KR101156581B1 - Epoxy resin composition and light-emitting semiconductor device coated with same - Google Patents

Abstract

The present invention relates to an epoxy resin composition and a light emitting semiconductor device coated thereby, comprising (a) an alicyclic epoxy resin, (b) nano-sized silica particles, (c) an acid anhydride curing agent and (d) quaternary phosphonium salt curing The resin composition of the present invention comprising a catalyst is transparent, has no surface adhesion, and has excellent adhesiveness, heat resistance, and moisture resistance, and is useful as a coating protective material for light emitting semiconductor devices such as UV light emitting diodes (LEDs) that can realize white LEDs. Can be used.

Description

EPOXY RESIN COMPOSITION AND LIGHT-EMITTING SEMICONDUCTOR DEVICE COATED WITH SAME

The present invention relates to an epoxy resin composition useful as a coating protective material of a light emitting semiconductor device such as a UV light emitting diode (LED) capable of implementing a white LED, and a light emitting semiconductor device coated thereby.

Generally, as a resin composition for coating protection of light emitting semiconductor elements, such as a light emitting diode (LED), the resin composition containing epoxy resins, such as a bisphenol-A epoxy resin or an alicyclic epoxy resin, and an acid anhydride type hardening | curing agent is used. However, since the said resin composition is low in moisture resistance and is colored (yellowing) by light deterioration, there existed a problem of causing the brightness fall in the light emitting semiconductor element to which the said resin composition was applied. In particular, in the case of a package implementing a white LED using a UV chip, there is a problem in that coloring (yellowing) and carbonization due to epoxy degradation due to light in the UV region occur.

Therefore, in order to improve moisture resistance and suppress coloring by light deterioration, a resin composition containing a silicone resin has been proposed. However, silicone resins have problems such as deterioration in workability due to sticky and peeling due to low adhesion.

With the recent miniaturization, thinning, and high output of the optical semiconductor device package, it is transparent, has no surface adhesiveness, and has excellent adhesion as a cover protection material of a light emitting semiconductor device, in particular, a UV LED encapsulation material that can realize a white LED using a UV chip. Along with the resistance and moisture resistance, the development of a resin composition that does not have a fear of coloring due to light deterioration is required.

Accordingly, an object of the present invention is a UV light emitting diode (LED) which is transparent, has no surface adhesiveness, is excellent in adhesiveness, moisture resistance, and heat resistance, and has no fear of coloration (yellowing) due to light deterioration. It is to provide an epoxy resin composition useful as a coating protective material of a light emitting semiconductor device such as).

Another object of the present invention is to provide a light emitting semiconductor device coated with the resin composition.

In order to achieve the above object,

(a) alicyclic epoxy resins,

(b) nano-sized silica particles,

(c) acid anhydride curing agents, and

(d) Quaternary phosphonium salt curing catalyst

It provides an epoxy resin composition comprising a.

The present invention also provides a light emitting semiconductor device coated with the resin composition.

The epoxy resin composition according to the present invention is transparent, has no surface adhesiveness, is excellent in adhesiveness, heat resistance and moisture resistance, and is particularly free from coloration (yellowing) due to light deterioration. As a result, it is useful as a coating protection material for light emitting semiconductor devices such as UV light emitting diodes (LEDs) that can realize white LEDs using UV chips and LEDs for miniaturization, thinness, and high power. It can exhibit reliable performance and excellent heat resistance without any concern.

The epoxy resin composition according to the present invention comprises (a) an alicyclic epoxy resin, (b) nano-sized silica particles, (c) an acid anhydride curing agent, and (d) a quaternary phosphonium salt curing catalyst as essential components. It features. Preferably, the epoxy resin composition according to the present invention is an alicyclic epoxy resin, nano-sized silica particles, acid anhydride curing agent and quaternary phosphonium salt curing catalyst, respectively, 20 to 70% by weight, 20 to 20% by weight of the total resin composition It may comprise 50% by weight, 5 to 50% by weight and 0.01 to 5% by weight.

Hereinafter, each component constituting the epoxy resin composition of the present invention will be described in detail.

(a) alicyclic epoxy resin

As the alicyclic epoxy resin used in the present invention, it is preferable to use a compound having a structure represented by the following general formula (1):

Wherein n is an integer from 1 to 8, preferably 1.

The alicyclic epoxy resin preferably has an epoxy equivalent of 140 to 165, and preferably has a viscosity at 25 ° C. of 350 to 650 cPs as measured by a Brookfield RVT TYPE.

The alicyclic epoxy resin is preferably used in an amount of 20 to 70% by weight based on the total weight of the resin composition because it can improve moisture resistance and durability. When the content of the alicyclic epoxy resin exceeds 70% by weight, there is a fear of coloring due to light deterioration.

(b) nano-sized silica particles

Nano-sized silica particles used in the present invention serves to improve the thermal stability, it is preferably used in an amount of 20 to 50% by weight relative to the total weight of the composition.

The alicyclic epoxy resin and nano-sized silica particles are important factors in determining the moisture resistance and thermal stability of the resin composition. Accordingly, within a range satisfying each content condition, the weight ratio of the alicyclic epoxy resin and the nano-sized silica particles is preferably in the range of 3: 7 to 7: 3, and is in the range of 4: 6 to 6: 4 More preferably, it is possible to improve the moisture resistance and heat stability of the resin composition in this weight ratio range. If the alicyclic epoxy resin is used in excess of the weight ratio range, the thermal stability may be lowered. If the silica particles are used in excess of the weight ratio range, the viscosity may be too high and workability may decrease when applied to the coating of the light emitting semiconductor device. There is concern.

(c) acid anhydride curing agents

The acid anhydride curing agent used in the present invention serves to crosslink the epoxy resin to form a crosslinked product. Specific examples thereof include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydro phthalic anhydride, and alkyl. Hexahydro phthalic anhydride (eg 3-methyl-hexahydro phthalic anhydride, 4-methyl-hexahydro phthalic anhydride, etc.), tetrahydro phthalic anhydride, naziic anhydride, methyl nazi anhydride, norbornane-2,3- Dicarboxylic acid anhydride, methyl norbornane-2,3-dicarboxylic acid anhydride and mixtures thereof.

The acid anhydride curing agent may be used in an amount of 5 to 50% by weight based on the total weight of the resin composition.

Preferably, the content of the acid anhydride curing agent may be 0.5 to 1.5 moles, more preferably 0.8 to 1.1 moles with respect to 1 mole of the epoxy functional group of the epoxy resin.

(d) Quaternary phosphonium salt curing catalyst

The quaternary phosphonium salt curing catalyst used in the present invention promotes the curing ability of the acid anhydride curing agent, and specific examples thereof include benzyltributylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide and tetrabutyl Phosphonium iodine, tetramethylphosphonium bromide, tetraethylphosphonium chloride, ethylenebis (triphenylphosphonium bromide), benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium hydroxide, 4 -Chlorobenzyltriphenylphosphonium chloride, cinnamiltriphenylphosphonium chloride, 4-ethoxybenzyltriphenylphosphonium bromide, phenacyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenyl Phosphonium Iodide, Tetrape Nyl phosphonium tetraphenyl borate and mixtures thereof are mentioned, Among these, benzyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, and 4-chlorobenzyl triphenyl phosphonium chloride are more preferable.

The quaternary phosphonium salt curing catalyst may be used in an amount of 0.01 to 5% by weight based on the total weight of the resin composition. If the content of the curing catalyst is less than 0.01% by weight, the effect of promoting the reaction between the epoxy resin and the curing agent may not be sufficiently obtained. If the content of the curing catalyst is more than 5% by weight, there is a fear of discoloration.

Preferably, the content of the curing catalyst may be 0.05 to 2% by weight relative to the total content ((a) + (b) + (c)) of the epoxy resin, silica particles and the curing agent.

(e) additives

The epoxy resin composition according to the present invention may further include a light scattering agent such as a phosphor for wavelength change, an antioxidant, an inorganic filler, a plasticizer, a reactive diluent, a non-reactive diluent, and the like.

The additives may be included in an appropriate amount within a range that does not impair the properties and effects of the epoxy resin composition.

The epoxy resin composition according to the present invention having the composition as described above is transparent, has no surface adhesiveness, is excellent in adhesiveness, heat resistance, and moisture resistance, and has no coloration (yellowing) due to light deterioration. Specifically, the resin composition has a refractive index of 1.4 to 1.6. As a result, it is useful as a coating protective material for coating and protecting a light emitting semiconductor device such as a UV light emitting diode (LED) that can implement a white LED using a UV chip.

Accordingly, the present invention provides a light emitting semiconductor device coated with the epoxy resin composition, the light emitting semiconductor device may be a UV LED capable of implementing a white LED using a UV chip.

In the case where the resin composition is applied by a method such as potting or injection in order to coat and protect the light emitting semiconductor device, the resin composition is preferably in a liquid state, and specifically, when measured by a Brookfield RVT TYPE, 25 ° C It is preferable that it is 100-50,000 cPs, and it is more preferable that it is 1,000-5,000 cPs.

In addition, in this invention, the hardening conditions of a coating protective material are 130-140 degreeC x 4 hours, arbitrarily selected according to the working conditions, and can be used suitably.

In the epoxy resin composition according to the present invention, the glass transition temperature of the cured product is 130 ° C. or higher and 140 to 180 ° C. as measured by differential scanning calorimetry (DSC) measurement.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Example 1

60 wt% of an alicyclic epoxy resin (CELLOXIDE 2021P, manufactured by Daicel Chemical Co., Ltd.) and 40 wt% of silica particles having an average size of 20 nm were mixed by using a dispersion apparatus to prepare “component (A)”.

Separately from above, 99 wt% of methylhexahydro phthalic anhydride (MHHPA, Nippon-Sai Nippon Co., Ltd.) as an acid anhydride curing agent, and 1 wt% of quaternary phosphonium salt (U-CAT5003, San Aprosa) as a curing catalyst were used. "Dispersion (B)" was prepared by mixing using a dispersion apparatus.

An epoxy resin composition was prepared by mixing 100 wt% of “Component (A)” and 70 wt% of “Component (B)” using a dispersing equipment.

Example 2, and Comparative Examples 1 and 2

Each resin composition was prepared in the same manner as in Example 1, except for using the compounds and contents shown in Table 1 below.

Comparative example  3

Bisphenol A type epoxy resin (KDS-8128, Kukdo Chemical Co., Ltd.) 16% by weight, alicyclic epoxy resin (CELLOXIDE 2021P, Daicel Chemical Co., Ltd.) 34% by weight, methyl hexahydrophthalic anhydride (MHHPA, Nippon Kasei) 49.5% by weight % And a quaternary phosphonium salt (U-CAT5003, San Aprosa) as a curing catalyst was blended to prepare a resin composition.

Comparative Example 4

A resin composition was prepared in the same manner as in Comparative Example 3, except that silicone resin (OE-6630, Dow Corning) was used instead of the bisphenol A epoxy resin.

Test Example 1

After the resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were cured under a condition of 4 hours at 140 ° C. on a 3 mm thick rod, transparency of the cured cured product was as follows. Surface adhesion, light degradation, moisture resistance, hardness and glass transition temperature were evaluated. The results are shown in Table 2 below.

1) Transparency: The presence or absence of discoloration of the rod-shaped hardened | cured material was visually confirmed.

2) Surface adhesiveness: The rod-like hardened | cured material was accelerated and the presence or absence of surface adhesiveness was confirmed.

3) Light deterioration: The rod-shaped cured product was left in a box oven at 150 ° C. for 50 hours and then visually checked for color change.

4) Moisture resistance: The rod-shaped cured product was left to stand for 48 hours under a Pressure Cooker Test (PCT) (121 ° C, 2 atm) condition and then visually checked for color change.

5) Hardness: Measured using a Shore D hardness meter.

6) Glass transition temperature: Measured by differential scanning calorimetry (DSC) measurement method.

Evaluation results Example 1 Example 2 Comparative Example 1 Comparative Example 2 Transparency Transparency Transparency Transparency Transparency Surface Adhesion none none none none Light deterioration transparent transparent yellow yellow Moisture resistance transparent transparent White White

As can be seen from Table 2, the cured products of the resin compositions of Examples 1 and 2 according to the present invention and the cured products of the resin compositions of Comparative Examples 1 and 2 showed excellent transparency and surface adhesion. However, the cured products of the resin compositions of Examples 1 and 2 according to the present invention do not discolor in terms of coloration and moisture resistance due to light deterioration, while the resins of Comparative Examples 1 and 2 containing different curing catalysts from the present invention. The cured product of the composition was discolored.

Test Example 2

The resin compositions prepared in Examples 1 and Comparative Examples 3 and 4 were cured under a condition of 4 hours at 140 ° C. on a 3 mm thick rod, and then cured cured products in the same manner as in Test Example 1 above. Surface adhesiveness, hardness, glass transition temperature and light degradation were evaluated. The results are shown in Table 3 below.

Condition Example 1 Comparative Example 3 Comparative Example 4 Surface Adhesion none none none Hardness (Shore D) 82 80 34 Glass transition temperature (캜) > 140 > 160 <0 Light deterioration none Light yellow none

As can be seen from Table 3, the cured product of the resin composition of Example 1 according to the present invention and the cured product of the resin compositions of Comparative Examples 3 and 4 did not have surface adhesiveness. However, the cured product of the resin composition of Example 1 according to the present invention had a high hardness and no coloring due to light deterioration, but the cured product of the resin composition of Comparative Example 3 showed coloring due to light deterioration, The hardened | cured material of the resin composition showed low hardness.

Claims (11)

(a) an alicyclic epoxy resin having a structure of Formula 1,
(b) nano-sized silica particles,
(c) acid anhydride curing agents, and
(d) a quaternary phosphonium salt curing catalyst,
The components (a) to (d) in an amount of 20 to 70% by weight, 20 to 50% by weight, 5 to 50% by weight and 0.01 to 5% by weight, respectively, based on the total weight of the resin composition; ) And (b) in a weight ratio ranging from 3: 7 to 7: 3,
Epoxy resin composition:

[Formula 1]

Wherein n is an integer from 1 to 8. delete delete delete The method of claim 1,
The acid anhydride curing agent is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydro phthalic anhydride, alkyl hexahydro phthalic anhydride, tetrahydro phthalic anhydride, nazi acid anhydride, methyl nazi anhydride, norbornane Epoxy resin composition, characterized in that it is selected from the group consisting of -2,3-dicarboxylic acid anhydride, methyl norbornane-2,3-dicarboxylic acid anhydride and mixtures thereof. The method of claim 1,
Epoxy resin composition, characterized in that the acid anhydride curing agent is contained in an amount of 0.5 to 1.5 moles with respect to 1 mole of the epoxy functional group of the epoxy resin. The method of claim 1,
The quaternary phosphonium salt curing catalyst is benzyltributylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodine, tetramethylphosphonium bromide, tetraethylphosphonium chloride, ethylenebis (tri Phenylphosphonium bromide), benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium hydroxide, 4-chlorobenzyltriphenylphosphonium chloride, cinnamiltriphenylphosphonium chloride, 4-e Group consisting of oxybenzyltriphenylphosphonium bromide, phenacyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium iodide, tetraphenylphosphonium tetraphenylborate and mixtures thereof Characterized by being selected from Epoxy resin composition. The method of claim 1,
The quaternary phosphonium salt curing catalyst is an epoxy resin composition, characterized in that contained in an amount of 0.05 to 2% by weight based on the total content of the epoxy resin, silica particles and the curing agent. The method of claim 1,
Epoxy resin composition, characterized in that the epoxy resin composition exhibits a viscosity of 100 to 50,000 cPs at 25 ° C as measured by a Brookfield viscometer (BROOKFIELD RVT TYPE). A light emitting semiconductor device coated with the epoxy resin composition according to claim 1. 11. The method of claim 10,
The light emitting semiconductor device, characterized in that the light emitting semiconductor device is a UV light emitting diode (LED) capable of implementing a white LED.