KR101814212B1 - Organopolysiloxane composition - Google Patents

Abstract

The present invention provides a curable organopolysiloxane composition having a elongation change amount and a tensile strength change amount of 50% or less, respectively, after elongation and tensile strength of a cured state specimen after storage at 200 ° C for 168 hours.

Description

[0001] Organopolysiloxane composition [0002]

The present invention relates to an organopolysiloxane composition for encapsulating light-emitting diode elements, which has high reliability even in a high-temperature practical use environment.

In general, epoxy resin has been conventionally used as a sealing material for light-emitting diode elements. Epoxy resin has excellent transparency but has a high elastic modulus, so cracks are generated between wire, chip and epoxy resin under various temperature conditions and temperature changes, and wire bonding is broken, resulting in collapse of crystal structure of semiconductor material The luminous efficiency may be lowered. In addition, epoxy resins are brighter and more unsatisfactory in terms of heat resistance and light fastness to shorter wavelength light. When ultraviolet light or the like is transmitted through the epoxy resin, the bond of the organic polymer is broken and the optical and chemical properties of the resin are deteriorated. As a result, the epoxy resin eventually changes to the yellow color of the encapsulant itself, which affects the color of the light beam, thereby lowering the lifetime of the light emitting device.

On the other hand, application of a silicone resin has been proposed as a solution to the above problems. Silicone is superior to epoxy resin in heat resistance, weather resistance and the like as compared with organic resin, and is not only transparent but also difficult to discolor and physically deteriorate, so that application to light emitting diodes is increasing. However, these silicone resins are excellent in mechanical strength and chemical stability, but studies for securing a higher luminance have been continuously carried out.

Since the silicone resin composition disclosed in Japanese Patent Application Laid-Open No. 2002-265787 increases the crosslinking density of the siloxane and is important for improving the refractive index and the like of the cured product by the π-π interaction between aromatic rings, the silicone resin composition having a phenyl group and an alkenyl group Specific organohydrogenpolysiloxane having a specific organopolysiloxane and a phenyl group is additionally cured to obtain a high hardness and high transparency resin.

However, when the phenyl-containing reactive polysiloxane is used to control the refractive index of the high-refractive index material, the reaction rate is slower than that of the methyl-based reactive polysiloxane due to the structural causes of the phenyl-containing polysiloxane.

When a phenyl-containing reactive polysiloxane is used, a lot of heat and time are required in the curing process in order to achieve the desired mechanical properties, but economically limited curing time and temperature must be applied in the process. Therefore, after mounting on an actual device, additional reaction proceeds due to heat generated in the use environment, thereby changing the mechanical properties such as modulus. This leads to an increase in the internal stress. In the extreme case, the increase of the internal stress can not be caused by the breakage of the wire. In most cases, deterioration or cracking of the interface causes accelerated oxidation and corrosion of the phosphor. Respectively.

In recent years, there has been an increasing demand to apply LEDs to a large-area liquid crystal display device or an illumination. As a result, a large number of chips are mounted on a dense package or the amount of applied current increases, It is becoming.

Therefore, there is a need for a sealing composition that does not change the mechanical properties of the sealing material due to post curing even in a high temperature use environment.

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and it is an object of the present invention to provide a curable organopolysiloxane composition having high reliability.

Another object of the present invention is to provide an encapsulant for a light emitting diode device comprising a cured product of the composition according to the present invention.

It is still another object of the present invention to provide a light emitting diode device in which a light emitting diode device is sealed by the sealing material according to the present invention.

The inventors of the present invention have found that the increase in internal stress due to post-curing of the sealing material is the most important factor in improving the reliability of the entire light-emitting diode device. In addition, due to the problem of reactivity of the phenyl group-containing reactive polysiloxane, the cause of the deterioration of the efficiency due to peeling, crack (crack), or breakage due to the increase of the internal stress has been repeatedly solved. As a result, The content, the structure, and the combination thereof, a sealant composition capable of suppressing internal stress change by postcuring was developed.

In order to achieve the above object, the present invention provides a curable organopolysiloxane composition having a elongation change amount and a tensile strength change amount of 50% or less, respectively, after elongation and tensile strength of a cured state specimen after storage at 200 ° C for 168 hours.

The composition may include compounds of the following formulas (1) to (3).

[Chemical Formula 1]

^{(R 1 R 2 R 3 SiO} 1/2) x · (R 4 R 5 SiO 2/2) y · (R 6 SiO 3/2) z

(2)

R ⁷ Si (OSiR ⁸ R ⁹ R ¹⁰ ) ₃

(3)

In this formula,

R ¹ to R ³ and R ⁸ to R ¹⁰ are each independently a monovalent hydrocarbon group of 1 to 12 carbon atoms excluding an alkenyl group or alkenyl group having 2 to 10 carbon atoms, provided that at least one of R ¹ to R ³ and R ⁸ to one or more of R ¹⁰ is an alkenyl group of 2 to 10 carbon atoms,

R ⁴ to R ⁷ are each independently a monovalent hydrocarbon group of 1 to 12 carbon atoms excluding an alkenyl group,

R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently hydrogen; Or a monovalent hydrocarbon group of 1 to 12 carbon atoms excluding an alkenyl group,

R ¹³ and R ¹⁴ are each independently a monovalent hydrocarbon group of 1 to 12 carbon atoms excluding an alkenyl group,

x, y and z satisfy 0 <x <1, 0 <y <1, 0 <z <1 and x + y + z =

n is an integer of 1 to 100;

The present invention also provides an encapsulant for a light emitting diode device comprising a cured product of the composition according to the present invention.

The present invention also provides a light emitting diode device in which a light emitting diode device is sealed by the sealing material according to the present invention.

When the composition according to the present invention is used as an encapsulant of a light emitting diode device, it suppresses post-curing according to the use environment, and thus prevents a change in internal stress, thereby providing high reliability and excellent lifetime of the device.

1 is a cross-sectional view of a light emitting diode device according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The definitions of the terms used in the present invention are as follows.

"Elongation change rate" means the percentage difference between the elongation value (heat resistance elongation) of the specimen after being stored at 200 ° C. for 168 hours and the elongation value (initial elongation) of the cured specimen. That is, the rate of elongation change means (initial elongation-heat resistance elongation) / initial elongation X 100. The composition of the present invention may have a rate of change of elongation of 50% or less, for example, 40% or less, 35% or less, or 30% or less.

Means the percentage of the difference between the tensile strength value (initial tensile strength) of the cured state specimen and the tensile strength value (heat resistance tensile strength) of the specimen after the cured state specimen is stored at 200 DEG C for 168 hours. That is, the amount of change in tensile strength means (heat resistance tensile strength-initial tensile strength) / initial tensile strength X 100. The composition of the present invention may have a tensile strength change of 50% or less, for example 45% or less, 40% or less, or 35% or less. The elongation and tensile strength are measured according to the KS6518 method.

The "hardness change amount" means the hardness value (initial hardness) of the cured state specimen and the percentage of the difference in the hardness value (heat resistance hardness) of the specimen after the cured specimen is stored at 200 ° C for 168 hours. That is, the change in hardness means (heat resistance hardness - initial hardness) / initial hardness X 100. The composition of the present invention may have a change in hardness of 30% or less, for example, 25% or less, 20% or less, or 15% or less. The composition of the present invention also has an initial hardness value of not less than shore D 20, such as not less than 25, or not less than 30. The hardness is measured according to JIS K 6253 method.

&Quot; Flexibility &quot; refers to a property that can be bent by the impact force. More specifically, at a temperature of 25 DEG C, a time of not less than 10 seconds in a completely bent state at a pressure of 60 g / cm &lt; ^{2 &} Means that no physical damage such as cutting, fracture and cracking of the specimen occurs until the elapsed time has elapsed. The composition according to the present invention can maintain flexibility even after storing the cured composition at 200 DEG C for 168 hours.

"Me" represents a methyl group, "Ph" represents a phenyl group, and "Vi" represents a vinyl group.

The term &quot; cured state &quot; means a state in which the composition is cured and is not particularly limited. For example, the composition is cured at 170 DEG C for 20 minutes and further cured at 150 DEG C for 3 hours.

"Specimen" means specimen specified in KS6518 for tensile strength and elongation, specimen specified in JISK 6253 for hardness, and specimen with thickness 2mm, width 1cm, and length 5cm in the case of flexibility.

The composition of the present invention may include, for example, compounds represented by the following formulas (1) to (3).

[Chemical Formula 1]

^{(R 1 R 2 R 3 SiO} 1/2) x · (R 4 R 5 SiO 2/2) y · (R 6 SiO 3/2) z

(2)

R ⁷ Si (OSiR ⁸ R ⁹ R ¹⁰ ) ₃

(3)

In this formula,

R ¹ to R ³ and R ⁸ to R ¹⁰ are each independently an alkenyl group having 2 to 10 carbon atoms or a monovalent hydrocarbon group having 1 to 12 carbon atoms excluding an alkenyl group, provided that at least one of R ¹ to R ³ and R ⁸ to R ¹⁰ is an alkenyl group having 2 to 10 carbon atoms,

R ⁴ to R ⁷ are each independently a monovalent hydrocarbon group of 1 to 12 carbon atoms excluding an alkenyl group,

R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently hydrogen; Or a monovalent hydrocarbon group of 1 to 12 carbon atoms excluding an alkenyl group,

R ¹³ and R ¹⁴ are each independently a monovalent hydrocarbon group of 1 to 12 carbon atoms excluding an alkenyl group,

x, y and z satisfy 0 <x <1, 0 <y <1, 0 <z <1 and x + y + z =

n is an integer of 1 to 100;

In the above formula,

R ¹ to R ³ and R ⁸ to R ¹⁰ are each independently an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, provided that at least one of R ¹ to R ³ and R ⁸ to R &lt; ¹⁰ &gt; is an alkenyl group having 2 to 8 carbon atoms,

R ⁴ to R ⁷ are each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms,

R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms,

R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms,

x, y and z satisfy 0 <x <0.7, 0.1 <y, 0.6, 0 <z <0.9 and x + y + z =

and n may be an integer of 1 to 30.

The definition of a substituent in the above formula is, for example,

R ¹ to R ³ and R ⁸ to R ¹⁰ are each independently an alkenyl group having 2 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms, provided that at least one of R ¹ to R ³ and R ⁸ to R &lt; ¹⁰ &gt; is an alkenyl group having 2 to 4 carbon atoms,

R ⁴ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms,

R ⁵ and R ⁶ are each independently an aryl group having 6 to 12 carbon atoms,

R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms,

R ¹³ and R ¹⁴ may each independently be an aryl group having 6 to 12 carbon atoms.

The definition of the substituent in the above formula is, for example,

R ¹ to R ³ and R ⁸ to R ¹⁰ are each independently vinyl, allyl, butenyl or hexenyl, methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl or naphthyl, provided that R ¹ to R ³ And at least one of R ⁸ to R ¹⁰ is vinyl, allyl, butenyl, or hexenyl,

R ⁴ to R ⁷ are each independently methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl, or naphthyl,

R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently hydrogen, methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl or naphthyl,

R ¹³ and R ¹⁴ are each independently methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl or naphthyl,

x, y and z satisfy the relationships 0.05? x? 0.3, 0.1? y? 0.4, 0.3? z? 0.8 and x + y + z =

and n may be an integer of 1 to 5.

In the composition of the present invention, the compound of Formula 1 as a main resin, M units ^{(R 1 R 2 R 3 SiO} 1/2), D units _{^{(R 4 R 5 SiO 2/}} 2) and T units (R ⁶ SiO and a _3/2). Of these units, only the M unit has an alkenyl group as a reactor, and the D unit and the T unit do not have a reactor, so post curing can be suppressed.

The compound of formula (1) may include, for example, the following compounds.

_{(ViMe 2 SiO 1/2)} x · (MePhSiO 2/2) y · (PhSiO 3/2) z

_{(Vi 2 MeSiO 1/2)} x · (MePhSiO 2/2) y · (PhSiO 3/2) z

_{(Vi 3 SiO 1/2)} x · (MePhSiO 2/2) y · (PhSiO 3/2) z

_{(ViMe 2 SiO 1/2)} x · (MePhSiO 2/2) y · (MeSiO 3/2) z

_{(Vi 2 MeSiO 1/2)} x · (MePhSiO 2/2) y · (MeSiO 3/2) z

_{(Vi 3 SiO 1/2)} x · (MePhSiO 2/2) y · (MeSiO 3/2) z

_{(ViMe 2 SiO 1/2)} x · (Ph 2 SiO 2/2) y · (PhSiO 3/2) z

_{(Vi 2 MeSiO 1/2)} x · (Ph 2 SiO 2/2) y · (PhSiO 3/2) z

_{(Vi 3 SiO 1/2)} x (Ph 2 SiO 2/2) y · (PhSiO 3/2) z

_{(ViMe 2 SiO 1/2)} x · (Ph 2 SiO 2/2) y · (MeSiO 3/2) z

_{(Vi 2 MeSiO 1/2)} x · (Ph 2 SiO 2/2) y · (MeSiO 3/2) z

_{(Vi 3 SiO 1/2)} x · (Ph 2 SiO 2/2) y · (MeSiO 3/2) z

_{(ViMe 2 SiO 1/2)} x · (Me 2 SiO 2/2) y · (PhSiO 3/2) z

_{(Vi 2 MeSiO 1/2)} x · (Me 2 SiO 2/2) y · (PhSiO 3/2) z

_{(Vi 3 SiO 1/2)} x · (Me 2 SiO 2/2) y · (PhSiO 3/2) z

_{(ViMe 2 SiO 1/2)} x · (Me 2 SiO 2/2) y · (MeSiO 3/2) z

_{(Vi 2 MeSiO 1/2)} x · (Me 2 SiO 2/2) y · (MeSiO 3/2) z

_{(Vi 3 SiO 1/2)} x (Me 2 SiO 2/2) y · (MeSiO 3/2) z

_{(ViMePhSiO 1/2) x ·} (MePhSiO 2/2) y · (PhSiO 3/2) z

_{(Vi 2 PhSiO 1/2)} x · (MePhSiO 2/2) y · (PhSiO 3/2) z

_{(ViMePhSiO 1/2) x ·} (Ph 2 SiO 2/2) y · (PhSiO 3/2) z

_{(Vi 2 PhSiO 1/2)} x · (Ph 2 SiO 2/2) y · (PhSiO 3/2) z

_{(ViMePhSiO 1/2) x ·} (Ph 2 SiO 2/2) y · (MeSiO 3/2) z

_{(Vi 2 PhSiO 1/2)} x · (Ph 2 SiO 2/2) y · (MeSiO 3/2) z

_{(ViMePhSiO 1/2) x ·} (Me 2 SiO 2/2) y · (PhSiO 3/2) z

_{(Vi 2 PhSiO 1/2)} x · (Me 2 SiO 2/2) y · (PhSiO 3/2) z

_{(ViMePhSiO 1/2) x ·} (Me 2 SiO 2/2) y · (MeSiO 3/2) z

_{(Vi 2 PhSiO 1/2)} x · (Me 2 SiO 2/2) y · (MeSiO 3/2) z

_{(Vi Ph 2 SiO 1/2} ) x · (MePhSiO 2/2) y · (PhSiO 3/2) z

_{(Vi 2 PhSiO 1/2)} x · (MePhSiO 2/2) y · (PhSiO 3/2) z

_{(Vi Ph 2 SiO 1/2} ) x · (MePhSiO 2/2) y · (MeSiO 3/2) z

_{(Vi Ph 2 SiO 1/2} ) x · (Ph 2 SiO 2/2) y · (PhSiO 3/2) z

_{(Vi Ph 2 SiO 1/2} ) x · (Ph 2 SiO 2/2) y · (MeSiO 3/2) z

_{(Vi Ph 2 SiO 1/2} ) x · (Me 2 SiO 2/2) y · (PhSiO 3/2) z

_{(Vi Ph 2 SiO 1/2} ) x · (Me 2 SiO 2/2) y · (MeSiO 3/2) z

In the above formula, x, y, and z are as described above.

The compound of Formula 1 may be contained in an amount of 50 to 90 parts by weight, for example, 55 to 85 parts by weight, or 50 to 80 parts by weight based on 100 parts by weight of the sum of the compounds represented by Formulas 1 to 3. By controlling the content of the compound of the formula (1) within the above range, sufficient mechanical strength can be ensured and, at the same time, flexibility degradation due to high crosslinking density can be prevented.

The composition of the present invention includes the compounds of formulas (2) and (3) as a crosslinking agent in addition to the compound of formula (1).

The compound of formula (2) has a reactive group which is an alkenyl group at the T unit end.

The compound of formula (2) may include, for example, the following compounds.

PhSi (OSiMe ₂ Vi) ₃

PhSi (OSiMePhVi) ₃

PhSi (OSiPh ₂ Vi) ₃

PhSi (OSiMeVi ₂ ) ₃

PhSi (OSiPhVi ₂ ) ₃

PhSi (OSiVi ₃ ) ₃

MeSi (OSiMe ₂ Vi) ₃

MeSi (OSiMePhVi) ₃

MeSi (OSiPh ₂ Vi) ₃

MeSi (OSiMeVi ₂ ) ₃

MeSi (OSiPhVi ₂ ) ₃

MeSi (OSiVi ₃ ) ₃

The compound of Formula 2 may be contained in an amount of 1 to 15 parts by weight, for example, 3 to 12 parts by weight, or 5 to 8 parts by weight based on 100 parts by weight of the sum of the compounds represented by Formulas 1 to 3. By controlling the content of the compound of the formula (2) within the above range, it is possible to prevent the post-curing from progressing due to the inability of the crosslinking reaction to proceed completely, and to prevent yellowing caused by excessive unreacted alkenyl groups.

The compound of formula (III) has a MD structure and has only reactor hydrogen at the M unit end.

The compound of formula (3) may include, for example, the following compounds.

Wherein n is as described above.

The compound of Formula 3 may be included in an amount of 5 to 45 parts by weight, for example, 10 to 40 parts by weight, or 15 to 30 parts by weight based on 100 parts by weight of the sum of the compounds represented by Formulas 1 to 3. When the content of the compound of the general formula (3) is lower than the above range, it is difficult to secure a sufficient crosslinking density, resulting in uncured or deteriorated mechanical properties. If the content is higher than the above range, The formation of voids in the ash and the formation of surface voids may cause a decrease in light efficiency.

The composition according to the present invention may further comprise a catalyst for the hydrosilylation reaction. The catalyst for hydrosilylation reaction is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of the general formula (1) or (2) and the silicon-bonded hydrogen atom of the general formula (3). The hydrosilylation catalyst is not particularly limited, and for example, a catalyst in the form of a platinum group element or a platinum group element compound can be used. For example, a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst may be used.

 Examples of the platinum-based catalyst include platinum fine powder, platinum black, chloroplatinic acid, an alcohol modified product of chloroplatinic acid, a chloroplatinic acid / diolefin complex, a platinum / olefin complex, a platinum-carbonyl complex such as platinum bis (acetoacetate) (Chloroplatinic acid / divinyltetramethyldisiloxane complex and chloroplatinic acid / tetravinyltetramethylcyclotetrasiloxane complex), platinum / alkenylsiloxane complexes (e.g., platinum bis (acetylacetonate)], chloroplatinic acid / alkenylsiloxane complexes For example, platinum / divinyltetramethyldisiloxane complexes and platinum / tetravinyltetramethylcyclotetrasiloxane complexes) and complexes of chloroplatinic acid with acetylenic alcohols. Platinum / alkenylsiloxane complexes are preferable in terms of hydrosilylation reaction performance.

The alkenyl siloxane for the complex is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclo Tetrasiloxane, an alkenylsiloxane oligomer obtained by substituting the methyl moiety of the foregoing alkenylsiloxane with, for example, ethyl, phenyl or the like, and vinyl of the foregoing alkenylsiloxane with, for example, allyl or hexenyl &Lt; / RTI &gt; 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because it produces platinum / alkenylsiloxane complexes with excellent stability.

The complex may be contained in the composition in a state dissolved in an organic solvent such as xylene.

The catalyst for the hydrosilylation reaction is compounded in such an amount as to accelerate the curing of the composition of the present invention, but the amount thereof is not particularly limited. The catalyst for the hydrosilylation reaction may be contained in an amount of 1 to 5 ppm, for example, 1.5 to 4 ppm, based on 100 parts by weight of the composition containing the compounds of the formulas (1) to (3). If it is contained in an amount of less than 1 ppm, curing may be insufficient, and if it exceeds 5 ppm, problems such as coloring may occur.

The composition of the present invention may further comprise an adhesion promoter or an adhesion promoter to provide an additional improvement in adhesion to the substrate to be contacted. The adhesion promoter is preferably an organosilicon compound adhesion promoter such as those known for hydrosilylation reaction-curable organopolysiloxane compositions. Typical examples include, in each case, a trialkoxysilyloxy group (e.g., trimethoxysilyloxy, triethoxysiloxyl) or trialkoxysilylalkyl group (e.g., trimethoxysilylethyl, triethoxysilylethyl) (E.g., vinyl, allyl), silicon-bonded methacryloxyalkyl groups (such as 3-methacryloxypropyl), and silicon-bonded epoxy-functional alkyl groups Having a functional group selected from the group consisting of glycidoxypropyl, 4-glycidoxybutyl, 2- (3,4-epoxycyclohexyl) ethyl and 3- (3,4-epoxycyclohexyl) And organosiloxane oligomers of linear, branched and cyclic structure having approximately 4 to 20 silicon atoms. Another common example is the reaction of an epoxy-functional ethyl polysilicate and an amino-alkyl trialkoxy silane with an epoxy-functional alkyl trialkoxy silane.

Specific examples are vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hydrogentriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2 - (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane and A reaction product of 3-aminopropyltriethoxysilane, a condensation reaction product of a silanol-terminated methylvinylsiloxane oligomer and 3-glycidoxypropyltrimethoxysilane, a silanol-terminated methylvinylsiloxane oligomer, But are not limited to, a condensation reaction product of t-butoxycarbonyloxypropyltriethoxysilane and a condensation reaction product of tris (3-trimethoxysilylpropyl) isocyanurate.

Compositions of the present invention may also contain inorganic fillers (e.g., silica, glass, alumina, zinc oxide, etc.), as long as they do not impair the objects of the present invention; Silicone rubber powder; Resin powder (e.g., silicone resin, polymethacrylate resin, etc.); Heat resisting agent; Antioxidants; Radical scavenger; Light stabilizer; dyes; Pigments; A flame retardant additive and a reaction retarder. For example, 2-Phenyl-3-butyn-2-ol may be used as the reaction retarder, but the present invention is not limited thereto.

The present invention also relates to a sealing material for a light emitting diode device comprising a cured product of the composition according to the present invention and a light emitting diode device including the same.

Hereinafter, the light emitting diode device of the present invention will be described in detail.

The light emitting diode device of the present invention is characterized in that the light emitting diode device is sealed therein by the cured product of the composition according to the present invention. It is needless to say that the composition used in the present invention can be used for semiconductor laser devices, organic EL devices, photodiode devices, phototransistor devices, solid-state image pickup devices, photocouplers, and light emitting devices in addition to such light emitting diode devices.

1 is a cross-sectional view of an exemplary light emitting diode device of the present invention. 1, a light emitting diode (LED) chip 13 is die bonded onto a die pad 16, and the light emitting diode (LED) chip 13 is bonded to a bonding wire 12 To the inner lead 14 by wire bonding. The light emitting diode (LED) chip 13 is encapsulated by the cured product 11 of the light emitting diode element encapsulant of the present invention.

(LED) chip 13 is die-bonded onto the die pad 16 and a light emitting diode (LED) chip 13 is bonded to the die pad 16 in order to manufacture the surface-mounted LED device 10 shown in FIG. Is wire-bonded to the inner lead (14) by the bonding wire (12). Then, the light-emitting diode element encapsulant of the present invention, particularly a sealing material, is introduced, and thereafter, preferably, deaerated and then cured by heating at 50 to 200 ° C.

Hereinafter, the present invention will be described in more detail with reference to examples and drawings. The following examples serve to illustrate the present invention and are not intended to limit the scope of the present invention.

Preparation of [Preparation Example ^{1] a-1 (M Vi} , Me2 0 .15 D Me, Ph 0 .25 T Ph 0 .60)

A flask equipped with a condenser, a thermometer, a line for nitrogen injection and a stirrer was charged with 118.98 g of phenyltrimethoxysilane, 13.98 g of divinyltetramethyldisiloxane, 27.13 g of?,? - dimethylhydroxysilylmethylphenylpolysiloxane, 100 g of toluene, 0.25 g of sulfonic acid was added and 50 g of distilled water was slowly added dropwise while stirring. The reactor was heated to slowly recover reaction by-products. Thereafter, washing with water was carried out until the reactant became neutral. Only an organic layer containing an organosiloxane was recovered and added to a separate flask, and the temperature was elevated to remove the condensed water additionally. In the next step, 0.16 g of a 20% aqueous solution of potassium hydroxide was added and the temperature was raised to remove the remaining silanol groups. The final residual solvent was removed by distillation under reduced pressure to obtain 100 g of organopolysiloxane having a network content of 1.2 mmol / g, a refractive index of 1.552 and a volatile content of 0.8%.

[Preparation Example ^{2] a-2 (M Vi} , Me2 0 .15 D Me, Ph 0 .2 T Ph 0 .65)

In the same manner as in Preparation Example 1 except that 128.9 g of phenyltrimethoxysilane and 21.7 g of?,? - dimethylhydroxysilyl-methylphenylpolysiloxane were used in Production Example 1, a vinyl content of 1.2 mmol / g, a refractive index of 1.554, 0.8 g of an organopolysiloxane having a network structure was obtained.

[Preparation Example ^{3] a-3 (M Vi} , Me2 0 .15 D Me, Ph 0 .15 T Ph 0 .7)

In the same manner as in Production Example 1 except that 138.81 g of phenyltrimethoxysilane and 16.28 g of?,? - dimethylhydroxysilyl-methylphenylpolysiloxane were used in Production Example 1, a vinyl content of 1.2 mmol / g, a refractive index of 1.556, 0.8 g of an organopolysiloxane having a network structure was obtained.

[Comparative Preparation Example 1] a-4 (D ^{Me , Ph} _{0 .15} D ^{Me , Vi} _{0 .15} T ^Ph _{0 .7} )

In the same manner as in Production Example 1, except that 12.3 g of tetravinyltetramethylcyclotetrasiloxane was replaced by 13.98 g of divinyltetramethyldisiloxane, the same procedure as in Production Example 1 was repeated to give 1.2 g / g of vinyl, 1.28 g of refractivity and 0.8% Thereby obtaining 100 g of the organopolysiloxane.

[Preparation Example 4] Preparation of b-2 (PhSi (OSiMe ₂ Vi) ₃ )

61 g of distilled water, 419 g of divinyltetramethyldisiloxane and 1.02 g of trifluoromethanesulfonic acid were charged into a flask equipped with a condenser, a thermometer, a line for injecting nitrogen, and a stirrer, and the temperature was raised to 60 ° C. 297 g of phenyltrimethoxysilane was gradually added The reaction was continued until the reaction was completed. The next step was washing with water until the reaction became neutral. The organopolysiloxane-containing organic layer was put in a separate flask to remove the low boiling point reaction product by vacuum distillation to obtain an organopolysiloxane having a vinyl content of 6.1 mmol / g, a refractive index of 1.48 and a viscosity of 10.9 cP.

[Comparative Production Example 2] Production of b-1

Preparation of < [alpha], [omega] -dimethylhydroxysilyl-methylphenylpolysiloxane >

100 g of methylphenyldichlorosilane was slowly added dropwise to the flask while stirring a mixture of 100 g of toluene and 161.4 g of water at low temperature and hydrolysis.

Thereafter, the stirring was stopped and the mixture was kept in a stationary state to separate the layers. The wastewater (HCl + H ₂ O) layer was separated from the flask, and then the same amount of water was added thereto. The washing process was repeated until the wastewater layer became neutral. After the wastewater layer was removed at the final stage, a toluene solution of methylphenyl organopolysiloxane having a terminal silanol group was prepared. The low boiling point reaction product was stripped to obtain an?,? - dimethylhydroxysilyl-methylphenylpolysiloxane having a refractive index of 1.54 and a viscosity of 600 cP.

Preparation of < [alpha], [omega] -vinyldimethylsilyl-methylphenylpolysiloxane &

3.2 g of the above-mentioned dimethylhydroxysilyl-methylphenylpolysiloxane, 8.5 g of divinyltetramethyldisiloxane and Acid clay were charged into a flask equipped with a condenser, a thermometer, a line for injecting nitrogen, and a stirrer, When the volatile content of the reaction product was measured and found to be 12% or less, the reaction was terminated and cooled to room temperature.

The colorless transparent organopolysiloxane obtained by filtering the reactants was removed by volatilization using a thin-film distillation apparatus to obtain a viscous organopolysiloxane having a volatile content of 0.35%, a vinyl content of 0.278 mmol / g, a refractive index of 1.543 and a viscosity of 4,943 cP.

The above organopolysiloxane was analyzed by nuclear magnetic resonance analysis for the above vinyl content, and it was confirmed that the organopolysiloxane was also synthesized with the aimed structure shown below

[Preparation Example 5] Preparation of c-1

27 g of distilled water, 0.77 g of trifluoromethylsulfonic acid and 244 g of diphenyldimethoxysilane were added dropwise to a flask equipped with a condenser, a thermometer, a line for nitrogen injection and a stirrer, and 269 g of tetramethyldisiloxane was slowly added dropwise thereto. The reaction was maintained. Thereafter, washing with water was carried out until the reactant became neutral. The siloxane component was transferred to another flask, and the low boiling point reaction product was distilled under reduced pressure to finally obtain colorless transparent organopolysiloxane having a viscosity of 4.63 cP, a refractive index of 1.498 and an Si-H content of 6.02 mmol / g.

[Comparative Preparation Example 3] Preparation of c-2

In a flask equipped with a condenser, a thermometer, a line for injecting nitrogen, and a stirrer, 172 g of toluene and 438 g of distilled water were placed, and a mixture of 253 g of dichlorosilane, 129 g of dimethyldichlorosilane and 172 g of toluene was slowly added dropwise at low temperature. Thereafter, the reaction was allowed to proceed by heating, and washing was continued until the reactant became neutral. At the last stage of the washing, the water layer was separated to obtain an organopolysiloxane having an α, ω-dimethylhydroxysilyl- (diphenylsiloxy) (methylhydrogensiloxy) structure diluted in toluene.

In a flask equipped with a separate condenser, a thermometer, a line for injecting nitrogen, and a stirrer, 201 g of the organopolysiloxane having an α, ω-dimethylhydroxysilyl- (diphenylsiloxy) (methylhydrogensiloxy) structure obtained in the above, 21 g of methyldisiloxane and 11 g of acid clay were added and reacted, and it was confirmed that the volatile content of the reaction product was 12% or less, and the reaction was terminated. Thereafter, acid clay, which is a solid phase reaction catalyst, was filtered out and the remaining organopolysiloxane was distillated under reduced pressure to obtain an organopolysiloxane of the following formula, having a viscosity of 52 cP, a refractive index of 1.52, and an Si-H content of 5.7 mmol / g .

[Examples and Comparative Examples]

The siloxane prepared in the preparation examples and comparative preparation examples was mixed with GPTMS (Glycidoxypropyltrimethoxysilane) as an adhesion promoter, platinum catalyst (f) as a catalyst and 2-Phenyl-3-butyn-2-ol Were mixed in proportions shown in Table 1 below to prepare a composition.

The platinum-based catalyst was diluted with an amount of 2% by weight of the compound of the following formula in xylene.

Furtherance Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 a-1 70 a-2 70 a-3 70 60 52 a-4 60 70 b-1 13.5 27 13.5 b-2 7 7 7 6.5 6.5 7 c-1 22 22 22 19 19 22 c-2 20 20 e One One One One One One One f 2.5 2.5 2.5 2.5 2.5 2.5 2.5 g 250 250 250 250 250 250 250

In Table 1, the amounts of a, b, c, d, and e compositions refer to parts by weight, and the amounts of f and g compositions are ppm relative to the total amounts a, b, c, d, and e.

[Test Example 1] Measurement of physical properties of composition

[Hardness]

The polyorganosiloxane cured specimens were cured at 170 DEG C for 20 minutes using a mold having a spacing of 6 mm, demolded in the mold, and cured in an oven at 150 DEG C for 3 hours. The hardness of the cured product was measured with a Type D durometer according to JISK 6253.

The heat-resistant conditions were the same as that for the polyorganosiloxane cured specimens prepared in the same manner as above, after further storing in a 200 ° C oven for 168 hours.

[Tensile, Elongation]

The polyorganosiloxane cured specimen was cured at 170 DEG C for 20 minutes using a mold having a gap of 2 mm, then demolded in a mold, and cured in an oven at 150 DEG C for 3 hours. The tensile and elongation of the cured product was measured by a method based on KS6518.

The heat-resistant conditions were the same as that for the polyorganosiloxane cured specimens prepared in the same manner as above, after further storing in a 200 ° C oven for 168 hours.

 [Test Example 2] Properties of LED PKG

The surface mounted LED lead frame was die-bonded and wire-bonded to the above lead frame using an open tool, top-view 3528 4 pad "B" type (Jingjin NeXT) from JINJINEXTECH. The polyorganosiloxane composition was dispensed, cured in an oven at 80 캜 for 1 hour, and cured at 150 캜 for 1 hour to prepare one lead frame (64 surface-mounted LEDs) per each test.

[Thermal shock]

Thermal shock: Experiments were carried out for 10 minutes at -40 ° C for 20 minutes and at 110 ° C for 20 minutes in an experiment with a temperature range of -40 ° C to 110 ° C.

[MSL]

After 168 hours of storage at 60 ° C and 90% of constant temperature and humidity, reflow (maximum temperature 260 ° C) was performed three times in total.

[1000 hours high temperature reliability]

The luminous flux was measured after an energization test at a constant temperature of 85 ° C for 1000 hours, and the initial luminous flux was calculated on the basis of 100%.

[Flexibility]

The cured polyorganosiloxane specimens were cured at 170 ° C for 20 minutes using a mold having a spacing of 2 mm and then demolded in a mold to prepare specimens having a thickness of 2 mm, a width of 1 cm and a length of 5 cm. The prepared specimens were further cured in a 150 &lt; 0 &gt; C oven for 3 hours.

The cured specimens were further stored in an oven at 200 ° C for 168 hours, and were then completely bent at a pressure of 60 g / cm ² at 25 ° C until one side of the specimen came into contact with each other. , Physical damage such as fracture and crack was observed, and when no physical damage occurred, it was indicated as O and when the damage occurred, X was indicated.

The results of the above test examples are shown in Table 2 below.

Furtherance Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Initial hardness 35 38 43 30 35 40 40 Heat resistance hardness 39 42 50 33 47 60 55 Hardness change rate (%) 11.4 10.5 16.3 10.0 34.3 50.0 37.5 Initial Seal 3 3.5 3.7 1.5 4 5.3 6 Heat proof seal 3.5 4 4.2 2 8 9.7 12 Tensile Change (%) 16.7 14.3 13.5 33.3 100.0 83.0 100.0 Initial elongation 70 75 77 100 50 42 45 Heat Elongation Rate 60 65 65 70 23 20 17 Elongation Change Rate (%) 14.3 13.3 15.6 30.0 54.0 52.4 62.2 Thermal shock 1/16 2/16 2/16 0/16 10/16 16/16 16/16 M.S.L 0/16 1/16 0/16 1/16 9/16 15/16 14/16 1000 hours
High temperature reliability 98% 98% 98% 98% 88% 85% 81% Flexibility O O O O X X X

Claims (9)

(1) to (3): < EMI ID =
Curable organopolysiloxane composition having a elongation change amount and a tensile strength change amount of 50% or less, respectively, of a specimen after storage at 200 ° C for 168 hours, with respect to the elongation and tensile strength of the cured state specimen:
[Chemical Formula 1]
(R ¹ R ² R ³ SiO _1/2 ) _x (R ⁴ R ⁵ SiO _2/2 ) _y (R ⁶ SiO _3/2 ) _z
(2)
R ⁷ Si (OSiR ⁸ R ⁹ R ¹⁰ ) ₃
(3)

In this formula,
R ¹ to R ³ and R ⁸ to R ¹⁰ are each independently an alkenyl group having 2 to 10 carbon atoms or a monovalent hydrocarbon group having 1 to 12 carbon atoms excluding an alkenyl group, provided that at least one of R ¹ to R ³ and R ⁸ to R ¹⁰ is an alkenyl group having 2 to 10 carbon atoms,
R ⁴ to R ⁷ are each independently a monovalent hydrocarbon group of 1 to 12 carbon atoms excluding an alkenyl group,
R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently hydrogen; Or a monovalent hydrocarbon group of 1 to 12 carbon atoms excluding an alkenyl group,
R ¹³ and R ¹⁴ are each independently a monovalent hydrocarbon group of 1 to 12 carbon atoms excluding an alkenyl group,
x, y and z satisfy 0 <x <1, 0 <y <1, 0 <z <1 and x + y + z =
n is an integer of 1 to 100;
The method according to claim 1,
Wherein the initial hardness of the cured state specimen is equal to or greater than Shore D 20 and the change in hardness of the specimen after storage at 200 ° C for 168 hours is 30% or less with respect to the initial hardness of the cured state specimen.
3. The method according to claim 1 or 2,
The composition was stored in a cured state at 200 ° C for 168 hrs. The specimen was held at a temperature of 25 ° C under a pressure of 60 g / cm ² until one side of the specimen came into contact with each other. Is not generated in the curable organopolysiloxane composition.
delete The method according to claim 1,
R ¹ to R ³ and R ⁸ to R ¹⁰ are each independently an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, provided that at least one of R ¹ to R ³ and R ⁸ to R < ¹⁰ &gt; is an alkenyl group having 2 to 8 carbon atoms,
R ⁴ to R ⁷ are each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms,
R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms,
R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms,
x, y and z satisfy 0 <x <0.7, 0.1 <y, 0.6, 0 <z <0.9 and x + y + z =
and n is an integer from 1 to 30. &lt; RTI ID = 0.0 &gt; 18. &lt; / RTI &gt;
6. The method of claim 5,
R ¹ to R ³ and R ⁸ to R ¹⁰ are each independently an alkenyl group having 2 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms, provided that at least one of R ¹ to R ³ and R ⁸ to R &lt; ¹⁰ &gt; is an alkenyl group having 2 to 4 carbon atoms,
R ⁴ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms,
R ⁵ and R ⁶ are each independently an aryl group having 6 to 12 carbon atoms,
R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms,
R ¹³ and R ¹⁴ are each independently an aryl group having 6 to 12 carbon atoms.
6. The method of claim 5,
R ¹ to R ³ and R ⁸ to R ¹⁰ are each independently vinyl, allyl, butenyl, hexenyl, methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl or naphthyl, provided that R ¹ to R ³ And at least one of R ⁸ to R ¹⁰ is vinyl, allyl, butenyl, or hexenyl,
R ⁴ to R ⁷ are each independently methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl, or naphthyl,
R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ are each independently hydrogen, methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl or naphthyl,
R ¹³ and R ¹⁴ are each independently methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl or naphthyl,
x, y and z satisfy the relationships 0.05? x? 0.3, 0.1? y? 0.4, 0.3? z? 0.8 and x + y + z =
and n is an integer from 1 to 5. &lt; RTI ID = 0.0 &gt; 5. &lt; / RTI &gt;
An encapsulant for a light-emitting diode device comprising a cured product of the composition according to claim 1 or 2.
Wherein the light emitting diode element is sealed by the sealing material according to claim 8.

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