethylene group, and the ratio of the number of moles of carbon atoms (C) to the number of moles of silicon atoms (Si) of the ethylene groups (C / Si) ) Is about 0.13. In addition, the ratio (Ar / Si) of the number of moles (Si) of all silicon atoms to the number of moles (Ar) of all the aryl groups present in the cured product was about 0.79, and the silicon atoms to the number of moles (T) of all T units in the cured product. The number of moles of Si was about 0.52, the ratio of moles of silicon atoms (D / Si) to the number of moles (D) of the total D units was about 0.30, and the number of moles (V) of all the vinyl groups in the cured product. The ratio (V / Si) of the number-of-moles (Si) of silicon atoms was zero.

The result of having measured physical property about the hardened | cured material of the said Example and a comparative example was put together in Table 1, and described.

Table 1

	High temperature reliability	Thermal shock resistance
Example 1	A	0/20
Example 2	A	0/20
Example 3	A	0/20
Example 4	A	0/20
Example 5	A	2/20
Example 6	B	4/20
Example 7	A	0/20
Example 8	A	3/20
Example 9	A	4/20
Example 10	B	5/20
Example 11	A	0/20
Example 12	A	0/20
Example 13	A	3/20
Comparative Example 1	C	15/20
Comparative Example 2	C	12/20
Comparative Example 3	C	14/20
Comparative Example 4	C	11/20
Comparative Example 5	C	14/20
Comparative Example 6	C	14/20
Comparative Example 7	C	20/20
Comparative Example 8	C	20/20

Claims

A reactant of a mixture comprising an aliphatic unsaturated bond functional polyorganosiloxane and a compound having a hydrogen atom bonded to a silicon atom, comprising a unit of formula (1), and the number of moles of carbon atoms present in A of formula (1) C) and a cured product in which the ratio (C / Si) of the number of moles (Si) of all silicon atoms is in the range of 0.15 to 0.55:

[Formula 1]

(R 2 SiO 1/2 A 1/2 )

In formula (1), each R is independently hydrogen, an epoxy group, an alkoxy group, or a monovalent hydrocarbon group, and A is an alkylene group having 1 to 4 carbon atoms.
The cured product according to claim 1, wherein the ratio (C / Si) of the number of moles (C) of carbon atoms and the number of moles (Si) of all silicon atoms in A of Formula 1 is in the range of 0.15 to 0.45.
The cured product according to claim 1, wherein the ratio (C / Si) of the number of moles (C) of carbon atoms and the number of moles (Si) of all silicon atoms in A of Formula 1 is in the range of 0.2 to 0.45.
The cured product according to claim 1, comprising an aryl group bonded to a silicon atom, wherein the ratio (Ar / Si) of the number of moles (Ar) of the aryl groups and the number of moles (Si) of all silicon atoms is in the range of 0.2 to 1.2.
The cured product according to claim 1, comprising an aryl group bonded to a silicon atom, wherein the ratio (Ar / Si) of the number of moles (Ar) of the aryl groups and the number of moles (Si) of all the silicon atoms is in the range of 0.4 to 1.0.
2. A trifunctional siloxane unit having an aryl group bonded thereto, wherein the ratio (T / Si) of the number of moles (T) of the trifunctional siloxane units and the number of moles (Si) of all silicon atoms is 0.3 to 0.6. Cured product in range.
The cured product according to claim 1, comprising a bifunctional siloxane unit, wherein the ratio (D / Si) of the number of moles (D) of the difunctional siloxane units and the number of moles (Si) of all silicon atoms is 0.6 or less.
The hardening body of Claim 1 containing the epoxy group couple | bonded with the silicon atom.
The cured product of claim 1 comprising a siloxane unit of formula

[Formula 3]

(R 1 R 2 2 SiO 1/2 )

In formula (3), R 1 is an alkenyl group, R 2 is a monovalent hydrocarbon group.
The cured product according to claim 9, wherein the ratio (V / Si) of the number of moles (V) of the siloxane units of formula (3) and the number of moles (Si) of all the silicon atoms is 0.15 or less.
The cured product of claim 1, wherein the aliphatic unsaturated bond functional polyorganosiloxane has an average unit of Formula 4:

[Formula 4]

P a Q b SiO (4-ab) / 2

In Formula 4, P is an alkenyl group, Q is an epoxy group or a monovalent hydrocarbon group, a and b are such that a + b is in the range of 1 to 2.2 and a / (a + b) is in the range of 0.001 to 0.5. It is a number.
The cured product of claim 1, wherein the compound having a hydrogen atom bonded to a silicon atom has an average unit of Formula 5

[Formula 5]

H c Q d SiO (4-cd) / 2

In the formula (5), Q is an epoxy group or a monovalent hydrocarbon group, 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 0.001 to 0.34.
The cured product of claim 1, wherein the compound having a hydrogen atom bonded to a silicon atom is a compound of formula:

[Formula 6]

R in formula (6) is each independently hydrogen, an epoxy group or a monovalent hydrocarbon group, at least one of R is an aryl group, n is a number from 1 to 2.
The ratio of the number of moles of hydrogen atoms (H) of the compound according to claim 1, wherein the number of moles (Ak) of aliphatic unsaturated bonds of the aliphatic unsaturated bond functional polyorganosiloxane and the hydrogen atoms bonded to the silicon atoms in the mixture (H) / Ak) cured product in the range of 1.05 to 1.3.
The semiconductor element sealed with the sealing material containing the hardening body of Claim 1.
An optical semiconductor device sealed with an encapsulant comprising the cured product of claim 1.
A liquid crystal display comprising the optical semiconductor element of claim 16.
An illumination comprising the optical semiconductor element of claim 16.