KR20120078497A - Silicone-based resin composition - Google Patents

Abstract

PURPOSE: A silicon-based resin composition is provided to have excellent transmittance, to stability to ultraviolet rays and heat, and to prevent yellowing, thereby capable of being used as transparent sealing material for optical semiconductor for LED, etc. CONSTITUTION: A silicon-based resin composition comprises organopolysiloxane in chemical formula 1: [R^1_aR^2_bVi_cSiO_(4-a-b-c)/2]_n, and organohydrogenpolysiloxane in chemical formula 2: [R^1_aR^2_bH_cSiO_(4-a-b-c)/2]_n, and a metallic catalyst in a platinum group. In chemical formulas, R^1 is selected from a C1-12 alkyl group, a C2-12 aryl group, a C2-12 aralkyl group, and a C2-12 alkenyl group, and R^2 is selected from hydroxy, methoxy, and ethoxy, Vi is a vinyl group, a is a number from 1.00-1.90, b is a number from 0.001-0.2, c is a number from 0.01-0.2, and n is a number from 10-100.

Description

Silicone resin composition {SILICONE-BASED RESIN COMPOSITION}

The present invention relates to a silicone resin composition.

An optical semiconductor device (semiconductor light emitting device) having a LED (light emitting diode) chip, which forms a pn bond in a semiconductor layer grown on a crystal substrate and uses the junction region as a light emitting layer, as a light emitting element is used for various display devices and display devices. It is widely used for such purposes.

Examples of the optical semiconductor device include visible light emitting devices and high temperature operating electronic devices using gallium nitride compound semiconductors such as GaN, GaAlN, InGaN, and InAlGaN, and recently developed in the fields of blue light emitting diodes and ultraviolet light emitting diodes. This is going on.

An optical semiconductor device including an LED chip as a light emitting element has a LED chip mounted on the light emitting surface side of a lead frame, electrically connects the LED chip and the lead frame by wire bonding, and serves as a protection and lens function of the light emitting element. It is sealed by resin.

Recently, white LEDs have attracted attention as a new light source, and it is said that the market will expand greatly in the future, mainly for lighting applications. White LED is applied to YN phosphor on a bare chip of GaN, mixed with blue light emission of GaN and yellow light emission of phosphor, and emits white light. . In addition, recently, a method of combining a plurality of phosphor materials by using an ultraviolet LED chip as a light source has been developed from the improvement of color tone. In addition, in order to use LED for a lighting use etc., the durability improvement is calculated | required.

On the other hand, an epoxy resin is often used as a sealing material used when sealing a light emitting element such as an LED (light emitting diode) chip. Epoxy resins are used for factors such as a transparent point and good workability. Generally, the epoxy resin for LED sealing consists of bisphenol A glycidyl ether, a hardening accelerator, such as methylhexahydro phthalic anhydride, an amine type, or phosphorus type.

However, since these components generate carbonyl groups by absorption of ultraviolet light, there is a drawback that they absorb visible light and yellow. In order to solve this problem, a method of using hydrogenated bisphenol A glycidyl ether has been proposed, but the performance is not sufficient.

Silicone resins are widely used to improve yellowing and lowering of luminance due to ultraviolet light. Silicone resin is excellent in transparency in an ultraviolet region, and there is very little fall of yellowing and transmittance by ultraviolet light. However, since the silicone resin has a low refractive index, light extraction efficiency is low. Accordingly, it is time to further develop a silicone-based resin having better refractive index and light transmittance.

The present invention is to provide a silicone-based resin composition which is excellent in transmittance and stable to ultraviolet rays or heat and can prevent yellowing.

One embodiment of the present invention is a silicone-based resin composition comprising an organopolysiloxane represented by Formula 1 below, an organohydrogenpolysiloxane represented by Formula 2 below, and a platinum group metal catalyst.

<Formula 1>

[R ¹ _a R ² _b Vi _c SiO _{(4-abc) / 2} ] _n

Wherein R ¹ is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R ² is hydroxyl Any one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is 10 To 100.)

<Formula 2>

[R ¹ _a R ² _b H _c SiO _{(4-abc) / 2} ] _n

Wherein R ¹ is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R ² is hydroxyl Period, methoxy and ethoxy, either a number from 1.00 to 1.90, b from 0.001 to 0.2, c from 0.01 to 0.2, n from 10 to 100.)

Another embodiment of the present invention is the organopolysiloxane represented by the formula (1) is a silicone resin composition having a mass average molecular weight of 1500 to 10,000.

Another embodiment of the present invention is an organopolysiloxane represented by the formula (1) is a silicone resin composition having a viscosity of 500 to 40000cps.

According to another embodiment of the present invention, the organopolysiloxane represented by Chemical Formula 1 may be prepared by a method of preparing an organopolysiloxane having a mass average molecular weight of 500 to 1500, followed by condensation reaction under an acid catalyst, followed by extraction with an organic solvent. Silicone resin composition.

Another embodiment of the present invention is an organopolysiloxane having a mass average molecular weight of 500 to 1500 is a silicone-based resin composition which is a compound represented by the following formula (3).

(3)

[R ¹ _a R ² _b Vi _c SiO _{(4-abc) / 2} ] _n

Wherein R ¹ is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R ² is hydroxyl Period, methoxy and ethoxy, either a number from 1.00 to 1.80, b from 0.09 to 0.5, c from 0.01 to 0.2, and n from 5 to 15.)

The silicone resin composition according to the present invention has excellent transmittance, is stable against ultraviolet rays and heat, and can prevent yellowing, so that sealing materials such as light emitting elements and light receiving elements in optical semiconductor devices (semiconductor light emitting devices) can be used. In particular, it is applicable as a transparent sealing material for optical semiconductors, such as LED.

1 illustrates an NMR spectrum of an organopolysiloxane prepared according to Preparation Example 1 of the present invention.
Figure 2 shows the NMR spectrum of the organopolysiloxane prepared according to Preparation Example 2 of the present invention.

According to one embodiment of the present invention, to provide a silicone-based resin composition comprising an organopolysiloxane represented by the following formula (1), an organohydrogenpolysiloxane represented by the following formula (2) and a platinum group metal catalyst.

<Formula 1>

[R ¹ _a R ² _b Vi _c SiO _{(4-abc) / 2} ] _n

Wherein R ¹ is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R ² is hydroxyl Any one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is 10 To 100.)

<Formula 2>

[R ¹ _a R ² _b H _c SiO _{(4-abc) / 2} ] _n

Wherein R ¹ is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R ² is hydroxyl Period, methoxy and ethoxy, either a number from 1.00 to 1.90, b from 0.001 to 0.2, c from 0.01 to 0.2, n from 10 to 100.)

R ¹ in Formulas 1 and 2 is at least ^{one selected} from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms.

The alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, Cyclohexyl group, octyl group, nonyl group, decyl group, etc. are mentioned.

Examples of the aryl group having 2 to 12 carbon atoms, preferably 6 to 10 carbon atoms include a phenyl group, tolyl group, xylyl group, and naphthyl group.

Examples of the aralkyl group having 2 to 12 carbon atoms, preferably 6 to 10 carbon atoms, include a benzyl group, a phenylethyl group and a phenylpropyl group.

Examples of the alkenyl group having 2 to 12 carbon atoms, preferably 6 to 10 carbon atoms include vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group and octenyl group. .

In addition, some or all of the remaining hydrogen atoms except the hydrogen atom bonded to the silicon atom in the alkyl group, aryl group, aralkyl group and alkenyl group may be substituted with halogen atoms such as fluorine, bromine, chlorine and cyano groups.

In the present invention, in order to obtain a high refractive index in the silicone resin, it is preferable to increase the a content in the organopolysiloxane represented by Formula 1 to contain a large amount of phenyl groups.

The organopolysiloxane represented by Formula 1 has a mass average molecular weight of 1500 to 10,000, and the organopolysiloxane preferably has a viscosity of 500 to 40000 cps. When the mass average molecular weight and viscosity are less than the above range, heat shock may occur due to shrinkage after curing, and when the mass average molecular weight and viscosity exceed the above range, turbidity may occur after blending.

The organopolysiloxane represented by Formula 1 satisfying the conditions of the mass average molecular weight and the viscosity may be prepared by a condensation reaction of an organopolysiloxane having a mass average molecular weight of 500 to 1500 under an acid catalyst and then extracted with an organic solvent. Can be.

The organopolysiloxane having the mass average molecular weight of 500 to 1500 is a compound represented by the following formula (3).

(3)

[R ¹ _a R ² _b Vi _c SiO _{(4-abc) / 2} ] _n

Wherein R ¹ is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R ² is hydroxyl Period, methoxy and ethoxy, either a number from 1.00 to 1.80, b from 0.09 to 0.5, c from 0.01 to 0.2, and n from 5 to 15.)

The definition of R ¹ in Formula 3 is the same as the definition of R ¹ in Formula ¹ .

The acid catalyst may include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and the like, but is not limited thereto.

In the present invention, by condensation reaction of the low molecular weight organopolysiloxane represented by Chemical Formula 3 under the acid catalyst, the alkoxy group defined by R ² in Chemical Formula 3, that is, the content of b is significantly reduced, and is represented by Chemical Formula 1 High molecular weight organopolysiloxanes can be prepared. By reducing the content of b, it is possible to obtain an effect of improving permeability and improving heat resistance.

The organic solvent is propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl glycol methyl acetate, ethyl Oxypropionate, methylethoxypropionate, butyl acetate, ethyl acetate, cyclohexanone, acetone, methyl isobutyl ketone, dimethylformamide, dipropylene glycol methyl ether, toluene, methyl cellosolve and ethyl cellosolve Alkyl alcohols such as methanol, ethanol, isopropyl alcohol, alkyl esters, alkyl ketones, and the like, but are not limited thereto.

The organopolysiloxane represented by Formula 3 may have a problem having a very low viscosity having a mass average molecular weight in the range of 500 to 1500, a high content of b defined in Formula 3 has a problem of permeability, and when stored for a long time Dehydration can occur between -OH, which may lead to stability problems.

The alkoxy corresponding to b defined in Chemical Formula 1 is prepared by preparing the organopolysiloxane represented by Chemical Formula 3 having the mass average molecular weight of 500 to 1500 by the above-described manufacturing method with a high molecular weight organopolysiloxane represented by Chemical Formula 1. Lowering the content of the group can be obtained to improve the stability.

In addition, the present invention can obtain the effect of improving the permeability by minimizing the silanol groups of the organopolysiloxane represented by the formula (1) prepared by the above-described manufacturing method.

The silicone resin composition according to the present invention includes an organohydrogenpolysiloxane represented by Formula 2, wherein a platinum group metal catalyst is added to the organopolysiloxane represented by Formula 1 and the organohydrogenpolysiloxane represented by Formula 2 Can be thermally cured.

The platinum group metal-based catalyst may include a platinum microvinyl methyl siloxane complex, a platinum 2,4-pentanedioate, a platinum divinyl tetramethyl disiloxane complex, a platinum carbonylcyclovinyl methyl siloxane complex, and the like. It is not limited to this.

The silicone resin composition according to the present invention includes 0.0001 to 1 parts by weight of a platinum group metal catalyst based on 100 parts by weight of the total organopolysiloxane represented by Formula 1 and the organohydrogenpolysiloxane represented by Formula 2.

If the platinum group metal-based catalyst is out of the range there is a problem that white turbidity or curing does not proceed.

At this time, the organopolysiloxane represented by the general formula (1) and the organohydrogenpolysiloxane represented by the general formula (2) of the content of Si-Vi and Si-H of the organohydrogenpolysiloxane of the organopolysiloxane 1: 1: 0.3 to 2.0 It is preferable to mix | blend in molar ratio of 1, and preferably 1: 0.8-1.2, and to include in silicone resin composition. When the molar ratio is within the above range, it is possible to obtain an effect of increasing hardness after curing.

The silicone resin composition of the present invention may optionally include additives in addition to the organopolysiloxane represented by Chemical Formula 1, the organohydrogenpolysiloxane represented by Chemical Formula 2, and the platinum group metal catalyst. The additive may be used without particular limitation as long as it is commonly used in the field to which the present invention belongs, and specifically, modifiers, inorganic fillers, antioxidants, and the like may be mentioned.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

Manufacturing example  1: represented by the formula (3) Of organopolysiloxane  Produce

60 g of phenyltrimethoxysilane, 10 g of vinyltrimethoxysilane, 25 g of diphenyldimethoxysilane, 60 g of dimethyldimethoxysilane and 200 g of isobutyl alcohol were added together, and hydrolyzed and polymerized at 80 ° C. for 10 hours. Extraction was performed using toluene, and dehydration and organic solvent were removed to prepare 120 g of organopolysiloxane (x) having a mass average molecular weight of 900.

Manufacturing example  2: represented by Formula 1 Of organopolysiloxane  Produce

1 ml of sulfuric acid was added to 100 g of organopolysiloxane (x) prepared according to Synthesis Example 1, followed by condensation reaction at 60 ° C. for about 1 hour, followed by extraction with toluene, dehydration and removal of organic solvent. 120 g of organopolysiloxane (y) having a molecular weight of 3000 and a viscosity of 1500 cps was prepared.

1 shows an NMR spectrum of an organopolysiloxane prepared according to Preparation Example 1, and FIG. 2 shows an NMR spectrum of an organopolysiloxane prepared according to Preparation Example 2.

As shown in FIGS. 1 and 2, it was confirmed that the alkoxy group of the organopolysiloxane (y) prepared according to Preparation Example 2 was significantly reduced through the peak of 3 to 4 ppm of the NMR spectrum.

Example  1 and 2 and Comparative example  One

Using the organopolysiloxane (x) according to Preparation Example 1, the organopolysiloxane (y) according to Preparation Example 2 and the organohydrogenpolysiloxane (Andisil, 3.0MMOLE / GM Crosslinker), shown in Table 1 below The silicone resin composition was prepared based on the blending amount. The compositions according to Examples 1 and 2 and Comparative Example 1 were cured by heating in an oven at 150 ° C. for 30 minutes after 1 hour at 80 ° C. to form a cured sheet having a thickness of 2 mm. The content units described in Table 1 below are parts by weight.

Example 1 Example 2 Comparative Example 1 (a) organopolysiloxane (x) 0 0 90 (a) organopolysiloxane (y) 90 80 0 (b) organohydrogenpolysiloxanes 10 20 10 (c) platinum-based catalysts 0.1 0.1 0.1 (d) additives 2 2 2

The transmittance and heat resistance results of the cured product prepared using the compositions according to Examples 1 and 2 and Comparative Example 1 were evaluated using the methods described below, and the results are shown in Table 2 below.

(1) Transmittance: The transmittance at 400 nm was measured for the fabricated specimens of 2 mm using UV-VIS.

(2) Heat resistance: Permeability was measured in units of 10 hours after aging in a 150 ° C. oven, and the time when the transmittance was reduced by 5% was expressed as a heat resistance value.

Permeability Heat resistance Example 1 98.1 200 hours Example 2 98.4 300 hours Comparative Example 1 92.7 70 hours

As shown in Table 2, in the case of Examples 1 to 2 it can be seen that the transmittance is very excellent compared to Comparative Example 1.

From this, the silicone resin composition according to the present invention has excellent permeability and excellent heat resistance to heat, and thus sealing materials such as light emitting elements and light receiving elements in optical semiconductor devices (semiconductor light emitting devices), in particular for optical semiconductors such as LEDs, etc. It was found to be suitable for use as a transparent sealing material.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (5)

A silicone-based resin composition comprising an organopolysiloxane represented by Formula 1, an organohydrogenpolysiloxane represented by Formula 2, and a platinum group metal catalyst.
<Formula 1>
[R ¹ _a R ² _b Vi _c SiO _{(4-abc) / 2} ] _n
Wherein R ¹ is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R ² is hydroxyl Any one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is 10 To 100.)

<Formula 2>
[R ¹ _a R ² _b H _c SiO _{(4-abc) / 2} ] _n
Wherein R ¹ is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R ² is hydroxyl Period, methoxy and ethoxy, either a number from 1.00 to 1.90, b from 0.001 to 0.2, c from 0.01 to 0.2, n from 10 to 100.)
The silicone-based resin composition of claim 1, wherein the organopolysiloxane represented by Chemical Formula 1 has a mass average molecular weight of 1500 to 10,000. The silicone resin composition of claim 1, wherein the organopolysiloxane represented by Chemical Formula 1 has a viscosity of 500 to 40000 cps. According to claim 1, wherein the organopolysiloxane represented by the formula (1) is a silicon-based prepared by a manufacturing method comprising the step of condensation reaction of the organopolysiloxane having a mass average molecular weight of 500 to 1500 under an acid catalyst and then extracted with an organic solvent Resin composition. The silicone-based resin composition according to claim 4, wherein the organopolysiloxane having a mass average molecular weight of 500 to 1500 is a compound represented by the following Chemical Formula 3.

(3)
[R ¹ _a R ² _b Vi _c SiO _{(4-abc) / 2} ] _n
Wherein R ¹ is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R ² is hydroxyl Period, methoxy and ethoxy, either a number from 1.00 to 1.80, b from 0.09 to 0.5, c from 0.01 to 0.2, and n from 5 to 15.)

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