KR20130128650A - Organopolysiloxane composition - Google Patents

Abstract

The present invention relates to an organopolysiloxane composition, wherein initial elongation of a hardened sample is 90% or greater and the initial hardness of a hardened sample is Shore D 35 or greater. The hardened sample according to the present invention has 25% or less of elongation change after stoage at 200 deg. C for 168 hours.

Description

Organopolysiloxane composition

The present invention relates to an organopolysiloxane composition for encapsulating a light emitting diode device having high reliability even in a high temperature practical use environment.

In general, an epoxy resin has been conventionally used as a sealing material for a light emitting diode element. Epoxy resin has excellent light transmittance, but because of its high elastic modulus, cracks occur between wires, chips, and epoxy resins and wire bonding is broken under various temperature conditions and temperature changes, resulting in the collapse of the crystal structure of semiconductor materials. Luminous efficiency may be lowered. Epoxy resins are also more unsatisfactory in terms of heat resistance and light resistance to lighter, shorter wavelength light. When ultraviolet rays or the like are transmitted to the epoxy resin, the bonds of the organic polymers are broken, thereby degrading the optical and chemical properties of the resin. As a result, the epoxy resin eventually turns the encapsulant to yellow, which affects the color of the light beams, thereby reducing the life of the light emitting device.

On the other hand, application of a silicone resin has been proposed as a way to solve the above problems. Compared with organic resins, silicon has superior heat resistance, weather resistance, and the like than epoxy resins, and is not only transparent, hardly discolored, and physically deteriorated. However, these silicone resins are excellent in mechanical strength and chemical stability, but research is being continuously conducted to secure higher luminance.

The silicone resin composition disclosed in Japanese Unexamined Patent Publication No. 2002-265787 has a phenyl group and an alkenyl group because the crosslink density of the siloxane is increased, and π-π interaction between aromatic rings is important for improving the refractive index of the cured product. The specific organohydrogen polysiloxane which has specific organo polysiloxane and a phenyl group is addition-hardened, and high hardness and high transparency resin are obtained.

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

In the case of using phenyl-containing reactive polysiloxane, a large amount of heat and time are required in the curing process to achieve the desired mechanical properties, but a process-economically limited curing time and temperature should be applied. Therefore, after the actual device is mounted, additional reaction proceeds by the heat generated in the use environment, thereby changing mechanical properties such as modulus. This results in an increase in internal stress, which in extreme cases leads to an inability to light due to a wire break, delamination of most interfaces, accelerated phosphor oxidation and corrosion due to cracking, which leads to reduced efficiency or the lifetime of the entire LED. Reduce

In addition, as demands for applying LEDs to large-area liquid crystal displays or lighting have increased recently, shock factors for heat are increasingly severe in terms of use environment, such as mounting a large number of chips in a dense package or increasing the amount of applied current. Is getting.

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

The present invention has been made to solve the problems of the prior art, an object of the present invention is to provide a curable organopolysiloxane composition excellent in 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.

Still another object of the present invention is to provide a light emitting diode device in which a light emitting diode element is sealed by the encapsulation material according to the present invention.

The present inventors found that the most important factor in improving the reliability of the entire LED device is the increase in the internal stress of the encapsulant. In addition, efficiency degradation may occur due to peeling, cracking or cracking due to internal stress increase. Lower modulus may be applied to alleviate the internal stress, but this may cause stickiness of the surface due to lowering of the crosslinking density. As a result of efforts to solve this problem, a crosslinking agent containing a cyclic isocyanurate structure was used to develop an encapsulant composition that can realize high mechanical strength even with low modulus.

In order to achieve the above object, the present invention provides a curable organopolysiloxane composition having an initial elongation of 90% or more measured by KS M 6518 for a cured state specimen, and an initial hardness of the cured state specimen of Shore D 35 or more.

The composition provides a curable organopolysiloxane composition crosslinked by a compound of Formula 1 below.

 [Formula 1]

In Formula 1,

Ra to Rc are hydrogen, alkenyl group having 2 to 12 carbon atoms or silicon,

Any one or two or more of Ra to Rc is an alkenyl group or silicon having 2 to 12 carbon atoms.

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 element is sealed by the encapsulation material according to the present invention.

When used as an encapsulant of a light emitting diode device, the composition according to the present invention can realize low modulus and high mechanical strength, and can provide high reliability and excellent life 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.

Definitions of terms used in the present invention are as follows.

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

"Tensile strength change" means the percentage difference between the tensile strength value (initial tensile strength) of the cured specimen and the tensile strength value (heat resistance tensile strength) of the specimen after storing the cured specimen for 168 hrs at 200 ° C. In other words, the change in tensile strength means (heat resistance tensile strength-initial tensile strength) / initial tensile strength X 100. The composition of the present invention may be 50% or less, for example 45% or less, 40% or less, or 35% or less in tensile strength change. The elongation and tensile strength measurement method is according to the KS6518 method.

By "hardness variation" is meant the percentage difference between the hardness value (initial hardness) of the cured state specimen and the hardness value (heat resistance hardness) of the specimen after storing the cured state at 200 ° C. for 168 hrs. That is, the hardness change amount means (heat resistance hardness-initial hardness) / initial hardness X 100. The composition of the present invention may be 30% or less, for example, 25% or less, 20% or less, or 15% or less. The compositions of the invention also have an initial hardness value of shore D 20 or greater, such as 25 or greater, or 30 or greater. The measuring method of the said hardness is based on JISK 6253 method.

"Flexible" means any of the various properties that can be bent by the inertia, specifically, the curing conditions at 25 ℃ specimens (having a thickness of 2mm, width 1cm, vertical 5cm) one of 60g / cm ² until it touches the surface is fit to each other in It means a state in which physical damage such as cutting, breaking, and cracking of the specimen does not occur until the time of 10 seconds or more is completely bent under pressure. The composition according to the present invention can maintain flexibility even after storing the cured composition at 200 ° C. for 168 hrs.

"Coloring degree (YI)" means the degree of discoloration of the cured specimens over time, and after curing the polyorganosiloxane cured specimens by using a mold having a spacing of 2 mm at 170 ° C. for 20 minutes, Demolded and cured in a 150 ° C. oven for 3 hours. The cured product was measured according to ASTM E313 using a Nippon Deshoku color difference meter 300A, and heat-resistant conditions were further determined by using a polyorganosiloxane cured specimen prepared in the same manner as described above in a 200 ° C. oven. After storage for a time it was measured by the same method. Specifically, in the present invention, the degree of coloring may refer to the degree of coloring in the above heat resistant conditions.

"Takcy" means the degree of force that the hardened surface exhibits adhesion properties even at a small pressure, and one side of the specimen (thickness 2mm, width 1cm, length 5cm) in the hardened state at 25 ° C In this state, dry nitrogen (pressure of 100g / cm ² ) is applied to the entire surface of the contacted surface after the elapse of 10 seconds or more in the state of complete contact with the pressure of 60g / cm 2 until it comes into contact with the coated surface without this void space. Visually observe the degree of powder remaining on the surface by spraying for less than 1 second, which is good when there is no powder on the surface, and poor when the powder is observed on the surface.

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

The term “cured state” means a state in which the composition is cured, but is not particularly limited, but means a state in which the composition is cured at 170 ° C. for 20 minutes and further cured at 150 ° C. for 3 hours.

"Sample" means a specimen as defined in KS M 6518 or JISK 6253.

As one example, the curable organopolysiloxane composition according to the present invention, the initial elongation measured by KS M 6518 with respect to the cured state specimens may be 90% or more, the initial hardness of the cured state specimens may be Shore D 35 or more. For example, the initial elongation measured by KS M 6518 for the cured state specimen of the composition may range from 90% or more, 100% or more, 90 to 130%, or 90 to 110%. In addition, the initial hardness of the cured state specimen of the composition may be in the range of Shore D 35 or more, Shore D 40 or more, Shore D 35 to 50, or Shore D 40 to 45. The curable organopolysiloxane composition according to the present invention can simultaneously realize excellent initial elongation and high hardness.

In addition, the composition, the change in elongation after storage of the cured state of the specimen at 200 ℃ for 168 hours 30% or less, after storing the cured state of the specimen at 200 ℃ for 168 hours may be less than 3.9 coloration measured by ASTM E313. . For example, after storing the cured specimen of the composition at 200 ° C. for 168 hours, the colorability measured by ASTM E313 may be in the range of 3.9 or less, 3.82 or less, 3.6 or less, 3.4 or less, 2 to 3.9, or 3 to 3.9. have.

The composition may have a change in elongation of 25% or less, 24% or less, or 15 to 25% after curing of the cured state at 200 ° C. for 168 hr. The curable organopolysiloxane composition according to the present invention provides a composition having a relatively small change in elongation and a small change in physical properties.

As another example, the initial tensile strength measured by ASTM D638 for the cured state of the composition of the composition may be 3.5 MPa or more, the tensile strength change of the specimen after 168hr storage at 200 ℃ may be 35% or less. For example, the initial tensile strength measured by ASTM D638 for the cured state specimen of the composition may be at least 3.5 MPa, at least 3.8 MPa, or in the range of 3.5 to 5 MPa. In addition, the amount of change in tensile strength of the specimen after storing the cured specimen at 200 ° C. for 168 hr may be 35% or less, 32% or less, 15 to 35%, or 20 to 35%. Since the curable organopolysiloxane composition according to the present invention has a relatively small change in tensile strength, it is possible to provide a highly reliable composition.

The composition was stored in a cured state of the specimen (thickness 2mm, width 1cm, length 5cm) at 200 ℃ 168hr, and bent at a pressure of 60g / cm ² until one side of the specimen abuts at 25 ℃ conditions 10 The physical damage of the specimen is not generated until the elapse of seconds.

In addition, the surface of the cured state of the composition is in contact with the calcium carbonate powder after contacting after elapse of 10 seconds or more in a state of complete contact with a pressure of 60 g / cm ² until the contact with the bottom surface is applied without voids When dry nitrogen (100g / cm ² pressure) is sprayed on the entire surface (1cm in width and 5cm in length) for less than 1 second, visual observation of the amount of powder remaining on the surface shows that there is no powder on the surface. It is characterized by little.

The composition of the present invention may be a structure crosslinked by a crosslinking agent comprising an isocyanurate cyclic structure. For example, a crosslinking agent including an isocyanurate cyclic structure may be represented by a compound of Formula 1 below.

 [Formula 1]

In Formula 1,

Ra to Rc are hydrogen, alkenyl group having 2 to 12 carbon atoms or silicon,

Any one or two or more of Ra to Rc is an alkenyl group or silicon having 2 to 12 carbon atoms.

The compound of formula 1 serves as a crosslinking agent constituting the organopolysiloxane composition. Specifically, at least one of Ra to Rc in the definition of Chemical Formula 1 is an alkenyl group or silicon having 2 to 12 carbon atoms, and the alkenyl or silicon includes a hydrogen group directly connected to each other, and performs a hydrosilylation reaction. It is a structure that is combined with other compositions through.

As one example, the compound of Formula 1 may be a structure of Formula 1-a.

 [Chemical Formula 1-a]

The composition according to the present invention further includes a compound of Formula 2, and the compound of Formula 2 may be a structure crosslinked by a compound of Formula 1.

 (2)

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

In Formula 2,

R ¹ to R ⁶ are each independently hydrogen, an alkenyl group having 2 to 12 carbon atoms, or a monovalent hydrocarbon group having 1 to 12 carbon atoms except for an alkenyl group, provided that at least one of R ¹ to R ³ , R ⁴ and Any one or more selected from the group consisting of R ⁵ and R ⁶ , and an alkenyl group having 2 to 12 carbon atoms,

x, y and z satisfy 0 <x <1, 0 <y <1, 0 ≦ z <1 and x + y + z = 1, respectively.

In one embodiment, in the formula 2,

R ¹ to R ⁶ are each independently hydrogen, an alkenyl group having 2 to 8 carbon atoms, or a monovalent hydrocarbon group having 1 to 10 carbon atoms except for an alkenyl group, provided that at least one of R ¹ to R ³ , R ⁴ and At least one selected from the group consisting of at least one of R ⁵ , and R ⁶ is an alkenyl group having 2 to 8 carbon atoms,

x, y and z satisfy 0 <x <1, 0 <y <1, 0 ≦ z <1 and x + y + z = 1, respectively.

As another embodiment, in Chemical Formula 2,

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

R ⁴ to R ⁶ are each independently methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl, or naphthyl,

x, y and z satisfy 0.05 ≦ x ≦ 0.3, 0.1 ≦ y ≦ 0.4, 0.3 ≦ z ≦ 0.8 and x + y + z = 1, respectively.

In this case, the compound of Formula 2 described above may have a structure of forming a crosslink through a hydrosilylation reaction with the compound of Formula 1. Specifically, the compound of Formula 1 may be defined as follows.

[Formula 1]

In Formula 1,

Ra to Rc are hydrogen, alkenyl group having 2 to 12 carbon atoms or silicon,

Any one or two or more of Ra to Rc is an alkenyl group or silicon having 2 to 12 carbon atoms, and is a structure combined with a compound of formula (2).

As another example, the composition according to the present invention may include a compound of Formula 3, and the compound of Formula 3 may have a structure crosslinked by a compound of Formula 1.

 (3)

In Formula 3,

R ⁷ to R ¹¹ are each independently hydrogen; Or a monovalent hydrocarbon group having 1 to 12 carbon atoms except for an alkenyl group, R ⁹ and R ¹⁰ are each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms except for an alkenyl group, and n is an integer of 1 to 100.

In one embodiment, in Chemical Formula 3,

R ⁷ to R ¹¹ are each independently hydrogen; Or a monovalent hydrocarbon group having 1 to 8 carbon atoms except for an alkenyl group, R ⁹ and R ¹⁰ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms except for an alkenyl group, and n is an integer of 1 to 60.

In another embodiment, in Chemical Formula 3,

R ⁷ , R ⁸ , R ¹¹ and R ¹² are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms,

R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms,

n is an integer of 1 to 30;

In this case, the compound of Formula 3 described above may have a structure of forming a crosslink through a hydrosilylation reaction with the compound of Formula 1. Specifically, the compound of Formula 1 may be defined as follows.

[Formula 1]

In Formula 1,

Ra to Rc are hydrogen, alkenyl group having 2 to 12 carbon atoms or silicon,

Any one or two or more of Ra to Rc is an alkenyl group or silicon having 2 to 12 carbon atoms, and is a structure bonded with a compound of formula (3).

As another example, the composition according to the present invention may include a compound of Formulas 1 to 3, and the compounds of Formulas 2 and 3 may have a structure crosslinked by a compound of Formula 2.

Compounds of formulas (2) and (3) are as described above. In this case, Chemical Formula 1 may be defined as follows.

 [Formula 1]

In Formula 1,

Ra to Rc are hydrogen, alkenyl group having 2 to 12 carbon atoms or silicon,

Any one or two or more of Ra to Rc is an alkenyl group or silicon having 2 to 12 carbon atoms, and is a structure bonded to one or more compounds of Formulas 1 and 3.

As one example, the composition of the present invention may include a cyclic isocyanurate structure. The cyclic isocyanurate structure serves as a crosslinking agent, for example, it may be represented by the formula (1).

The compound of Formula 1 may be included in 1 to 15 parts by weight, for example 1 to 12 parts by weight, or 1 to 5 parts by weight based on 100 parts by weight of the composition. By adjusting the content of the compound of formula 1 in the above range, it is possible to achieve high mechanical strength despite the low modulus.

As yet another example, according to the composition of the present invention, the compound of formula (II) as the main resin M units ^{(R 1 R 2 R 3 SiO} 1/2), D units _{^{(R 4 R 5 SiO 2/}} 2) and a T units _{^{(R 6 SiO 3/2)}} . For example, only M units in the unit may have an alkenyl group, which is a reactor, and D units and T units may not have a reactor, and in this case, post curing may be suppressed. In the present invention, as an example of the compound of Formula 2, the case of having a alkenyl group as a reactor in the D unit or T unit is not excluded.

The compound of Formula 2 may include, for example, the following compound.

_{(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

_{(ViPh 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

_{(ViPh 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 Chemical Formula 2 may be included 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 of Formulas 1 to 3. By adjusting the content of the compound of formula (2) in the above range, it is possible to ensure a sufficient mechanical strength, and at the same time prevent the decrease in flexibility due to high crosslink density.

In addition, the compound of Formula 3 may have a MD structure and a structure having a reactor hydrogen only at the M unit terminal. The compound of Formula 3 may include, for example, the following compound.

N is as described above.

The compound of Formula 3 may be included in 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 of Formulas 1 to 3. When the content of the compound of Formula 3 is lower than the above range, it is difficult to secure sufficient crosslinking density, so that uncuring may occur or mechanical properties may be lowered. Pore formation and surface void formation in the ash may cause a decrease in light efficiency.

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

 Platinum-based catalysts include fine platinum powder, platinum black, chloroplatinic acid, alcohol modified compounds of chloroplatinic acid, chloroplatinic acid / diolefin complexes, platinum / olefin complexes, platinum-carbonyl complexes [e.g. platinum bis (acetoacetate) and Platinum bis (acetylacetonate)], chloroplatinic acid / alkenylsiloxane complexes (e.g., chloroplatinic acid / divinyltetramethyldisiloxane complexes and chloroplatinic acid / tetravinyltetramethylcyclotetrasiloxane complexes), platinum / alkenylsiloxane complexes ( Examples are platinum / divinyltetramethyldisiloxane complexes and platinum / tetravinyltetramethylcyclotetrasiloxane complexes) and complexes of chloroplatinic acid and acetylene alcohols. Platinum / alkenylsiloxane complexes are preferred in view of hydrosilylation reaction performance.

Alkenylsiloxane for the complex is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclo Tetrasiloxane, the alkenylsiloxane oligomer obtained by substituting the methyl portion of the preceding alkenylsiloxane with, for example, ethyl, phenyl, etc. and the vinyl of the former alkenylsiloxane, eg, with allyl or hexenyl It can be exemplified by the alkenylsiloxane oligomer obtained by. 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because it produces a platinum / alkenylsiloxane complex with good stability.

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

Although the catalyst for hydrosilylation reaction is mix | blended in the quantity which accelerates hardening of the composition of this invention, its compounding quantity is not specifically limited. The catalyst for the hydrosilylation reaction may be included in an amount of 1 to 5 ppm, for example 1.5 to 4 ppm, based on 100 parts by weight of the composition including the compound of Formulas 1 to 3. Curing may be insufficient when included below 1 ppm, and problems such as coloring may occur when included above 5 ppm.

The composition of the present invention may further comprise an tackifier or an adhesion promoter in order to provide further improvement of adhesion to the contacting substrate. This adhesion promoter is preferably an organosilicon compound-based adhesion promoter such as that known for hydrosilylation reaction-curable organopolysiloxane compositions. As a typical example, in each case a trialkoxysiloxy group (eg trimethoxysiloxy, triethoxysiloxy) or trialkoxysilylalkyl group (eg trimethoxysilylethyl, triethoxysilylethyl), Hydrosilyl groups, silicon-bonded alkenyl groups (eg vinyl, allyl), silicon-bonded methacryloxyalkyl groups (eg 3-methacryloxypropyl) and silicon-bonded epoxy-functional alkyl groups (eg 3 Org having a functional group selected from the group consisting of: glycidoxypropyl, 4-glycidoxybutyl, 2- (3,4-epoxycyclohexyl) ethyl and 3- (3,4-epoxycyclohexyl) propyl) Organosiloxanes of linear, branched, and cyclic structures having organosilanes and approximately 4 to 20 silicon atoms. Other common examples are epoxy-functional ethylpolysilicates and reactants of aminoalkyltrialkoxysilanes with epoxy-functional alkyltrialkoxysilanes.

Specific examples include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hydrogentriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2 With-(3,4-ethoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane Reactant of 3-aminopropyltriethoxysilane, condensation reaction of silanol-terminated methylvinylsiloxane oligomer with 3-glycidoxypropyltrimethoxysilane, silanol-terminated methylvinylsiloxane oligomer and 3-metha Condensation reactants of krilloxypropyltriethoxysilane and tris (3-trimethoxysilylpropyl) isocyanurate.

Compositions of the present invention may also contain inorganic fillers (such as silica, glass, alumina, zinc oxide, etc.), provided they do not impair the object of the present invention; Silicone rubber powder; Resin powders such as silicone resins, polymethacrylate resins, and the like; Heat resistant agent; Antioxidants; Radical scavengers; Light stabilizers; dyes; Pigments; It can be mix | blended as an additional arbitrary component chosen from a flame retardant additive, a reaction delay agent, etc. Reaction delay agents may be used, for example, 2-Phenyl-3-butyn-2-ol, but is not limited thereto.

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

The light emitting diode device of the present invention will now be described in detail.

The light emitting diode device of the present invention is characterized in that the light emitting diode element is enclosed therein by the cured product of the composition according to the present invention described above. The composition used in the present invention can be used for light receiving and emitting devices for semiconductor laser devices, organic ELs, photodiode devices, phototransistor devices, solid-state imaging devices, and photocouplers in addition to such light emitting diode devices.

1 is a cross-sectional view of a representative light emitting diode device of the present invention. In the light emitting diode (LED) device 10 shown in FIG. 1, a light emitting diode (LED) chip 13 is die coupled onto a die pad 16 on a substrate 15, which is a light emitting diode (LED) chip 13. Silver is wire bonded to the inner lead 14 by a bonding wire 12. This light emitting diode (LED) chip 13 is sealed by the hardened | cured material 11 of the light emitting diode element sealing material of this invention.

In order to fabricate the surface mounted light emitting diode (LED) device 10 shown in FIG. 1, a light emitting diode (LED) chip 13 is die bonded onto the die pad 16, and a light emitting diode (LED) chip 13 is provided. Is wire-bonded to the inner lead 14 by a bonding wire 12. Next, the light-emitting diode element encapsulant of the present invention, in particular the encapsulant, is introduced, preferably degassed, and then cured by heating to 50 to 200 ° C.

Hereinafter, the present invention will be described in more detail with reference to Examples and drawings. The following examples are provided to illustrate the present invention, but the scope of the present invention is not limited thereto.

Preparation of [Preparation Example ^{1] a-1 (M Vi} , Me2 0 .15 D Me, Ph 0 .15 T Ph 0 .7)

138.81 g of phenyltrimethoxysilane, 13.98 g of divinyl tetramethyldisiloxane, 16.28 g of α, ω-dimethylhydroxysilyl-methylphenylpolysiloxane, 100 g of toluene, methane 0.25 g of sulfonic acid was added and 50 g of distilled water was slowly added dropwise while stirring. The fruit of the reactor was heated to slowly recover the reaction byproducts. Thereafter, water washing was performed until the reaction was neutral. The organic layer containing the organosiloxane was collected, added to a separate flask, and heated to further remove condensed water. In the next step, 0.16 g of 20% aqueous potassium hydroxide solution was added thereto, and the temperature was raised to remove residual silanol groups. The last residual solvent was removed by distillation under reduced pressure to obtain 100 g of an organopolysiloxane having a network structure of 1.2 mmol / g of vinyl, a refractive index of 1.556, and a volatile matter of 0.8%.

Production Example 2 Preparation of a-2

Condenser, thermometer, and 70% of ^{a-1 (M Vi, Me2} 0 .15 D Me, Ph 0 .15 T Ph 0 .7) produced in Production Example 1 in a flask of 60 ℃ with a stirrer and a line for injecting nitrogen attached Toluene solution was injected. 3 parts by weight of triallyl isocyanurate, 18.6 parts of α, ω-vinyldimethylsilyl-methylphenylpolysiloxane, and platinum complexed with divinyltetramethyldisiloxane were added to 100 parts by weight of the injected toluene solution. The catalyst in the diluted form was added in an amount such that the total solid content was 2.5 ppm based on the platinum atom, and uniformly mixed, and 1.2 parts by weight of the c-3 component prepared by the method of Preparation Example 5 was slowly added dropwise. After heating the fruit of the reactor to proceed with the reaction, distillation under reduced pressure to obtain an organopolysiloxane containing a vinyl content 1.2mmol / g, refractive index 1.552, isocyanurate ring structure of 0.8% volatile matter.

Production Example 3 Preparation of b

<Production of α, ω-dimethylhydroxysilyl-methylphenylpolysiloxane>

100 g of methylphenyldichlorosilane was slowly added dropwise and hydrolyzed in the state of stirring a mixture of 100 g of toluene and 161.4 g of water in a flask at low temperature, and it polymerized by heating up.

After the stirring was stopped and the mixture was kept in a stationary state, the layers were separated, and the wastewater (HCl + H ₂ O) layer was separated from the flask, followed by washing with water in the same amount. The washing process was repeated until the wastewater layer became neutral, and then the wastewater layer was removed in the last step, and then a toluene solution of methylphenyl organopolysiloxane having a terminal silanol was prepared. The low boiling point reactant was stripped to obtain α, ω-dimethylhydroxysilyl-methylphenylpolysiloxane having a refractive index of 1.54 and a viscosity of 600 cP.

<Production of α, ω-Vinyldimethylsilyl-methylphenylpolysiloxane>

Into a flask equipped with a condenser, a thermometer, a nitrogen injection line, and a stirrer, 100 g of the dimethylhydroxysilyl-methylphenylpolysiloxane, 8.5 g of divinyl tetramethyldisiloxane, and 3.2 g of acid clay were added thereto, and the temperature was increased. Volatile content of the reaction was measured and when the reaction became 12% or less, the reaction was terminated and cooled to room temperature.

The colorless and transparent organopolysiloxane obtained by filtering the reaction product was removed 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 organopolysiloxane was analyzed by nuclear magnetic resonance analysis of the vinyl content and confirmed that it was synthesized in the target structure.

Comparative Preparation Example 1 Preparation of c-2 (PhSi (OSiMe ₂ Vi) ₃ )

Into a flask equipped with a condenser, a thermometer, a nitrogen injection line, and a stirrer, 61 g of distilled water, 419 g of divinyl tetramethyldisiloxane, and 1.02 g of trichloromethanesulfonic acid were added and the temperature was raised to 60 ° C., followed by 297 g of phenyltrimethoxysilane. The reaction was maintained after dropping. Layer separation was carried out in the next step and the organic layer containing organopolysiloxane was added to a separate flask to distilled under reduced pressure 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.

Production Example 5 Preparation of c-3

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

[Examples and Comparative Examples]

The siloxanes prepared in Preparation Examples and Comparative Preparation Examples above were GPTMS (Glycidoxypropyltrimethoxysilane) (d) as an adhesion imparting agent, platinum-based catalyst (e) as a catalyst, and 2-phenyl-3-butyn-2-ol (2-) as a reaction delaying agent. Phenyl-3-butyn-2-ol) (f) was mixed and mixed in the ratio of Table 1 to prepare a composition. In addition, c-1 used triallyl isocyanurate (Triallyl Isocyanurate, ACOS).

Platinum-based catalysts were used in which a compound of the following formula was diluted in an amount of 2% by weight in xylene.

Furtherance Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 a-1 60 5 10 35 60 70 60 a-2 80 75 69 35 b 16 8 13.5 15 c-1 3 2 c-2 6.5 7 c-3 20 19 19 20 19 19 22 24 d One One One One One One One One e 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 f 250 250 250 250 250 250 250 250

In Table 1, the amounts of a, b, c and d composition mean parts by weight, and the amounts of e and f composition are ppm relative to the total amount of a, b, c and d.

Test Example  1: Measurement of physical properties of the composition

[Hardness]

The polyorganosiloxane curing specimens were cured for 20 minutes at 170 ° C. using a mold having a space of 6 mm, demolded in the mold, and cured in an oven at 150 ° C. for 3 hours. The hardness of hardened | cured material was measured with the type D durometer based on JISK 6253.

Heat resistance conditions were measured by the same method after the polyorganosiloxane cured specimen prepared in the same manner as above and further stored in an oven at 200 ℃ for 168 hours.

[Tension, elongation]

The polyorganosiloxane curing specimens were cured for 20 minutes at 170 ° C. using a mold having a gap of 2 mm, demolded in the mold, and cured in an oven at 150 ° C. for 3 hours. Tensile and elongation of hardened | cured material were measured by the method based on KS M 6518.

Heat resistance conditions were measured by the same method after the polyorganosiloxane cured specimen prepared in the same manner as above and further stored in an oven at 200 ℃ for 168 hours.

[Coloring (YI) and Color (HPHA color)]

The polyorganosiloxane curing specimens were cured for 20 minutes at 170 ° C. using a mold having a gap of 2 mm, demolded in the mold, and cured in an oven at 150 ° C. for 3 hours. The cured product was measured in accordance with ASTM E313 and ASTM D1209 using a Nippon Deshoku company color difference meter 300A, heat-resistant conditions were further 200 ℃ polyorganosiloxane cured specimen prepared in the same manner as described above After storage for 168 hours in the oven was measured in the same manner.

Test Example  2: LED PKG Physical properties of

The surface mounted LED lead frame was used by Jinjin Nextech's open tool, top-view 3528 4 pad “B” type (Jeong NeXT Corporation), and was die-bonded and wire-bonded to the lead frame. The polyorgano siloxane composition was dispensed and cured in an oven at 80 ° C. for 1 hour, followed by curing reaction at 150 ° C. for 1 hour, thereby preparing one lead frame (64 surface mounted LEDs) for each experiment.

[Thermal shock]

Thermal Shock: In the experiment having a temperature range from -40 ° C to 110 ° C, a total of 10 experiments were performed for 20 minutes at -40 ° C and 20 minutes at 110 ° C.

[MSL]

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

[1000 hours high temperature reliability]

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

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

Furtherance Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Initial Hardness (Shore D) 40 45 40 41 43 30 43 25 Initial Tension (MPa) 4 4.5 3.9 4.1 4.2 1.5 3.7 One Heat Resistance Tension (MPa) 5 5.5 4.8 5.2 5.5 2 4.2 1.4 Tensile Change Rate (%) 25 22.2 23.1 26.8 31.0 33.3 13.5 40.0 Initial Elongation (%) 100 100 110 105 100 100 77 150 Heat Elongation (%) 80 80 85 80 80 70 65 68 Elongation rate of change (%) -20.0 -20.0 -22.7 -23.8 -20.0 -30.0 -15.6 -54.7 Initial YI 0.89 1.04 1.05 1.08 0.98 0.93 1.05 1.03 Heat resistant YI 3.38 3.54 3.5 3.82 3.9 4.57 3.96 15.3 Initial APHA 11 17 12 14 11 13 11 23 Heat resistant APHA 53 62 49 53 55 57 55 122 Thermal shock 0/16 0/16 0/16 0/16 0/16 0/16 3/16 0/16 M.S.L 0/16 0/16 0/16 0/16 0/16 1/16 0/16 5/16 1000 hours
High Temperature Reliability 97% 96% 98% 97% 98% 94% 93% 87% Flexibility Good Good Good Good Good Good Good Good Takcy Good Good Good Good Good Bad Bad Bad

10: LED device
11: hardened material of encapsulant
12: bonding wire
13: LED chip
14: inner lead
15: substrate
16: die pad

Claims (10)

A curable organopolysiloxane composition having an initial elongation of 90% or more and a hardness of Shore D 35 or more, measured by KS M 6518, for a cured state specimen. The method of claim 1,
A curable organopolysiloxane composition having an elongation change of 25% or less after storing the cured state specimen at 168 hr at 200 ° C. The method of claim 1,
Initial tensile strength, measured by KS M 6518, on hardened specimens is at least 3.5 MPa,
A curable organopolysiloxane composition having a change in tensile strength of 35% or less after 168hr storage at 200 ° C. The method of claim 1,
The composition was stored in a cured state (thickness 2mm, width 1cm, length 5cm) at 200 ° C. for 168hr, and then bent at a pressure of 60g / cm ² for 10 seconds until one side of the specimens contacted each other at 25 ° C. Curable organopolysiloxane composition, characterized in that the physical damage of the specimen does not occur until time passes. The method of claim 1,
The composition is a curable organopolysiloxane composition having a structure crosslinked by a compound of formula (I):
[Formula 1]

In Chemical Formula 1,
Ra to Rc are hydrogen, alkenyl group having 2 to 12 carbon atoms or silicon,
Any one or two or more of Ra to Rc is an alkenyl group or silicon having 2 to 12 carbon atoms. The method of claim 1,
The composition comprises a compound of formula 1 and 2,
The curable organopolysiloxane composition has a structure crosslinked by a compound of formula 1:
[Formula 1]

(2)
^{(R 1 R 2 R 3 SiO} 1/2) x · (R 4 R 5 SiO 2/2) y · (R 6 SiO 3/2) z
In Chemical Formula 1,
Ra to Rc are hydrogen, alkenyl group having 2 to 12 carbon atoms or silicon,
Any one or two or more of Ra to Rc is an alkenyl group or silicon having 2 to 12 carbon atoms, and has a structure combined with a compound of formula (2),
In Formula 2,
R ¹ to R ⁶ are each independently hydrogen, an alkenyl group having 2 to 12 carbon atoms, or a monovalent hydrocarbon group having 1 to 12 carbon atoms except for an alkenyl group, provided that at least one of R ¹ to R ³ , R ⁴ and Any one or more selected from the group consisting of R ⁵ and R ⁶ , and an alkenyl group having 2 to 12 carbon atoms,
x, y and z satisfy 0 <x <1, 0 <y <1, 0 ≦ z <1 and x + y + z = 1, respectively. The method of claim 1,
The composition comprises a compound of formulas (1) and (3)
The curable organopolysiloxane composition has a structure crosslinked by a compound of Formula 1:
[Formula 1]

(3)

In Chemical Formula 1,
Ra to Rc are hydrogen, alkenyl group having 2 to 12 carbon atoms or silicon,
Any one or two or more of Ra to Rc is an alkenyl group or silicon having 2 to 12 carbon atoms, and has a structure combined with a compound of formula (3),
In Formula 3,
R ⁷ to R ¹¹ are each independently hydrogen; Or a monovalent hydrocarbon group having 1 to 12 carbon atoms except for an alkenyl group, R ⁹ and R ¹⁰ are each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms except for an alkenyl group, and n is an integer of 1 to 100. The method of claim 5, wherein
The composition comprises a compound of formula 1 to 3,
A curable organopolysiloxane composition having a structure crosslinked by a compound of formula (2):
[Formula 1]

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

In Chemical Formula 1,
Ra to Rc are hydrogen, alkenyl group having 2 to 12 carbon atoms or silicon,
Any one or two or more of Ra to Rc is a alkenyl group or silicon having 2 to 12 carbon atoms, and is a structure combined with any one or more compounds of Formulas 1 and 3,
In Formula 2,
R ¹ to R ⁶ are each independently hydrogen, an alkenyl group having 2 to 12 carbon atoms, or a monovalent hydrocarbon group having 1 to 12 carbon atoms except for an alkenyl group, provided that at least one of R ¹ to R ³ , R ⁴ and Any one or more selected from the group consisting of R ⁵ and R ⁶ , and an alkenyl group having 2 to 12 carbon atoms,
x, y and z satisfy 0 <x <1, 0 <y <1, 0 ≦ z <1 and x + y + z = 1, respectively
In Formula 3,
R ⁷ to R ¹¹ are each independently hydrogen; Or a monovalent hydrocarbon group having 1 to 12 carbon atoms except for an alkenyl group, R ⁹ and R ¹⁰ are each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms except for an alkenyl group, and n is an integer of 1 to 100. An encapsulant for a light emitting diode device comprising a cured product of the composition according to any one of claims 1 to 8. A light emitting diode device in which a light emitting diode element is encapsulated by an encapsulant according to claim 9.

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