JP2011225779A - Transparent resin composition and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition with excellent transparency and transparency after thermal history, heat resistance, and reliability, and is especially preferred for sealing an optical semiconductor device.SOLUTION: The transparent resin composition comprises (A) a (meth)acrylic modified silicone compound, (B) a (meth)acrylic resin having a carbonate group, and (C) a curing catalyst, as essential components, wherein 20-95 pts.mass of the component (A) and 5-80 pts.mass of the component (B) are contained per a total of 100 pts.mass of the component (A) and the component (B). The optical semiconductor device sealed by curing the composition is also provided.

Description

  The present invention relates to a resin composition for sealing an optical semiconductor such as an LED, a phototransistor, a photodiode, or a CCD, and a transparent molded product such as a lens. More specifically, the present invention relates to a transparent resin composition having an appropriate range of elastic modulus and Tg, or having resistance to ultraviolet rays and heat deterioration, and an optical semiconductor device sealed using the same.

  The optical semiconductor is sealed with a transparent resin to protect it from the external environment. However, the transparent resin used for sealing the optical semiconductor element is required to have transparency, moisture resistance, and heat resistance. Resins and silicone resins are used (see, for example, Patent Documents 1 to 3). In addition, acrylic resin is originally used for molded products using transparent resin such as lenses, but recently, reflow resistance has been required, and acrylic resin has excellent dimensional stability and heat resistance. It has come to be required.

JP 2006-307087 A WO2007 / 129536 pamphlet Special table 2008-537968 gazette

In order to improve heat resistance, it is preferable to introduce a silicone skeleton. However, in order to obtain dimensional stability, it is preferable to add an organic filler such as an epoxy resin or an acrylic resin or an inorganic filler such as silica. However, acrylic resin is preferable to epoxy resin in order to maintain transparency in an environment irradiated with ultraviolet rays.
In addition, in the system where the epoxy resin is cured with an acid anhydride, the volatilization of the acid anhydride is also large, and it becomes difficult for both the epoxy resin and the acrylic resin to react when used in combination with the acrylic resin. Therefore, it is preferable to cationically cure the epoxy resin. .
The present invention has been made in order to cope with such a conventional situation, and is sealed with a resin composition excellent in transparency, heat resistance and reliability, and particularly preferable for sealing an optical semiconductor device and a cured product thereof. It is an object of the present invention to provide an optical semiconductor device.

As a result of intensive studies to achieve the above object, the present inventors have made (meth) acryl-modified silicone compound, a (meth) acrylic resin having a carbonate group, and a curing catalyst as essential components, thereby achieving transparency. The present inventors have found that a transparent resin composition and an optical semiconductor device excellent in heat resistance and reliability, particularly preferable for sealing an optical semiconductor device, can be obtained, and the present invention has been completed.
In addition, by incorporating a (meth) acrylic resin having an oxetane group, a compound having a glycidyl group and a carbon-carbon double bond, or an inorganic filler, heat resistance reliability, adhesion to a substrate, and low shrinkage are further improved. Can be achieved.
That is, the present invention comprises (1) (A) (meth) acryl-modified silicone compound, (B) (meth) acrylic resin having a carbonate group, and (C) a curing catalyst as essential components. In the total amount of 100 parts by mass of (B), the component (A) is contained in a proportion of 20 to 95 parts by mass, and the component (B) is contained in a proportion of 5 to 80 parts by mass. Transparent resin composition,
(2) The transparent resin composition according to the above (1), wherein the content of the component (C) is 0.1 to 1 part by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B),
(3) The above (1) or (2) further comprising (D) 10 to 70 parts by mass of (meth) acrylic resin having an oxetane group with respect to 100 parts by mass in total of the component (A) and the component (B). Transparent resin composition according to
(4) The above (1) to (4) further containing (E) 10 to 50 parts by mass of a compound having a glycidyl group and a carbon-carbon double bond with respect to 100 parts by mass in total of the component (A) and the component (B). A transparent resin composition according to any one of 3) and (5) an optical semiconductor device that is sealed by curing the transparent resin composition according to any one of (1) to (4) above. Is.

  According to the present invention, there are provided a resin composition excellent in transparency, heat resistance, and reliability after being subjected to transparency and heat history, particularly preferable for sealing an optical semiconductor device, and an optical semiconductor device sealed with a cured product thereof. Provided.

Hereinafter, the present invention will be described in detail.
First, the component (A) will be described.
In the (meth) acryl-modified silicone compound of component (A) used in the present invention, the (meth) acryl group may be introduced at any position such as a side chain or a terminal of the silicone skeleton. As specific examples, X-22-164 manufactured by Shin-Etsu Chemical Co., Ltd. (silicone skeleton is introduced at the methacrylic ester position, functional group equivalent 190), X-22-164As (silicone skeleton is introduced at the methacrylic ester position). Equivalent 450), X-22-164A (silicone skeleton is introduced at the methacrylic ester position, functional group equivalent 860), and the like can be used.
Other examples include (meth) acryloxypropyl-terminated polydimethylsiloxane, [(meth) acryloxypropyl] methylsiloxane, and a copolymer of [(meth) acryloxypropyl] methylsiloxane and dimethylsiloxane. In addition, those in which a methyl group is introduced at the terminal of the (meth) acryl group of the compound can also be used. The number of functional groups in one molecule is preferably 2 or more, but one having 1 functional group may be used.
The functional group equivalent is preferably in the range of 100 to 1000. Within this range, the tackiness of the obtained transparent resin composition and the heat resistance of the cured product are improved.
The ratio of the component (A) in the transparent resin composition of the present invention is essential to be 20 to 95 parts by mass in 100 parts by mass of the total amount of the components (A) and (B), and 50 to 95 parts by mass. It is preferable that
The heat resistance of the obtained transparent resin composition or its hardened | cured material falls that the ratio of a component (A) is less than 20 mass parts. Moreover, when it exceeds 95 mass parts, a crack and peeling will arise in hardened | cured material.

Next, the component (B) will be described.
The (meth) acrylic resin having a carbonate group as the component (B) is any (meth) acrylic having a carbonate group as long as the cured product of the obtained transparent resin composition is colorless and transparent and hardly discolored. Resins may be used alone or in combination. As a specific example, UM-90 (1/3) DM (copolymerized methacrylic oligomer having a cyclohexane group in a skeleton and a methacrylic oligomer having a linear alkyl group in a 1: 3 ratio) manufactured by Ube Industries, Ltd., UM- 90 (3/1) DM [copolymerization of a methacryl oligomer having a cyclohexane group in the skeleton and a methacryl oligomer having a linear alkyl group at a ratio of 3: 1].
As other examples of the (meth) acrylic resin having a carbonate group, a (meth) acryl oligomer having a carbonate group and an alkyl group in the skeleton, and those having a cycloalkyl group or a heterocyclic ring introduced in place of the alkyl group can also be used. However, a compound having an aromatic ring, an amino group or a thiol group is not preferred in order to have ultraviolet resistance.
Further, it is obtained by reacting at least one selected from glycidyl (meth) acrylate, 4-butyl glycidyl (meth) acrylate, 3,4-cyclohexylmethyl (meth) acrylate and polyethylene glycol diglycidyl ether with carbon dioxide. And a resin obtained by polymerizing a 5-membered cyclic carbonate group-containing acrylic monomer.
The ratio of the component (B) in the transparent resin composition of the present invention is essential to be 5 to 80 parts by mass in 100 parts by mass of the total amount of the components (A) and (B), and 5 to 50 masses. Part.
When the proportion of the component (B) is less than 5 parts by mass, cracks and peeling occur in the cured product. Moreover, when it exceeds 80 mass parts, the obtained transparent resin composition or its cured product heat resistance will fall.

Next, the component (C) will be described.
The curing catalyst for component (C) may be a thermosetting catalyst or a photocuring catalyst. Examples thereof include azobisisobutyronitrile (AIBN), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), benzoyl peroxide, dicumyl peroxide, benzophenone, acetophenone, and the like. Moreover, a trialkylsulfonium salt, a triarylsulfonium salt, a diaryliodonium salt, etc. are mentioned, You may use together single or 2 types or more.
The ratio of the curing catalyst which is the component (C) in the transparent resin composition of the present invention is preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). is there. If the proportion of component (C) is less than 0.1 parts by mass, curing may be insufficient. On the other hand, if it exceeds 1 part by mass, the heat resistance, molding workability, and electrical properties of the cured product are deteriorated.

Next, the component (D) will be described.
The (meth) acrylic resin having an oxetane group of component (D) in the transparent resin composition of the present invention has a structure between the oxetane group and the (meth) acrylic group as long as the cured product is colorless and transparent and hardly discolors. Any (meth) acrylic resin having an oxetane group may be used alone or in combination. Specific examples include OXMA [(meth) acrylic acid ester polymer having an oxetane group] manufactured by Ube Industries.
Moreover, it is preferable that the ratio of this component (D) is 10-70 mass parts with respect to 100 mass parts of total amounts of a component (A) and a component (B), More preferably, it is 10-40 mass parts. .
When the ratio of the component (D) is less than 10 parts by mass, improvement in adhesion and reliability are not so much observed. When the proportion of the component (D) exceeds 70 parts by mass, the curability deteriorates, the tackiness due to the uncured surface remains, and it tends to become dirty. Moreover, workability is poor. Moreover, when there are many uncured parts, the reliability and weather resistance of the semiconductor device encapsulated with the transparent resin composition of the present invention will deteriorate.

Next, the component (E) will be described.
The compound having a glycidyl group and a carbon-carbon double bond as the component (E) in the transparent resin composition of the present invention may be one having a glycidyl group and a (meth) acryl group, or a glycidyl group, an ethylene group or a butadiene group. Any glycidyl group and a compound having a carbon-carbon double bond may be used singly or in combination as long as the cured product is colorless and transparent and hardly discolors. Specific examples include glycidyl methacrylate, epoxidized polybutadiene (manufactured by Adeka, BF-1000) and the like.
Here, it is preferable that the ratio of a component (E) is 10-50 mass parts with respect to 100 mass parts of total amounts of a component (A) and a component (B), More preferably, it is 10-30 mass parts. .
When the ratio of the component (E) is less than 10 parts by mass, improvement in adhesion and improvement in reliability are hardly observed. When the proportion of the component (E) exceeds 50 parts by mass, the ultraviolet resistance of the semiconductor device encapsulated with the transparent resin composition of the present invention is lowered or brittle, which is not preferable.

In the present invention, an inorganic filler can be blended unless it is contrary to the purpose. The inorganic filler may be any inorganic filler as long as it is not colored when dispersed, but more preferably an inorganic filler having an average primary particle size of about 5 to 40 nm, either alone or in combination. May be. Examples thereof include silica, titanium oxide, zirconia oxide, zinc oxide, barium oxide, calcium carbonate, aluminum oxide, and the like. These can be used alone or in combination of two or more.
The average primary particle diameter of the inorganic filler can be measured using, for example, a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd., apparatus name: LA-920).
Moreover, the range which becomes 1-60 mass parts with respect to 100 mass parts of total amounts of a component (A) and a component (B) for the ratio of this inorganic filler is preferable, and the range used as 10-50 mass parts is more preferable. . If the proportion of the inorganic filler is less than 10 parts by mass, the heat resistance, dimensional stability and mechanical strength of the cured product cannot be sufficiently improved, and if it exceeds 60 parts by mass, it can be sufficiently dispersed. It becomes difficult, and the moldability (fluidity), the heat resistance of the cured product, the mechanical strength, the dimensional stability, etc. are reduced.
In the case of blending the inorganic filler in the resin, it is preferable to use a planetary stirrer or a three roll as a particularly effective method for normal temperature, heat mixing, or uniform dispersion.

In addition, (meth) acrylic resins, epoxy compounds, oxetane compounds, coupling agents, antioxidants, mold release agents and the like other than those described above are used in the transparent resin composition of the present invention unless they are contrary to the object of the present invention. be able to.
Examples of the (meth) acrylic resin include monofunctional or bifunctional or higher (meth) acrylic compounds, (meth) acrylic compounds having a cyclic group, and copolymers. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Examples thereof include polymers or copolymers such as cyclohexyl (meth) acrylate. These may be used individually by 1 type, and may mix and use 2 or more types.
Epoxy compounds include glycidyl ester type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional type epoxy resin, triglycidyl isocyanurate, various novolac type epoxy resins, alicyclic type epoxy resins, dicyclopentadiene type. An epoxy resin, a biphenyl type epoxy resin, etc. are mentioned.
As the oxetane compound, monofunctional such as 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, 3-ethyl-3-hydroxymethyloxetanyl methacrylate, bis [(1-ethyl (3-oxetanylmethylether))], Bifunctional or higher oxetane compounds are exemplified.
Antioxidants include 2,6-di-t-butyl-p-hydrotoluene, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, etc. Phenolic antioxidants, phosphorus antioxidants such as tris (2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, diphenylisodecyl phosphite, amine acid antioxidants such as diphenylamine, etc. Is mentioned.
As a coupling agent, silane coupling agents such as 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, tetraisopropylbis (dioctylphosphite) titanate, Examples thereof include titanate coupling agents such as tetraoctyl bis (dioctyl phosphite) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tristearoyl titanate, and isopropyl tridodecylbenzenesulfonyl titanate.

  In addition, the mixing with the said inorganic filler and another component can use normal stirring methods, such as heat mixing.

The optical semiconductor device of the present invention can be produced by sealing various optical semiconductor elements using the transparent resin composition. Examples of the optical semiconductor element that can be sealed include an LED, a photodiode, a phototransistor, a photothyristor, and a photoconductor.
As a sealing method or a molding method, a LIM molding method (liquid resin injection molding method), a compression molding method, a casting method, or the like can be applied. The resin composition of the present invention is heated and cured, and an optical semiconductor device sealed with the cured product is finally obtained.
The temperature at which the transparent resin composition of the present invention is heat-cured is about 100 to 170 ° C, preferably 120 to 150 ° C.
The cured product in the optical semiconductor device thus obtained has excellent transparency, exhibits transparency even after receiving a heating history, and is also high in a temperature cycle test (TCT (Thermo Cycle Test)). It has reliability.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples. In the following examples and comparative examples, “part” represents “part by mass”.

[Example 1]
As the (meth) acrylic modified silicone compound of component (A), 90 parts by mass of a methacrylic modified silicone resin [trade name X-22-164, manufactured by Shin-Etsu Chemical Co., Ltd.] and (meth) acrylic having a carbonate group of component (B) As a resin, a methacrylic resin having a carbonate group [manufactured by Ube Industries, Ltd., trade name: UM-90 (1/3) DM], 10 parts by mass, as a curing catalyst for component (C), dicumyl peroxide [Nippon Yushi Co., Ltd., trade name: Park Mill D] 0.1 parts by mass were mixed at 25 ° C. using a flask to obtain a liquid transparent resin composition.

[Examples 2 to 10, Comparative Examples 1 to 4]
A liquid transparent resin composition was obtained by the same procedure as in Example 1 except that the resin composition was as described in Table 1.

<Fabrication of semiconductor device>
The transparent resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 4 were cast into a frame of an SMD (surface mount device) of an LED (light emitting device), and the temperature was 100 ° C. for 2 hours and 150 ° C. for 2 hours. A semiconductor device which was heat-cured and sealed with a transparent resin composition was produced.

<Evaluation items>
[Tackiness]
Metal powder was sprayed on the molded product, air was blown to remove the metal powder, and whether or not it could be removed was determined according to the following criteria.
○: Can be removed.
X: Cannot be removed.

[transparency]
The transparent resin composition was thermoformed under the conditions of 100 ° C. for 2 hours and 150 ° C. for 2 hours to produce a 20 mm × 20 mm × 1 mm test piece. About this test piece, the light transmittance (%) of wavelength 460nm was measured using the spectrophotometer (V-570) by JASCO Corporation.

[Room temperature elastic modulus, Tg]
The transparent resin composition was thermoformed under the conditions of 100 ° C. for 2 hours and 150 ° C. for 2 hours to prepare a 48 mm × 5 mm × 2 mm test piece. About this test piece, it measured using the dynamic viscoelasticity measuring apparatus (DMS110) by a Seiko company.

[Heat-resistant]
The transparent resin composition was thermoformed at 100 ° C. for 2 hours and 150 ° C. for 2 hours to obtain a test piece of 20 mm × 20 mm × 1 mm. This test piece was allowed to stand at 150 ° C. for 168 hours, and the light transmittance at a wavelength of 460 nm was measured using a spectrophotometer [manufactured by JASCO Corporation, V-570] and evaluated according to the following criteria (BaSO ₄ Standard plate is 100%).
◎: 85% or more of transmittance ○: 80% or more, less than 85% △: 75% or more, less than 80% ×: less than 75%

[TCT]
A transparent resin composition is cast into an SMD frame of an LED (light emitting device), and heat-molded at 100 ° C. for 2 hours and at 150 ° C. for 2 hours, and in a gas phase, −40 ° C. (30 minutes) → room temperature (5 minutes) ) → 120 ° C. (30 minutes) → room temperature (5 minutes) was repeated 100 times, and the number of cracks and peeling NG was counted.

  As is clear from Table 1, in all examples, TCT and tackiness were good. In addition, heat resistance is improved by using oxetanyl methacrylate or glycidyl methacrylate in combination. On the other hand, in Comparative Examples 1 and 2 using a (meth) acryl-modified silicone compound or a (meth) acrylic resin having a carbonate group alone, cracks and peeling occurred in the temperature cycle test. As in Comparative Examples 3 and 4, those using conventional general-purpose epoxy-modified silicone compounds and silicone rubbers were inferior in various properties.

Components (A) to (F) used in Examples and Comparative Examples are as follows.
<Component (A)-(Meth) acrylic modified silicone compound>
(1) X-22-164: Methacryl-modified silicone resin (functional group equivalent 190) manufactured by Shin-Etsu Chemical Co., Ltd.
(2) X-22-164As: methacryl-modified silicone resin (functional group equivalent 450) manufactured by Shin-Etsu Chemical Co., Ltd.
(3) X-22-164A: methacryl-modified silicone resin (functional group equivalent 860) manufactured by Shin-Etsu Chemical Co., Ltd.
<Component (B)-(Meth) acrylic resin having carbonate group>
(1) UM-90 (1/3) DM: a methacrylic oligomer copolymer having a carbonate group manufactured by Ube Industries, Ltd. (a methacrylic oligomer having a cyclohexane group / an oligomer having a linear alkyl group) Polymerized)
(2) UM-90 (3/1) DM: a methacrylic oligomer copolymer having a carbonate group manufactured by Ube Industries, Ltd. (methacrylic oligomer having a cyclohexane group / methacrylic oligomer having a linear alkyl group = 3/1 Copolymerized)
<Component (C) -Curing Catalyst>
(1) Park mill D: Dicumyl peroxide manufactured by NOF Corporation (2) SI110L: Benzylmethyl-p-hydroxyphenylsulfonium hexafluorophosphate manufactured by Sanshin Kasei Co., Ltd .: 48.5% by mass, γ -Butyrolactone: 50.4% by mass-Hydroxyphenyldimethylsulfonium methyl sulfate: 1.5% by mass of mixture <component (D)>
OXMA: Oxetanyl methacrylate (molecular weight 184) manufactured by Ube Industries, Ltd.
<Ingredient (E)>
(1) GMA: Glycidyl methacrylate (reagent grade) manufactured by Kanto Chemical Co., Inc.
(2) BF-1000: Epoxidized polybutadiene manufactured by ADEKA Corporation [viscosity 366 Pas (25 ° C.)]
<Comparative ingredients>
(1) X-22-169As: Epoxy-modified silicone oil (functional group equivalent 500) manufactured by Shin-Etsu Chemical Co., Ltd.
(2) MHPA: Methylhexahydrophthalic anhydride manufactured by Shin Nippon Rika Co., Ltd. (3) YE5822: Liquid silicone rubber manufactured by Momentive

  The transparent resin composition of the present invention can be suitably used as a resin for curing and sealing various optical semiconductor elements, specifically photodiodes, phototransistors, photothyristors, photoconductors, and the like.

Claims (5)

  (A) (meth) acryl-modified silicone compound, (B) (meth) acrylic resin having a carbonate group, and (C) a curing catalyst as essential components, in a total amount of 100 parts by mass of component (A) and component (B) The transparent resin composition characterized by containing the said component (A) in the ratio of 20-95 mass parts, and containing the said component (B) in the ratio of 5-80 mass parts.   The transparent resin composition according to claim 1, wherein the content of the component (C) is 0.1 to 1 part by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B).   The transparent resin composition according to claim 1 or 2, further comprising (D) 10 to 70 parts by mass of (meth) acrylic resin having an oxetane group with respect to a total of 100 parts by mass of the component (A) and the component (B). object.   Furthermore, (E) The compound which has a glycidyl group and a carbon-carbon double bond is contained in 10-50 mass parts with respect to a total of 100 mass parts of a component (A) and a component (B). The transparent resin composition as described.   The optical semiconductor device formed by sealing by hardening the transparent resin composition in any one of Claims 1-4.