KR101211088B1 - Led heat-resistance silicon curable compositions having increased reactivity - Google Patents

Abstract

PURPOSE: A heat-resistant silicone curable composition is provided to have low shrinkage ratio, hardness characteristic, crack resistance and excellent optical transmittance which are characteristics of silicone rubber after curing by heat. CONSTITUTION: A heat-resistant silicone curable composition comprises 84-95 weight% of organic polysiloxane, 4-15 weight% of organic polyhydrogensiloxane which has two or more Si-H functional groups in a molecule, and 0.05-1 weight% of precious metal hydrosilation catalyst. The polyorganosiloxane is (a-1)polyorganosiloxane which is formed by reacting two or more alkenyl groups in a molecule and a coupling agent or a mixture of the component (a-1) and the polyorganosiloxane with two or more alkenyl groups in a molecule.

Description

LED Heat-Resistance Silicon Curable Compositions having Increased Reactivity

The present invention relates to a heat resistant silicone curing composition for LEDs with improved reactivity.

Recently, the light emitting diode has a low voltage and a long life, and is applied to many business fields in order to save energy. In particular, it is widely applied to the backlight of the liquid crystal display and home and industrial use. Light emitting diodes have advantages such as high brightness, fast switching response, easy light emission control, and easy design depending on the use. In addition, a light emitting device having various wavelengths may be obtained by mixing a fluorescent material with an organic composition to encapsulate a light emitting diode.

Conventionally, the organic composition used in encapsulating a light emitting device used epoxy resin. Epoxy resins not only have high adhesion but also have an excellent role in protecting chips from external environments. However, there is a disadvantage that the epoxy cured product is easily discolored by heat or light generated while using the light emitting diode. When the cured product is discolored, the transmittance of the diesel fuel is reduced and the original color of the diode is changed. In order to overcome such drawbacks, a composition using an epoxy-silicon mixture has been developed, but there is a shortcoming in that it is insufficient to compensate for the inherent disadvantages of epoxy. In order to prevent discoloration of hardened | cured material, the development of the composition using a silicone compound is progressing actively. The silicone composition has a disadvantage of less discoloration of the cured product due to light or heat but inferior adhesion to the diode housing. If the adhesive force is reduced, the diode is exposed to the external environment, which significantly shortens its lifespan.

Numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated herein by reference in their entirety to better understand the state of the art to which the present invention pertains and the content of the present invention.

The present inventors earnestly tried to develop a heat-resistant silicone curing composition for LEDs for encapsulating a light emitting diode using polyorganosilicon resin for light emitting diodes. As a result, we have developed a polyorganosilicon composition having elasticity, low shrinkage, hardness, crack resistance and excellent light transmittance, which are characteristic of silicone rubber even after the composition has been cured by heat. The present invention was completed by confirming high and low moisture permeability.

Accordingly, it is an object of the present invention to provide a heat resistant silicone curing composition for LEDs.

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

According to one aspect of the present invention, the present invention provides a heat-resistant silicone curable composition for LEDs having improved reactivity comprising the following components:

(a) a polyorganosiloxane having two or more alkenyl groups in a molecule and a coupling agent reacted, or (ii) a poly having two or more alkenyl groups in the component (iii) and a molecule. As a mixture of organosiloxanes, 84-95% by weight of polyorganosiloxanes relative to the total composition;

(b) 4-15% by weight of polyorganohydrogensiloxane, based on the total composition, having at least two Si-H functional groups in the molecule; And

(c) 0.05-1% by weight of noble metal silicon hydride catalyst based on total composition.

The present inventors have diligently researched to develop a heat-resistant silicone curable composition for LEDs for encapsulating a light-emitting diode using polyorganosilicon resin for a light-emitting diode, so that even after the composition has been cured by heat, elastic rubber, low shrinkage, A polyorganosilicon composition having hardness characteristics, crack resistance and excellent light transmittance was developed, and in particular, it was confirmed that the adhesion was high and the moisture permeability was low regardless of the material of the diode housing.

The present invention relates to a curable composition used to encapsulate a light emitting diode, and to a composition using a polyorganosilicone resin having excellent transmittance and thermal stability. Unlike organic compounds, polyorganosilicone resins are used to encapsulate light emitting diodes due to their excellent resistance to light and heat. However, polyorganosilicone resins have disadvantages of poor compatibility with other compounds and poor adhesion after curing. If the adhesive strength with the housing drops after curing, the lifetime of the diode will be reduced due to exposure of the diode to normal atmosphere. One of the biggest advantages of the light emitting diode is that the lifetime of the light emitting diode causes a very large wavelength. In general, some light emitting diodes are used to complete a single product using a few as many as several dozen or more diodes. In order to make up for such drawbacks, a composition mixed with a high adhesive epoxy resin was studied, but miscibility with the polyorganosilicon resin was insufficient to ensure storage stability of the composition.

In general, compositions using polyorganosilicon resins use a coupling agent that serves to improve adhesion between the composition and the housing to increase adhesion. A coupling agent contains an alkoxysilane group, an epoxy group, a vinyl group, etc., and is a compound which generally consists of two or more of these functional groups. The coupling agent has a characteristic of being miscible with the polyorganosilicon compound depending on the proportion of the silicon element in the molecule. The higher the specific gravity of the silicon element is, the more the miscible property increases, but there are disadvantages in that other properties of the cured product may be degraded.

In the present invention, a coupling agent having poor compatibility with the silicone composition is reacted with a polyorganosilicon resin having two or more alkenyl groups in a molecule to improve storage stability and adhesion. Polyorganosilicone resins can be broadly divided into low-viscosity silicone resins containing vinyl groups at the end and vinyl-functional QM (VQM) resins having vinyl groups and SiO ₂ groups. VQM resin is a solid or high viscosity resin and its physical properties depend on the content of SiO ₂ groups. In general, VQM resin is used in a solvent-dissolved state or dissolved in a low viscosity silicone resin for ease of use. VQM resins will contain hydroxyl groups that do not fully progress to SiO ₂ groups during synthesis. If the hydroxyl group is forcibly removed during the synthesis, the VQM resin has a disadvantage in that the solubility in general solvents is reduced. When the solubility in solvents is poor, solubility in general silicone resins is also lowered, making it difficult to obtain a homogeneous product in preparing the composition. Therefore, in the present invention, the alkoxy silane compound was reacted with the hydroxy group present in the VQM resin to improve the storage stability and adhesion of the product. As the alkoxy silane compound, a commonly used silane coupling agent may be used, and the amount of the alkoxy silane compound may be used in an amount of 0.05-5 equivalent% based on the total monomers of the VQM resin. If the amount of the coupling agent is less than 0.05 equivalent%, the improvement of the physical properties of the composition is inadequate. If the coupling agent is used more than 5 equivalent%, there is a disadvantage inferior in miscibility and hygroscopicity.

According to a preferred embodiment of the present invention, the present invention provides a heat-resistant silicone curable composition for an LED, wherein the polyorganosiloxane having two or more alkenyl groups in the molecule of component (a) is represented by the following general formula (1):

Formula 1

In the above Formula _{1, R 1, R 2,} R 3, R 4, R 5 and R ₆ are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-22 aryl, C _{3 -20} An allyl or hydroxy group, where l, m, n and o are numbers satisfying 1> l≥0, 1> m≥0, 1> n≥0 and 1> o≥0, provided they are l + m + n + o = 1 and n + o≥0).

The term "alkyl" in the context of the present invention refers to an aliphatic hydrocarbon group. The alkyl moiety may be a "saturated alkyl" group, meaning that it does not contain any alkenes or alkyne moieties. The alkyl moiety may be a “unsaturated alkyl” moiety, meaning that it contains at least one alkene or alkyne moiety. In saturated or unsaturated alkyl may be branched, straight chain or cyclic.

Alkyl groups may have 1-20 carbon atoms. The alkyl group may be medium sized alkyl having 1-10 carbon atoms, but preferably lower alkyl having 1-6 carbon atoms. For example, C ₁ -C ₄ alkyl has 1-4 carbon atoms in the alkyl chain, ie the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t- It may be selected from the group consisting of butyl.

The alkyl group may be optionally substituted or unsubstituted. When substituted, the substituents are cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, merceto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, O- Individually from carboxy, isocyanato, thiocyanato, isothiocyanato, amino including nitro, cyryl, trihalomethanesulfonyl, mono- and di-substituted amino groups, and protective derivatives thereof And one or more groups independently selected. Typical alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. It is not limited to this.

The term “alkenyl” refers to a straight or branched unsubstituted or substituted unsaturated hydrocarbon group having the specified carbon number, for example ethenyl, vinyl, propenyl, isopropenyl, butenyl, isobutenyl, n -pentenyl and n -Hexenyl.

The term "aryl" in the context of the present invention has at least one ring having a shared pi electron field and carboxylic aryl (eg phenyl) and heterocyclic aryl groups (eg pyridine) It means an aryl group containing. The aryl includes monocyclic or fused ring polycyclic (ie rings that divide adjacent pairs of carbon atoms) groups.

To have the term "allyl (Allyl)" molecular structure _{H 2 C = CH-CH 2} R in the context of the present invention, a methylene group (-CH ₂ -) attached to the vinyl group (-CH = CH ₂₎ to Allyl positions include, but are not limited to, all of the functional groups mentioned above, such as alkyl, aryl, heteroaryl, hydroxyl, amine, carbonyl group and derivatives thereof.

In the present specification, the term “hydroxyl” has a molecular formula of R—OH and means a functional group including a hydrogen atom covalently linked to an oxygen atom. The neutral form of the hydroxyl group is a radical, The anionic form of the hydroxyl group is called hydroxide.

 If the alkenyl group is located at both ends, the elasticity is good after curing, but the hardness and adhesive strength are lowered. If the alkenyl group is too large, the elasticity may be reduced after curing to cause surface cracking of the cured product. Suitable amounts of alkenyl groups in formula (1) are preferably in the range of 0.05 to 0.5 moles per 100 g of component. In particular, in the case of component (a), the polyorganosiloxane may be used by mixing a compound having n + o = 0 and a compound having n + o> 0 in the formula (1). In the case of polyorganosiloxane having a repeating unit of n + o = 0, the compound has a low viscosity and serves to relieve stress after curing. In order to relieve stress, it is advantageous that the alkenyl group is located at the terminal of the molecule. The polyorganosiloxane having a repeating unit of n + o> 0 plays a role of improving reinforcement like the inorganic filler after curing. In the case of using an inorganic filler, the transmittance of the light is reduced, and thus the material can be replaced. In the case where a compound having a repeating unit of n + o = 0 and a compound having n + o> 0 are used in combination, the ratio may be different depending on the use. If a lot of compounds with n + o = 0, the stress after curing is relaxed, but the hardness is poor.

  In the composition of the present invention, component (a) is 84-95% by weight of polyorganosiloxane, preferably 90-95% by weight relative to the total composition.

According to a preferred embodiment of the present invention, the polyorganosiloxane produced by the reaction of the polyorganosiloxane having two or more alkenyl groups in the molecule of the component (a) and the coupling agent is represented by the following formula (2) Provide a heat resistant silicone curing composition:

(2)

In the above Formula _{2, R 1, R 2,} R 3, R 4, R 5, R 6 and R ₇ are each independently C _{1 -20} alkyl, C _{2 -20} alkenyl, C _6-22 aryl, C _3-20 is an allyl or a hydroxyl group, R ₈ and R ₉ represents a glycidyl group, a vinyl siloxane group or hydrogen functional siloxane groups include, l, m, n, o, p and q are 1> l≥0, 1> m≥0, 1> n≥0, 1> o≥0, 1> p≥0 and 1> q≥0, provided they are l + m + n + o + p + q = 1 and l + m + n + o> 0 and p + q> 0).

The monomer (p + q) containing these functional groups is 0.05-5 equivalent% with respect to the total equivalent of polyorganosiloxane. If the amount is too small, the original adhesive properties cannot be obtained, and if the amount is too large, there is a disadvantage in that miscibility and hygroscopicity are poor. The compound represented by the formula (2) may be used in admixture with the compound represented by the formula (1) in preparing a curable silicone composition, or may be used alone without using the compound represented by the formula (1). If used alone may be difficult to adjust the viscosity.

Coupling agents that react with polyorganosiloxanes (eg, VQM resins) having two or more alkenyl groups in the molecule include vinyl trialkoxysilanes, allyl trialkoxysilanes, 3-glycidoxypropyl trialkoxysilanes, and 3-methacryloxy Propyl trialkoxysilanes or compounds having the following formulas (5) to (11) can be used:

Formula 5

6

Formula 7

Formula 8

Formula 9

Formula 10

Formula 11

In Formulas 5 to 11, a and b are integers of 1-30.

Coupling agents that react with polyorganosiloxanes (eg, VQM resins) having two or more alkenyl groups in the molecule are preferably vinyl trialkoxysilanes, allyl trialkoxysilanes, 3-glycidoxypropyl trialkoxysilanes or 3- Methacryloxypropyl trialkoxysilane, more preferably vinyl trialkoxysilane or 3-glycidoxypropyl trialkoxysilane, still more preferably vinyl trimethoxysilane, vinyl triethoxysilane, 3-glyci Doxypropyl trimethoxysilane or 3-glycidoxypropyl triethoxysilane.

In the composition of the present invention, the coupling agent is 0.5-20% by weight of polyorganosiloxane relative to the total composition, preferably 0.5-15% by weight, more preferably 1-8% by weight, even more preferably 1 -5 wt%.

The said coupling agent can also be used in mixture of 1 or more types. Compounds containing an epoxy group and an alkoxysilane group showed good effects on the adhesion. The chemical reaction of the polyorganosiloxane (VQM resin) having two or more alkenyl groups with the coupling agent may be represented by, for example, Scheme 1 below.

Scheme 1

R ₁ and R ₂ in the above Scheme 1 each independently represents a C _{1 -20} alkoxy group or C _{1 -20} alkyl, R ₃ represents a group of functions including a glycidyl group, a vinyl group is a siloxane or hydrogen siloxane. The term "alkoxy" refers to the group -O, and, for example, methoxy, ethoxy and the like, it is not the number of carbon atoms of the C _1-20 alkoxy when the substituted substituent includes.

Synthesis of new resin using VQM resin can be easily synthesized by mixing with alkoxysilane, but it is necessary to shorten the reaction time by raising the reactor temperature to 80 ° C. Byproduct methanol is removed under reduced pressure. In general, since the VQM resin is a solid or high viscosity resin, it is advantageous to proceed with the reaction after dissolving in a solvent or a low viscosity silicone resin. Examples of the solvent include benzene, toluene or xylene which are aromatic compounds. Low viscosity silicone resin may be a resin having a 500 ~ 6,000 cPS containing a vinyl group at both ends. The viscosity of the low viscosity resin can be selected and used depending on the application. If a solvent is used, it must be removed under reduced pressure after completion of the reaction. If possible, distillation under reduced pressure below 100 ° C. is advantageous. If the temperature is higher than this, side reactions proceed and the color changes, thereby reducing the permeability of the resin. The reaction time is appropriate for 5 hours at 80 ℃. As the reaction proceeds, the viscosity increases, and when the viscosity stops, the reaction may be terminated.

According to a preferred embodiment of the present invention, the polyorganohydrogensiloxane having two or more Si-H functional groups in the molecule of the component (b) provides a heat-resistant silicone curable composition for LED, characterized in that :

(3)

In Chemical Formula 3, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently C _1-20 alkyl, C _6-22 aryl, hydrogen, or a hydroxy group, and R ₈ and R ₉ is hydrogen or methyl, l ', m', n ', o', p 'and q' are 1>l'≥0,1>m'≥0,1>n'≥0,1> o '≥0, 1>p'≥0 and 1>q'≥0, provided they are l' + m '+ n' + o '+ p' + q '= 1 and l' + m '+ n' + o '> 0 and p' + q '≧ 0).

It is preferable that the quantity of the silicon atom which has the said Si-H functional group is 2-30 mol% with respect to the quantity of all the silicon atoms. If the amount is larger than this, the elasticity, which is an inherent characteristic of the cured silicone, is lowered. If the amount is smaller than this, the alkenyl group and the curing reaction do not sufficiently occur, resulting in a decrease in hardness. It is common to mix the Si—H functional groups in an amount of 0.5 to 4.0 equivalents relative to the total alkenyl groups in preparing the compositions. The most common ratio uses about 1.5 times Si-H equivalents relative to alkenyl. However, it may be used in a wider range depending on the purpose of the final cured product.

In the composition of the present invention, component (b) is 4-15% by weight of polyorganohydrogensiloxane, preferably 4-10% by weight based on the total composition.

In the composition of the present invention, the noble metal hydride catalyst (component c) is a catalyst in which an alkenyl group and a Si-H functional group promote an addition curing reaction. Preferably, the noble metal hydrosilation catalyst is a platinum-containing catalyst, the platinum-containing catalyst, for example 1, platinum black, (2) Halon halogenated platinum _{(PtCl 4, H 2 PtCl 4} . 6 H 2 O, NaPtCl. 4 H ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ ), (3) complexes between platinum and olefins, alcohols, ethers, aldehydes, ketones or vinylsiloxanes, (4) bis (gamma-picolin) -platinum dichloride, (5 ) Trimethylenedipyridine-platinum dichloride, (6) dicyclopentadiene-platinum dichloride, (7) cyclooctadiene-platinum dichloride, (8) cyclopentadiene-platinum dichloride, (9) bis (alky) Nil) bis (triphenylphosphine) -platinum complex or (10) bis (alkynyl) (cyclooctadiene) -platinum complex. The platinum catalyst may be used alone or in a mixture of two or more thereof. The amount of the platinum catalyst is generally 1 to 1000 ppm, more preferably 5 to 500 ppm, as a metal equivalent to the total polyorganosiloxane compound.

In the composition of the present invention, component (c) is 0.05-1% by weight of the noble metal hydride catalyst based on the total composition, preferably 0.1-0.5% by weight.

The composition of the present invention may further include an additive in addition to the components (a) to (c) to supplement the physical properties after curing, for example, a cyclic siloxane having an alkenyl group in the molecule, and a cyclic siloxane having a Si-H functional group in the molecule. , Coupling agents or curable pot life regulators. Additives may not be used in some cases.

According to a preferred embodiment of the present invention, the additive is a low molecular cyclic organosiloxane represented by the following formula (4).

Formula 4

In the above Formula 4, R ₁ and R ₂ are each independently C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{6 -22} aryl or represents hydrogen, n = an integer of 1-8. In the case of the compound represented by the formula (4), an equivalent of an alkenyl group, an aryl group or a hydro group is easy, and may be used as a viscosity modifier.

The above-mentioned coupling agent may be used to improve the adhesive force. In the case of a coupling agent, the main feature is that it contains at least one epoxy group, alkenyl group, hydro group or alkoxy group. For example, common coupling agents include vinyl trialkoxysilane, allyl trialkoxysilane, 3-glycidoxypropyl trialkoxysilane and 3-methacryloxypropyl trialkoxysilane. If not used in some cases, the transmittance excellent in storage stability and cured product permeability of the composition can be obtained.

Additives used to control pot life in the curing process include acetylenic alcohols, cycloalkenylsiloxanes, triazole phosphines, mercaptans, amines, hydrazines, fumarates, malates, and the like. Among these, ethynyl cyclohexanol, methyl butynol, and dimethyl hexinol are excellent, and can be used 1 type or in mixture of 2 or more types. The amount used may vary depending on the amount of catalyst and the desired pot life.

The composition of the present invention may have different physical properties depending on the composition of the polyorganosiloxane. According to a preferred embodiment of the present invention, the composition of the present invention is characterized in that the heat-resistant silicone curing composition for LED, characterized in that the transmittance decrease 0.1-5% and the refractive index (Refractive index) 1-2.

The composition prepared using the above-described materials should minimize contamination by metallic foreign particles and particulate foreign materials in order to be used as a die bonding material. The composition preparation is placed in each stirrer and stirred until the mixture is uniformly mixed and there is no change in viscosity. If the viscosity remains constant, the composition is filtered and then packaged in a suitable container and stored at low temperature.

The features and advantages of the present invention are summarized as follows:

(a) It is a heat-resistant silicone curing composition for LED which uses the polyorganosilicon resin for light emitting diodes of this invention, and improved reactivity.

(b) The composition of the present invention has the characteristics of elasticity, low shrinkage, hardness, crack resistance and excellent light transmittance which are characteristic of silicone rubber even after curing by heat, in particular, it has high adhesion and moisture regardless of the material of the diode housing. Low permeability.

(c) The composition of the present invention can be used as a protective film for protecting the light emitting diode from the external environment.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Example

Experimental Method

① Transmittance: The transmittance was measured at 460 nm using a UV-VIS spectrum analyzer.

② Refractive Index: The composition was molded and cured to a thickness of 2 mm and measured using an Abbe refractometer.

③ Heat resistance: The composition was molded and cured to a thickness of 2 mm to observe a color change after 1,000 hours at 150 ° C.

④ Crack resistance: Absorb moisture in the 85 ℃ / 85RH% chamber for 72 hours, then leave it at room temperature for 24 hours, and then perform 260 ℃ IR Reflow three times to check the penetration of the die.

⑤ Adhesive force: 80 mil ² sapphire chip is adhered to polyphthalamide (PPA), ceramic or metal PCB (Metal Printed Circuit Board) and 80 ℃ / 1 hour + 120 ℃ / 1 hour + 160 ℃ / 1 hour After curing in an oven under the conditions, the shear adhesive force was measured by Dage 4000 Die shear tester (Dage).

Synthetic example

           VQM resin and silane compound were added to a reactor equipped with a stirrer and a distillation apparatus, followed by stirring for 1 hour. After confirming that both compounds were well dissolved, the temperature inside the reactor was raised to 80 ° C. and stirred for 5 hours. After the reaction, the pressure was reduced to 10 mmHg at the same temperature to completely remove the byproduct methanol and the unreacted silane compound. After the reactor temperature was lowered to room temperature, the vacuum was released to measure the viscosity of the resin.

Viscosity Measurement of New Resin Resin No. VQM Resin Silane compound New Resin
Viscosity (cPs) usage
(g) Viscosity (cPs) Compound name usage
(g) S1 100 6,000 3-glycidoxypropyl
Trimethoxysilane 5 9,800 S2 100 6,000 3-glycidoxypropyl
Trimethoxysilane 2 7,500 S3 100 6,000 Vinyl trimethoxysilane 5 8,200 S4 100 6,000 Vinyl trimethoxysilane 2 6,900 S5 100 6,000 3-glycidoxypropyl
Triethoxysilane 5 9,500 S6 100 6,000 3-glycidoxypropyl
Triethoxysilane 2 7,100 S7 100 6,000 Vinyl triethoxysilane 5 8,000 S8 100 6,000 Vinyl triethoxysilane 2 6,700

Example  1-6

The synthesized siloxane polymer was put in a plannerary mixer (Daehwa Tech) and stirred sufficiently so that the two polymers (100 g) could be mixed. 5 g of polyhydrogen dimethylsiloxane (hydrogen content: 0.7 mol / 100 g, viscosity: 40 cPs), 1,3-dimethyl-1,1,3,3-tetramethyldisiloxane platinum complex (Aldrich) 0.25 g of platinum catalyst solution (Gelest) (platinum content 4% by weight) diluted in 1,3-diethenyl-1,1,3,3-tetramethylsiloxane (Aldrich), 3-glycidyloxy as an adhesion aid 1 g of propyltrimethoxysilane (Gelest) and 0.05 g of ethynyl cyclohexanol (TCI), a pot life regulator, were added and stirred for 3 hours. The composition was removed from the filter and stored in a container at low temperature. The stored composition was used after stabilizing the viscosity for a sufficient time at room temperature before use.

Resin Composition and Physical Properties of Each Composition (1) Resin No. Example 1 Example 2 Example 3 Example 4 Example 5 S1 70 g - - - - S2 - 70 g 70 g - - S3 - - - 70 g - S4 - - - - 70 g S5 - 30 g - - - S6 30 g - 30 g - - S7 - - - - 30 g S8 - - - 30 g - Initial transmittance (%) 95.2 95.1 95.3 95.4 95.1 Transmittance (%)
(1,000 hours elapsed) 94.1 93.1 94.8 94.6 91.8 Permeability Reduction (%) 1.1% 2.1% 0.52% 0.8% 3.47% Refractive index
(Refractive Index) 1.41 1.42 1.42 1.41 1.41 Heat resistance Yellowing Yellowing Yellowing Yellowing Yellowing Crack resistance × × × × × Adhesion Great Great Very good Great Great

Resin Composition and Physical Properties of Each Composition (2) Resin No. Example 6 S1 - S2 - S3 - S4 70 g S5 - S6 - S7 - S8 30 g Initial transmittance (%) 95.4 Transmittance (%)
(1,000 hours elapsed) 94.9 Permeability Reduction (%) 0.52% Refractive index
(Refractive Index) 1.42 Heat resistance Yellowing Crack resistance × Adhesion Very good

Comparative example

The mixture was sufficiently stirred so that two resins (100 g) of VQM and PVQM2 were mixed in a planner mixer (Daehwa Tech). Platinum catalyst solution in which 1,3-dimethyl-1,1,3,3-tetramethyldisiloxane platinum complex was diluted in 1,3-diethenyl-1,1,3,3-tetramethylsiloxane in this mixer (platinum Content 4 wt%) 0.25 g, 1 g of 3-glycidyloxypropyl trimethoxysilane as an adhesion aid and 0.05 g of ethynyl cyclohexanol as a pot life regulator were added and stirred for 3 hours. The composition was removed from the filter and stored in a container at low temperature. The stored composition was used after stabilizing the viscosity for a sufficient time at room temperature before use.

Physical properties of each composition Resin Comparative Example 1 Comparative Example 2 Comparative Example 3 VQM 70 g 30 g 50 g PVQM 30 g 70 g 50 g Initial transmittance (%) 95.1 95.2 95.1 Transmittance (%)
(1,000 hours elapsed) 80.5 83.7 82.2 Permeability Reduction (%) 15.4% 12.1% 13.6 Refractive index
(Refractive Index) 1.42 1.41 1.41 Heat resistance Yellowing Yellowing Yellowing Crack resistance ○ × ○ Adhesion Very low Very low Very low

Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that the specific technology is merely a preferred embodiment, and the scope of the present invention is not limited thereto. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (10)

Heat Resistant Silicone Curing Compositions for Reactive Enhanced Light Emitting Diodes, Including:
(a) a polyorganosiloxane having two or more alkenyl groups in the molecule (iii), vinyl trialkoxysilane, allyl trialkoxysilane, 3-glycidoxypropyl trialkoxysilane, 3-methacryloxypropyl trialkoxysilane, and A polyorganosiloxane produced by the reaction of a coupling agent selected from the group consisting of the following formulas (5) to (11), polyorganosiloxanes characterized by the following formula (2), or (ii) two in the above components (iii) and molecules A mixture of polyorganosiloxanes having alkenyl groups or more, 84-95% by weight of polyorganosiloxanes based on the total composition;
(b) 4-15% by weight of polyorganohydrogensiloxane, based on the total composition, having at least two Si-H functional groups in the molecule; And
(c) 0.05-1% by weight of a noble metal silicon hydride catalyst based on the total composition;
(2)

Formula 5

6

Formula 7

Formula 8

Formula 9

Formula 10

Formula 11

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-22 aryl, C _3-20 allyl or hydroxy group; R ₈ and R ₉ are functional groups including a glycidyl group, a vinyl siloxane group, and a hydrogen siloxane group; l, m, n, o, p and q satisfy 1> l≥0, 1> m≥0, 1> n≥0, 1> o≥0, 1> p≥0 and 1> q≥0 Number; Provided that they are l + m + n + o + p + q = 1 and satisfy l + m + n + o> 0 and p + q>0; In Formulas 7 to 8, a and b are integers of 1-30.
delete delete The heat-resistant silicone curable composition for an LED according to claim 1, wherein the polyorganohydrogensiloxane having two or more Si-H functional groups in the molecule of component (b) is represented by the following general formula (3):
(3)

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently C _1-20 alkyl, C _6-22 aryl, hydrogen or hydroxy group; R ₈ and R ₉ are hydrogen or a methyl group; l ', m', n ', o', p 'and q' are 1>l'≥0,1>m'≥0,1>n'≥0,1>o'≥0,1> p ' A number satisfying ≧ 0 and 1> q ′ ≧ 0; However, these are the numbers satisfying l '+ m' + n '+ o' + p '+ q' = 1 and l '+ m' + n '+ o'> 0 and p '+ q'≥0.
The catalyst of claim 1, wherein the noble metal hydride catalyst of component (c) is (1) platinum black, (2) platinum halide (PtCl ₄ , H ₂ PtCl ₄ 6H ₂ O, NaPtCl ₄ H ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ ), (3) complexes between platinum and olefins, alcohols, ethers, aldehydes, ketones or vinylsiloxanes, (4) bis (gamma-picolin) -platinum dichloride, (5) trimethylenedipyridine-platinum Dichloride, (6) dicyclopentadiene-platinum dichloride, (7) cyclooctadiene-platinum dichloride, (8) cyclopentadiene-platinum dichloride, (9) bis (alkynyl) bis (triphenylforce) Fin) -platinum complex or (10) bis (alkynyl) (cyclooctadiene) -platinum complex, heat-resistant silicone curable composition for LEDs.
The heat-resistant silicone curable composition for LEDs further comprises an additive, wherein the additive is a cyclic siloxane, a cyclic siloxane having a Si-H functional group in a molecule, a coupling agent or a curable pot life regulator. Heat Resistant Silicone Curing Composition
The heat-resistant silicone curable composition for an LED according to claim 6, wherein the cyclic siloxane is represented by the following Chemical Formula 4:
Formula 4

R ₁ and R ₂ are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-22 aryl, or hydrogen, and n = 1-8.

delete The method of claim 6, wherein the curable pot life control agent is an acetylene alcohol, cycloalkenylsiloxane, triazole phosphine, mercapto derivatives, amine derivatives, hydrazine derivatives, fumarate derivatives or malate derivatives for Heat Resistant Silicone Curing Composition.
The heat-resistant silicone curable composition for an LED according to claim 1, wherein the composition has a transmittance reduction of 0.1-5% and a refractive index of 1-2.