KR102125023B1 - Epoxy resin composition for photosemiconductor element molding and method for preparation of the same - Google Patents

Abstract

(R₁은

이고, R₂는

이며, R'는 탄소수 1~4개의 탄화 수소이고, n 1~7의 정수이다.) 상기 카르복시기 말단의 경화제의 카르복실기 수 및 상기 산무수물 경화제의 산무수물기 수의 비율이 52:48 내지 75:25인 것을 특징으로 한다.The present invention discloses an epoxy resin composition for sealing an optical semiconductor element and a method for manufacturing the same. The epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention includes an epoxy resin, a curing agent, and a curing accelerator, and the curing agent includes a curing agent at the terminal of the carboxyl group represented by the following Chemical Formula 1 and an acid anhydride curing agent,
[Formula 1]

(R ₁ is

And R ₂ is

, R'is a hydrocarbon having 1 to 4 carbon atoms, and is an integer of n 1 to 7.) The ratio of the number of carboxyl groups of the curing agent at the end of the carboxyl group and the number of acid anhydride groups of the acid anhydride curing agent is 52:48 to 75: It is characterized by being 25.

Description

EPOXY RESIN COMPOSITION FOR PHOTOSEMICONDUCTOR ELEMENT MOLDING AND METHOD FOR PREPARATION OF THE SAME

The present invention relates to an epoxy resin composition for sealing an optical semiconductor device and a method for manufacturing the same, and more specifically, to minimize thermal stress at a high temperature by minimizing a modulus at a glass transition temperature or higher to achieve high temperature heat resistance and thermal cycling of reflow. The present invention relates to an epoxy resin composition for sealing an optical semiconductor device having durability in a test and a method for manufacturing the same.

Epoxy resins are the most widely used synthetic resins, and are used in all fields of industry such as paint, adhesives, and waterproofing. They are used in all fields of industry such as electricity, civil engineering, and construction. In addition to curing agents and curing accelerators, coupling agents, diluents, fillers, Additives such as plasticizers and modifiers can be used together.

Optical semiconductor devices are divided into light emitting devices that convert electrical signals into light and light receiving devices that convert optical signals into electrical signals.

In using a transparent molding compound (hereinafter referred to as'CMC') to protect the optical semiconductor device from the external environment, CMC not only protects the optical semiconductor device from the external environment, but also the optical semiconductor device. Transparency is required to transmit light having a wavelength generated therefrom. In addition, it is necessary to secure reliability that does not affect the characteristics of the optical semiconductor even when the optical semiconductor element is used for a long time.

In order to encapsulate an optical semiconductor device using an epoxy resin, an epoxy composition in which a curing agent and an additive are mixed with an epoxy resin has been recently produced.

Recently, electronic products being developed have been further reduced in size and weight while performing more improved functions. This further promotes high density mounting and surface mounting of the optical semiconductor package. In order to secure the durability of the electrical components, it is necessary to repeat the rapid temperature changes at high and low temperatures to evaluate resistance, and to have conditions for resistance to internal stress due to rise in vapor pressure in the resin-sealed optical semiconductor and expansion of the sealing resin shrinkage. .

Companies that use resin-sealed optical semiconductor element parts melt and mount metal solder through infrared reflow at 260°C high temperature for the purpose of attaching the parts to the circuit board. When passing through the row, internal stress increases due to an increase in vapor pressure and an expansion of the shrinkage of the epoxy resin in the optical semiconductor package sealed with the epoxy resin, which causes a decrease in reliability, and it is necessary to develop an optimized composition to solve this.

Accordingly, there is a demand for a transparent sealing material in which an epoxy resin composition serving as a sealing material for an optical semiconductor element has higher heat resistance and the like than conventional properties.

For example, in an epoxy resin composition for sealing an optical semiconductor element, as a method of improving reliability and adhesion in a thermal stress test such as a temperature cycle test, it is preferable to melt-mix a biphenyl-type epoxy resin and a phenol alkyl resin in advance. A technique has been proposed that uses an epoxy resin composition obtained by preparing an epoxy resin composition using a preliminary mixture and a curing accelerator as a sealing material for an optical semiconductor device (Japanese Patent Registration No. 3432445).

In addition, as a method for having excellent solder resistance to the sealing material (epoxy resin composition) absorbed under high temperature conditions, a specific combination of phenol resin (component b1) and acid anhydride (component b2) was conceived as a curing agent for the epoxy resin. , Based on the results of these studies, it was proposed to develop better solder resistance when reflowing solder (Republic of Korea Patent Registration No. 10-1543821).

However, these technologies are required for the reliability of automotive electronic components, 30℃/60% relative humidity for 192 hours, and then pre-treatment conditions under three reflow conditions and thermal cycle test evaluation temperature Ta -40℃ ~ 105 There is a problem in durability that can withstand a total of 1,000 times with a single temperature of ℃.

In addition, the epoxy resin composition is mainly used an acid anhydride curing agent excellent in colorless transparency. Acid anhydride as a curing agent has a long pot life, low viscosity, little irritation to the skin, and can be used for all types of epoxy resins, but the physical properties of the cured product depend on post-cure, but have high temperature stability and electrical performance compared to amine cured products. It has the advantage of high heat distortion temperature and excellent physical and electrical properties at high temperatures.

However, in the case of acid anhydride, since the reaction with epoxy is slow, a curing catalyst such as tertiary amine, imidazole, ammonium salt or phosphonium salt is generally added. It is common to shorten the curing time.

In addition, when the optical semiconductor is sealed by a transfer molding method with an epoxy resin composition known so far, the viscosity of the epoxy composition is not properly maintained, and bubbles are generated inside the cavity of the package during the process, or the epoxy resin leaks out of the cavity. Various defect factors often occur in mounting a semiconductor device on a substrate, and studies to remove it continue.

Japanese Patent Registration No. 3432445, "Epoxy resin composition and semiconductor device for optical semiconductors" Republic of Korea Patent Registration No. 10-1543821, "Epoxy resin composition for optical semiconductor element sealing and optical semiconductor device using the same"

An embodiment of the present invention includes a curing agent and an acid anhydride curing agent at the terminal of the carboxyl group represented by Chemical Formula 1, thereby maintaining a low glass transition temperature to minimize thermal stress below the glass transition temperature, thereby sealing the optical semiconductor device with minimal thermal stress It is intended to provide an epoxy resin composition.

The embodiment of the present invention includes a curing agent and an acid anhydride curing agent at the end of the carboxyl group represented by Chemical Formula 1, thereby keeping the glass transition temperature low and minimizing modulus above the glass transition temperature to minimize thermal stress at high temperatures to minimize reflow. An object of the present invention is to provide an epoxy resin composition for sealing an optical semiconductor device having improved heat resistance and high temperature resistance.

In an embodiment of the present invention, by including a solid epoxy resin and a liquid epoxy resin, by preparing a precursor of the epoxy resin to provide an epoxy resin composition for optical semiconductor device sealing that can minimize the occurrence of defects in the manufacture of the optical semiconductor package.

An embodiment of the present invention is an optical semiconductor device encapsulant having excellent light transmittance and heat resistance by using an epoxy resin composition for sealing a semiconducting optical semiconductor device in a semi-cured state (non-stage state, which is an intermediate step of a curing reaction) at room temperature. Want to provide.

The epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention includes an epoxy resin, a curing agent and a curing accelerator, and the curing agent includes a curing agent at an end of a carboxyl group represented by Formula 1 below, and an acid anhydride curing agent, and the carboxyl group The ratio of the number of carboxyl groups of the terminal curing agent and the number of acid anhydride groups of the acid anhydride curing agent is 52:48 to 75:25.

[Formula 1]

이고, R₂는

이며, R'는 탄소수 1~4개의 탄화 수소이고, n 1~7의 정수이다.) (R ₁ is

And R ₂ is

, R'is a hydrocarbon having 1 to 4 carbon atoms, and is an integer of n 1 to 7.)

The curing agent at the end of the carboxyl group may contain 54 parts by weight to 82 parts by weight, compared to 100 parts by weight of the curing agent, and the acid anhydride curing agent may include 18 parts by weight to 46 parts by weight relative to 100 parts by weight of the curing agent.

The curing agent at the terminal of the carboxyl group may include the following Chemical Formula 2 or Chemical Formula 3.

[Formula 2]

(m은 6 또는 7의 정수이다.)

(m is an integer of 6 or 7.)

[Formula 3]

The acid anhydride curing agent is hexahydro phthalic anhydride, tetrahydro phthalic anhydride, methylhexahydro phthalic anhydride, methyltetrahydro anhydride and methyltetrahydrophthalic anhydride and cyclohexane anhydride It may include at least one of 1,2,4-tricarboxylic-1,2-acid (cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride).

The epoxy resin may include a solid state epoxy resin having a softening point of 55°C to 125°C and a liquid state epoxy resin having a viscosity of 100cps to 20,000cps at 25°C.

The solid state epoxy resin is at least one of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, cresol novolac epoxy resin, bisphenol A type novolac epoxy resin and triglycidyl isocyanurate containing two or more epoxy groups in the molecule. It can include any one.

The liquid epoxy resin is at least one of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, acid anhydride modified epoxy (Haxa-hydrophtalic acid Diglycidyl ether) and aliphatic epoxy resin It can contain.

The epoxy resin composition for sealing an optical semiconductor device may further include a release agent having a refractive index value of 1.438 to 1.533.

The mold release agent may include a silicone oil containing a methylphenyl siloxane skeleton.

The epoxy resin composition for sealing an optical semiconductor device may further include at least one of a colorant, a coupling agent, an antioxidant, carbon black, an inorganic filler, and a phosphor.

The colorant may block light in the visible light region of 380 nm to 700 nm, and transmit light in the near infrared region of 700 nm or more.

The epoxy resin composition for sealing an optical semiconductor device may be in a semi-cured (B-STAGE) state at 20°C to 30°C.

The optical semiconductor device encapsulant according to an embodiment of the present invention includes an epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention.

A method of manufacturing an epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention comprises: preparing a semi-cured epoxy resin precursor by melt mixing to include a curing agent in the epoxy resin; And adding a curing accelerator to the semi-cured epoxy resin precursor to melt mixing, wherein the curing agent includes a carboxyl group-terminal curing agent and an acid anhydride curing agent represented by Formula 1 below, and the number of carboxyl groups at the carboxyl-terminal terminal curing agent. And the acid anhydride group number of the acid anhydride curing agent is 52:48 to 75:25.

[Formula 1]

이고, R₂는

이며, R'는 탄소수 1~4개의 탄화 수소이고, n 1~7의 정수이다.) (R ₁ is

And R ₂ is

, R'is a hydrocarbon having 1 to 4 carbon atoms, and is an integer of n 1 to 7.)

The epoxy resin may include a solid state epoxy resin having a softening point of 55°C to 125°C and a liquid state epoxy resin having a viscosity of 100cps to 20,000cps at 25°C.

In the step of preparing a semi-cured epoxy resin precursor by melt mixing to include a curing agent in the epoxy resin, the epoxy resin and the curing agent may be melt-mixed at a temperature of 90°C to 140°C.

In the step of melt mixing by adding a curing accelerator to the semi-cured epoxy resin precursor, the mixture may be melt-mixed at a temperature of 80°C to 120°C.

In the step of melt mixing by adding a curing accelerator to the semi-cured epoxy resin precursor, a release agent may be further added to the semi-cured epoxy resin precursor.

An embodiment of the present invention includes a curing agent and an acid anhydride curing agent at the terminal of the carboxyl group represented by Chemical Formula 1, thereby maintaining a low glass transition temperature to minimize thermal stress below the glass transition temperature, thereby sealing the optical semiconductor device with minimal thermal stress An epoxy resin composition can be provided.

The embodiment of the present invention includes a curing agent and an acid anhydride curing agent at the end of the carboxyl group represented by Chemical Formula 1, so that the glass transition temperature is low and above the glass transition temperature, the modulus is minimized to minimize thermal stress at high temperature to minimize the thermal stress at high temperatures. It is possible to provide an epoxy resin composition for sealing an optical semiconductor device with improved properties and durability in a thermal cycling test.

In an embodiment of the present invention, by including a solid epoxy resin and a liquid epoxy resin, an epoxy resin composition for sealing an optical semiconductor device capable of minimizing occurrence of defects in manufacturing an optical semiconductor package by manufacturing a precursor of an epoxy resin may be provided.

An embodiment of the present invention is an optical semiconductor device encapsulant having excellent light transmittance and heat resistance by using an epoxy resin composition for sealing a semiconducting optical semiconductor device in a semi-cured state (non-stage state, which is an intermediate step of a curing reaction) at room temperature. Can provide.

1 is a cross-sectional view showing an optical semiconductor package including an encapsulant for a semiconductor device including an epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and the contents described in the accompanying drawings, but the present invention is not limited or limited by the embodiments.

The terminology used herein is for describing the embodiments and is not intended to limit the present invention. In the present specification, the singular form also includes the plural form unless otherwise specified in the phrase. As used herein, "comprises" and/or "comprising" refers to the components, steps, operations and/or elements mentioned above, the presence of one or more other components, steps, operations and/or elements. Or do not exclude additions.

As used herein, "example", "example", "side", "example", etc. should be construed as any aspect or design described being better or more advantageous than another aspect or designs. It is not done.

Also, the term'or' refers to the inclusive'inclusive or' rather than the exclusive'exclusive or'. That is, unless stated otherwise or unclear from the context, the expression'x uses a or b'means any of the natural inclusive permutations.

Also, the singular expression (“a” or “an”) used in the specification and claims generally means “one or more” unless the context clearly indicates otherwise that it is of the singular form. It should be interpreted as.

The terms used in the description below have been selected to be general and universal in the related technical field, but may have other terms according to technology development and/or changes, conventions, and preferences of the technician. Therefore, the terms used in the following description should not be understood as limiting the technical idea, but should be understood as exemplary terms for describing the embodiments.

Also, in certain cases, some terms are arbitrarily selected by the applicant, and in this case, detailed meanings will be described in the corresponding description. Therefore, the terms used in the description below should be understood based on the meaning of the term and the entire contents of the specification, not just the name of the term.

Meanwhile, terms such as first and second may be used to describe various components, but the components are not limited by the terms. The terms are used only to distinguish one component from another component.

Unless otherwise defined, all terms (including technical and scientific terms) used in the present specification may be used as meanings commonly understood by those skilled in the art to which the present invention pertains. In addition, terms defined in the commonly used dictionary are not ideally or excessively interpreted unless specifically defined.

On the other hand, in the description of the present invention, when it is determined that a detailed description of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, terms used in the present specification (terminology) are terms used to properly represent an embodiment of the present invention, which may vary according to a user, an operator's intention, or a custom in a field to which the present invention pertains. Therefore, definitions of these terms should be made based on the contents throughout the specification.

The epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention includes an epoxy resin, a curing agent and a curing accelerator.

In particular, the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention includes a curing agent and an acid anhydride curing agent at the end of the carboxyl group represented by Chemical Formula 1, thereby maintaining a low glass transition temperature to minimize thermal stress to minimize thermal stress I can do it.

In addition, the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention includes a curing agent and an acid anhydride curing agent at the terminal of the carboxyl group represented by Chemical Formula 1, thereby minimizing modulus at a glass transition temperature or higher to reduce thermal stress at high temperatures. Minimization can improve the reflow's high temperature and heat resistance and durability in thermal cycling tests.

Hereinafter, an epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention will be described in detail as follows.

The epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention includes an epoxy resin.

Preferably, the epoxy resin may include a solid state epoxy resin having a softening point of 55°C to 125°C and a liquid state epoxy resin, and the liquid state epoxy resin has a viscosity at room temperature (25°C) of 100 cps to 20,000 cps. It is preferred.

If the softening point of the solid epoxy resin is less than 55°C, the viscosity at 90°C or higher is low, so it takes a long time to prepare the semi-cured epoxy resin precursor, and if it exceeds 125°C, the viscosity is too high and the discharge process is not smooth. have.

In addition, the weight ratio of the epoxy resin in the solid state and the liquid state may be 70:30 to 100:0.

The solid state epoxy resin is at least one of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, cresol novolac epoxy resin, bisphenol A type novolac epoxy resin, and triglycidyl isocyanurate containing two or more epoxy groups in the molecule. It can contain one.

The liquid epoxy resin includes at least one of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, haxa-hydrophtalic acid diglycidyl ether, and aliphatic epoxy resin. can do.

The epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention includes a curing agent that reacts with an epoxy resin to form a crosslinked structure.

Preferably, the curing agent included in the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention includes a curing agent at the end of the carboxyl group represented by Formula 1 and an acid anhydride curing agent.

[Formula 1]

이고, R₂는

이며, R'는 탄소수 1~4개의 탄화 수소이고, n 1~7의 정수이다.) (R ₁ is

And R ₂ is

, R'is a hydrocarbon having 1 to 4 carbon atoms, and is an integer of n 1 to 7.)

The curing agent at the end of the carboxyl group may contain 54 parts by weight to 82 parts by weight relative to 100 parts by weight of the curing agent, and if the curing agent at the terminal of the carboxyl group is 54 parts or less, the final cured product of the reaction composition (cured product of the epoxy resin composition for sealing an optical semiconductor element) If the glass transition temperature cannot be sufficiently lowered, and the curing agent at the end of the carboxyl group is 82 parts by weight or more, there is a problem in that crosslinking of the reactants is insufficient, so that strength suitable for transfer molding is not exhibited.

The acid anhydride curing agent may include 18 parts by weight to 46 parts by weight relative to 100 parts by weight of the curing agent, and if the acid anhydride curing agent is 18 parts by weight or less, crosslinking of the reactant is insufficient, so that strength suitable for transfer molding does not appear, and the acid anhydride curing agent If it is 46 parts by weight or more, there is a problem that the glass transition temperature of the final cured product (cured product of the epoxy resin composition for sealing an optical semiconductor element) cannot be sufficiently lowered.

In addition, the curing agent included in the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention has a ratio of the number of carboxyl groups at the end of the carboxyl group and the number of acid anhydrides at the acid anhydride curing agent is 52:48 to 75:25. , By including a curing agent and an acid anhydride curing agent at the end of the carboxyl group to have the above-mentioned range, while having a strength suitable for transfer molding, the glass transition temperature of the final cured product (cured product of the epoxy resin composition for sealing an optical semiconductor element) can be sufficiently lowered. have.

For example, the curing agent at the end of the carboxyl group may include 1 to 3 carboxyl groups per curing agent at the end of the carboxyl group, and the acid anhydride curing agent may include 1 to 2 acid anhydride groups per acid anhydride curing agent. .

When the curing agent included in the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention uses HF-08 (Ester of alicyclic acid anhydride and polyalkylene glycol) containing two carboxy groups as a curing agent at the end of the carboxy group, acid MH-700G (4-methylhexahydrophthalic anhydride/Hexahydrophthalic anhydride = 70/30), which is an acid anhydride curing agent containing one anhydride group, may be mixed and used. Therefore, the glass transition temperature of the final cured product (cured product of the epoxy resin composition for sealing an optical semiconductor element) can be adjusted.

The curing agent at the end of the carboxyl group represented by Formula 1 may include the following Formula 2 or Formula 3.

[Formula 2]

(m은 6 또는 7의 정수이다.)

(m is an integer of 6 or 7.)

[Formula 3]

Acid anhydride curing agents include hexahydro phthalic anhydride, tetrahydro phthalic anhydride, methylhexahydro phthalic anhydride, methyltetrahydro phthalic anhydride and cyclotetra anhydride-1 ,2,4-Tricarboxyl-1,2-acid (cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride).

The epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention is transfer-cured to a curing reaction of a semi-cured epoxy resin precursor prepared by the first reaction of an epoxy resin and a curing agent and a final semi-cured epoxy resin produced using the same. It further comprises a curing accelerator added to cure in time, the curing accelerator may include 0.05 parts by weight to 7 parts by weight relative to 100 parts by weight of the total composition, preferably 0.2 parts by weight to 3 parts by weight.

If the curing accelerator is less than 0.05 parts by weight, the curing accelerating effect is not sufficiently exhibited. If the curing accelerator exceeds 7 parts by weight, discoloration occurs in the cured product of the epoxy resin composition.

The curing accelerator is not particularly limited, and may include at least one of tertiary amine, imidazole, quaternary ammonium salt, organometallic salt, and phosphorus compound, and preferably, the curing accelerator may include phosphorus compound or imidazole. .

The epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention may further include a release agent, and the release agent may contain 0.2 to 5 parts by weight compared to 100 parts by weight of the total composition, and the release agent is less than 0.2 parts by weight If the back side does not exhibit releasability, and the curing agent exceeds 5 parts by weight, phase separation may occur in the release agent that does not react with the resin, and if a sticky phenomenon is found in manufacturing in powder form, it becomes difficult to manufacture a tablet of a certain weight, and the cured product There is a problem that the light transmittance falls.

The higher the refractive index, the higher the refractive index, while maintaining the light transmittance of the cured epoxy resin, the content can be increased, thus exhibiting a favorable effect on expression of release properties.

Preferably, as a release agent included in the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention, a release agent having a refractive index value of 1.438 to 1.533 may be used. Accordingly, the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention may include a mold release agent having a refractive index value of 1.438 to 1.533, thereby allowing mold release in a mold while maintaining light transmittance.

The mold release agent may include a silicone oil containing a methylphenyl siloxane skeleton.

Epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention, in a range that does not impair the properties such as light transmittance of the epoxy resin composition, at least any one of a colorant, a coupling agent, an antioxidant, carbon black, an inorganic filler and a phosphor It may contain one more.

The colorant can block light in the visible light region of 380 nm to 700 nm, and transmit light in the near infrared region of 700 nm or more.

The colorant is an azo anthraquinone-based pigment mixture (Kayaset Black G, kayaset Black B), anthraquinone- and aminoketone pigment mixture (Kayaset Black AN), and anthraquinone-based pigment mixture (Kayaset Red AG, Kayaset Red). A-2G, Kayaset Green AB), and at least one of Sumikakala's anthraquinone pigment mixture (OPTOGEN RED 500) may be used, but is not limited thereto.

The coupling agent is not particularly limited, but a silane coupling agent or titanate coupling agent may be used. The silane coupling agent is at least one of an epoxysilane-based, aminosilane-based, cationicsilane-based, vinylsilane-based, acrylsilane-based, and mercaptosilane-based You can use one.

The antioxidant is not particularly limited, but ascorbic acid, 2,6-di-tert-butyl-p-cresol (2,6-di-tert-butyl-p-cresol), 4-methoxyphenol, 2, 2-thiobis(4-methyl-6-t-butylphenol), 2,6-g,t-butylphenol, steric hindrance phenolic antioxidant, and phosphite antioxidant.

When light dispersibility is required in the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention, the epoxy resin composition may further include a filler, and the filler may include at least one of an inorganic filler and carbon black. Can be.

There are no particular restrictions on the type of inorganic filler, but specific examples include fused silica, crystalline silica, aluminum hydroxide (Al(OH)3), and magnesium hydroxide (Mg(OH)). 2), at least one of barium sulfate (BaSO4), magnesium carbonate (magnesium carbonate, MgCO3), and barium carbonate (BaCO3).

Carbon black includes Cysto 5HIISAF-HS, Cysto KH, Systo 3HHAF-HS, Systo NH, Systo 3M, Systo 300HAF-LS, Systo 116HMMAF-HS, Systo 116MAF, Systo FMFEF-HS, Sisto SOFEF, Sisto VGPF, Sisto SVHSRF-HS and Sisto SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, #2700, # 2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, # 3030, #3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX- 200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (Daegu Corporation); RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN- 820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA and RAVEN-1170 (Columbia Carbon Co., Ltd.) may include at least one.

The phosphor is not particularly limited, but a semiconductor nanoparticle phosphor may be used, and the phosphor may be a known semiconductor nanoparticle phosphor having a diameter of 0.1 nm or more and 100 nm or less. In general, the particle phosphor size may be 5 μm to 20 μm, and the narrower the particle size distribution, the better.

The phosphor can emit fluorescence upon receiving the excitation light, and since the semiconductor nanoparticle phosphor is a phosphor particle having high luminous efficiency, the luminous efficiency of the optical semiconductor element can be improved.

Further, by adjusting the particle diameter or material composition of the phosphor, the energy band gap of the phosphor can be set. By adjusting the particle diameter or material composition of the phosphor, the wavelength of the fluorescence emitted from the phosphor (more specifically, the wavelength spectrum) can be controlled.

The epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention may be in a semi-cured (B-STAGE) state at 20°C to 30°C.

Usually a thermosetting resin (thermosetting resin) refers to a resin that does not melt even after curing with any solvent or heat once cured, and the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention also applies to this. However, in the case of the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention, it should be manufactured so that it can be cured for encapsulation of the optical semiconductor device in a manufacturing process of an optical semiconductor device.

The epoxy resin is a thermosetting resin, and once cured by heating, the cured product is not melted by heat and does not dissolve by a solvent. However, in consideration of the ease of handling, after mixing and melting various liquid and solid phase resins and additives by heating and melting, the reaction is stopped before the complete curing reaction is achieved. Shows. Therefore, a thermosetting resin, which is a completely cured product, can be obtained after a certain period of time at a certain temperature depending on the purpose of use.

Accordingly, the term "semi-hardening" referred to in the specification of the present invention means a state in which the reaction is stopped before a complete curing reaction is performed for use for a final purpose, and those skilled in the art usually refer to "B-stage".

Accordingly, the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention can improve not only transparency but also solder resistance (reflow resistance).

The prepared form of the epoxy resin composition for sealing an optical semiconductor element according to an embodiment of the present invention may be a powder state or a tablet obtained by tableting a powder. In order to obtain an epoxy resin composition in a powder state or a tablet state obtained by tableting the powder, the epoxy resin composition for optical semiconductor element sealing according to the embodiment of the present invention can be appropriately mixed and then premixed.

The obtained mixture can be mixed and kneaded using a method such as a dry blending method or a melt blending method as appropriate, and the kneaded mixture is cooled to room temperature, subjected to a aging process, pulverized, and tabletted if necessary.

The epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention may be used as an optical semiconductor device encapsulant such as a light receiving sensor, a light emitting diode (LED), or a charge coupling device (CCD).

1 is a cross-sectional view showing an optical semiconductor package including an optical semiconductor device encapsulant comprising an epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention.

The optical semiconductor package includes a lead frame 110, an optical semiconductor element 120 mounted on the lead frame 110, a gold wire 130 and light that electrically connects the optical semiconductor element 120 and the lead frame 110. An encapsulant 140 that seals the semiconductor device 120 may be included.

The optical semiconductor package may include an epoxy resin composition for sealing an optical semiconductor element according to an embodiment of the present invention as an encapsulant 140 for sealing the optical semiconductor element 120.

In addition, the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention has a cylindrical shape in a semi-cured state (non-stage state that is an intermediate step of a curing reaction) at room temperature, so that the encapsulant has excellent light transmittance and heat resistance. Can be represented.

A method of manufacturing an epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention comprises the steps of preparing a semi-cured epoxy resin precursor by melt-mixing the epoxy resin to include a curing agent and adding a curing accelerator to the semi-cured epoxy resin precursor And melt mixing.

Since the method of manufacturing an epoxy resin composition for sealing an optical semiconductor element according to an embodiment of the present invention includes the same components as the epoxy resin composition for sealing an optical semiconductor element according to an embodiment of the present invention, description of the same components It will be omitted.

First, the manufacturing method of the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention proceeds to prepare a semi-cured epoxy resin precursor by melt-mixing so that a curing agent is included in the epoxy resin.

The curing agent includes a curing agent at the end of the carboxyl group represented by Formula 1 and an acid anhydride curing agent, and the ratio of the number of carboxyl groups at the carboxyl terminal curing agent to the number of the acid anhydride groups at the acid anhydride curing agent is 52:48 to 75:25.

[Formula 1]

이고, R₂는

이며, R'는 탄소수 1~4개의 탄화 수소이고, n 1~7의 정수이다.) (R ₁ is

And R ₂ is

, R'is a hydrocarbon having 1 to 4 carbon atoms, and is an integer of n 1 to 7.)

The epoxy resin may include a solid state epoxy resin having a softening point of 55°C to 125°C and a liquid state epoxy resin, and preferably, the liquid state epoxy resin may have a viscosity of 100 cps to 20,000 cps at room temperature (25°C). have.

In the step of preparing a semi-cured epoxy resin precursor by melt mixing to include a curing agent in the epoxy resin, the epoxy resin and the curing agent may be melt-mixed at a temperature of 90°C to 140°C.

If the melt mixing temperature of the epoxy resin and the curing agent is less than 90°C, there is a problem that they are not mixed, and when the melt mixing temperature of the epoxy resin and the curing agent exceeds 140°C, discoloration occurs.

The method of manufacturing an epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention may prepare a semi-cured resin precursor, and immediately melt-mix and react with a low temperature to prepare a final semi-cured resin, but optionally a semi-cured resin precursor It may include the step of cooling for a period of time.

This is to prevent the curing reaction of the semi-cured epoxy resin precursor from occurring, and the cooling process may be stored in a low-temperature warehouse maintained at 5° C. or less, and the semi-cured epoxy resin precursor is conveyed through a step of manufacturing the epoxy resin precursor. When discharged to the top, the cooling water in the above-described temperature range may be flowed from the lower portion of the conveyor belt, and the cooling method is not particularly limited.

Subsequently, in the method of manufacturing the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention, a step of adding a curing accelerator to the semi-cured epoxy resin precursor to melt mixing is performed.

For this reason, a semi-cured epoxy resin can be produced by subjecting the semi-cured resin precursor to low temperature melt mixing/reaction.

In the step of melt mixing by adding a curing accelerator to the semi-cured epoxy resin precursor, the mixture may be melt-mixed at a temperature of 80°C to 120°C.

If the melt-mixing temperature of the semi-cured epoxy resin precursor and the curing accelerator is less than 80°C, there is a problem that it is not mixed, and when the melt-mixing temperature of the semi-cured epoxy resin precursor exceeds 120°C, there is a problem that it is cured and gelled.

The above-mentioned temperature may have a slight curing reaction of the semi-cured epoxy resin precursor, but this is negligibly negligible, and even if the curing reaction occurs, it is not a level that cannot be used in a subsequent optical semiconductor device process.

In the step of melt mixing by adding a curing accelerator to the semi-cured epoxy resin precursor, a release agent may be further added to the semi-cured epoxy resin precursor.

The mold release agent may contain 0.2 parts by weight to 5 parts by weight based on 100 parts by weight of the total composition, and when the mold release agent is less than 0.2 parts by weight, mold release does not occur, and when the curing agent exceeds 5 parts by weight, phase separation occurs in the release agent that does not react with the resin. There is a problem.

In addition, the step of melt-mixing by adding a curing accelerator to the semi-cured epoxy resin precursor may further include at least one of a colorant, a coupling agent, an antioxidant, carbon black, an inorganic filler, and a phosphor.

In addition, in the step of melt mixing by adding a curing accelerator to the semi-cured epoxy resin precursor, a polyfunctional epoxy resin such as a heterocyclic epoxy resin may be added. The polyfunctional epoxy resin can rapidly increase the crosslink density during the reaction, so that it does not react when the semi-cured epoxy resin precursor is prepared, and is mechanically physical properties of the semi-cured epoxy resin that is finally produced by injecting it into a low-temperature melt mixing and reaction step. And optical properties.

As a polyfunctional epoxy resin, a polyfunctional epoxy resin having a trifunctional or higher functionality of at least one of a cresol novolac epoxy resin, a triglycidyl isocyanurate epoxy resin, and a solid arylcyclic epoxy resin having a cyclohexane structure epoxy terminal, The addition amount may be 2 parts by weight to 30 parts by weight compared to 100 parts by weight of the epoxy resin.

In addition, the manufacturing method of the epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention is added to various additives within a range that does not impair the physical properties of the semi-cured epoxy resin of the present invention in addition to the aforementioned materials It is possible to obtain semi-cured epoxy resins.

The semi-cured epoxy resin prepared by low-temperature melt mixing and reaction may be pulverized as necessary to prepare in a tablet form, and then provided to a process for manufacturing an optical semiconductor device. In addition, when forming a transfer for encapsulating the optical semiconductor device, it may be finally cured (C-stage) after being molded in the optical semiconductor element.

The semi-cured epoxy resin of the present invention manufactured according to the method of manufacturing an epoxy resin composition for sealing an optical semiconductor device according to an embodiment of the present invention is transparent and has a discoloration resistance, so that it is a light receiving device, a light emitting diode (LED) or a charge coupling device ( CCD), etc., can be usefully used to encapsulate optical semiconductor devices.

Example 1

A carboxyl-terminal curing agent (NPG-CA) using polyhydric alcohol is prepared. First, a liquid acid anhydride curing agent (trade name MH-700G) and glycol (neopentyl glycol) are quantitatively weighed and mixed to react to prepare a curing agent having both terminal carboxyl groups (NPG-CA).

The acid anhydride curing agent MH-700G is weighed at a ratio of 19 parts by weight and neopentyl glycol at 6 parts by weight, mixed into a container made of glass, and the temperature of the mixture is maintained at 90° C. while stirring at a low speed of 50 rpm. As the reaction proceeds, as the reaction progresses, the temperature of the mixture increases to 140° C. due to exothermic reaction, and the temperature of the reactant gradually decreases for 90 minutes after the completion of the reaction. Thereafter, the temperature of the reactant is maintained at the original set temperature of 90°C. This time is judged as the completion point of the reaction between the glycol and the acid anhydride curing agent.

In the container containing the NPG-CA thus prepared, 21 parts by weight of an acid anhydride curing agent, 16 parts by weight of a liquid epoxy resin YD-128W and 84 parts by weight of a solid epoxy YD-011H were added, and the reaction mixture was raised to 120° C. and then 60 It was kept for a minute to react. After the reaction, the mixture was placed in a cooling tray and cooled to room temperature of 28°C to prepare a semi-cured epoxy resin precursor having a softening point of 60°C to 84°C.

At this time, the ratio of the number of carboxyl groups and acid anhydride groups of the curing agent containing 25 parts by weight of the curing agent (NPG-CA) at the end of the carboxyl group, which is a reactant of neopentyl glycol and the acid anhydride curing agent MH-700G and 21 parts by weight of the acid anhydride curing agent MH-700G 52:48.

The solid-state semi-cured epoxy resin precursor prepared in this way is pulverized through a high-speed rotary grinder and passed through an iron net having a diameter of 3 mm to make a powder having a size of 3 mm or less. As a powdered epoxy resin precursor and an additive, imidazole 2E4MZ, a curing accelerator, is mixed at 1,000 rpm using a high-speed mixer at a ratio of 1.2 parts by weight, and then finished mixing the dough using an extruder maintained at 80°C to 120°C. The product passed through the extruder is cooled to room temperature of 28°C. Then, it is crushed again using a high-speed grinder, and then the powdered product is stored in a plastic container.

Prepare a tablet in the form of a cylinder by applying a certain pressure on a predetermined powder phase for convenient handling before use in the transfer molding equipment.

Example 2

Except that the carboxyl-terminal curing agent (HF-08) used in commercial proportions without using a carboxyl-terminal curing agent (NPG-CA) with polyhydric alcohol was used in a proportion of 49 parts by weight, and the acid anhydride curing agent MH-700G was added in a proportion of 16 parts by weight It was prepared in the same manner as in Example 1.

At this time, the ratio of the number of carboxyl groups and acid anhydride groups of the curing agent including 49 parts by weight of the curing agent HF-08 at the end of the carboxyl group and 16 parts by weight of the acid anhydride curing agent MH-700G is 60:40.

Example 3

It was prepared in the same manner as in Example 1, except that the commercialized carboxyl group terminal curing agent (HF-08) was added at a proportion of 13 parts by weight and added at an acid anhydride curing agent at a proportion of 15 parts by weight.

At this time, the ratio of the number of carboxyl groups and acid anhydride groups of the curing agent including 25 parts by weight of the curing agent NPG-CA at the end of the carboxyl group and 13 parts by weight of HF-08 and 15 parts by weight of the acid anhydride curing agent MH-700G is 63:37.

Example 4

It was prepared in the same manner as in Example 1, except that the commercialized carboxyl group terminal curing agent (HF-08) was added in a proportion of 22 parts by weight and added in an acid anhydride curing agent in a proportion of 10 parts by weight.

At this time, the ratio of the carboxyl group and the number of acid anhydride groups of the curing agent including 25 parts by weight of the curing agent NPG-CA at the end of the carboxyl group, 22 parts by weight of HF-08 and 10 parts by weight of the acid anhydride curing agent MH-700G is 75:25.

Comparative Example 1

A commercially available carboxyl terminal curing agent (HF-08) added in a proportion of 26 parts by weight and an acid anhydride curing agent added in a proportion of 8 parts by weight, wherein the carboxyl terminal curing agent NPG-CA 25 parts by weight, HF-08 26 parts by weight and acid anhydride The ratio of the number of carboxyl groups and acid anhydride groups of the curing agent containing 8 parts by weight of the curing agent MH-700G was prepared in the same manner as in Example 1, except that it was 80:20.

Comparative Example 2

It was prepared in the same manner as in Example 1, except that the commercialized carboxyl group terminal curing agent (HF-08) was added in a proportion of 32 parts by weight and added in an amount of 5 parts by weight of the acid anhydride curing agent.

At this time, the ratio of the number of carboxyl groups and acid anhydride groups of the curing agent including 25 parts by weight of the curing agent NPG-CA at the end of the carboxyl group, 32 parts by weight of HF-08 and 5 parts by weight of the acid anhydride curing agent MH-700G is 87:13.

Comparative Example 3

It was prepared in the same manner as in Example 1 except that NPG-CA was prepared by weighing 15 parts by weight of the acid anhydride curing agent MH-700G and 5 parts by weight of neopentyl glycol and 25 parts by weight of the acid anhydride curing agent. .

At this time, the ratio of the number of carboxyl groups and acid anhydride groups of the curing agent including 20 parts by weight of the curing agent NPG-CA at the end of the carboxyl group and 25 parts by weight of the acid anhydride curing agent MH-700G is 38:62.

Comparative Example 4

Except for using a commercially available carboxyl terminal curing agent (HF-08) at a ratio of 31 parts by weight without using a polyhydric alcohol carboxyl terminal curing agent (NPG-CA) and an acid anhydride curing agent MH-700G at 25 parts by weight. It was prepared in the same manner as in Example 1.

At this time, the ratio of the number of carboxyl groups and acid anhydride groups of the curing agent including 31 parts by weight of HF-08 curing agent at the end of the carboxyl group and 25 parts by weight of the acid anhydride curing agent MH-700G is 38:62.

Comparative Example 5

40 parts by weight of acid anhydride curing agent, 16 parts by weight of liquid epoxy resin YD-128W and 84 parts by weight of solid epoxy YD-011H was added to raise the reaction mixture to 130°C, then reacted for 10 hours, discharged to the cooling tray, and then discharged to 28°C It was prepared in the same manner as in Example 1, except that the solidified semi-cured epoxy resin precursor having a softening point of 60°C to 84°C was cooled to room temperature.

At this time, the ratio of the number of carboxyl groups and acid anhydride groups of the curing agent is 0:100.

[Table 1] is a table showing the properties of the epoxy resin composition for optical semiconductor device sealing according to Examples 1 to 4 of the present invention.

[Table 1]

[Table 2] is a table showing the properties of the epoxy resin composition for optical semiconductor device sealing according to Comparative Examples 1 to 5.

[Table 2]

The glass transition temperature was molded into a dedicated mold for each prepared epoxy resin composition (curing condition: 150°C for 4 minutes) to prepare a test piece (size: diameter 50 mm, thickness 1 mm) of the cured product. The specimen was heated at 150° C. for 3 hours to complete curing. The specimen after curing was completely terminated was measured with a differential scanning calorimeter (DSC: DSC Q2000, manufactured by TA Instruments Inc.), and the midpoint of the two bending points appearing before and after the glass transition temperature was used as the glass transition temperature (°C). .

Referring to [Table 1] and [Table 2], the epoxy resin composition for optical semiconductor device sealing according to Examples 1 to 4 of the present invention has low glass transition temperatures of 80°C, 56°C, 71°C and 63°C, respectively. However, it can be seen that the epoxy resin compositions for sealing optical semiconductor elements according to Comparative Examples 3 to 5 exhibit relatively high glass transition temperatures of 95°C, 90°C and 115°C, respectively. However, Comparative Examples 1 and 2 have relatively low glass transition temperatures of 52°C and 49°C, but cannot be used for sealing optical semiconductor devices because molding is impossible.

Solder resistance is molded by transfer molding (forming for 4 minutes at 150°C, and post-curing for 3 hours at 150°C) with an optical semiconductor device (SiN photodiode: 3.08mmХ3.08mmХ thickness 0.52mm) with each epoxy resin composition. A surface mount type optical semiconductor package was prepared. At this time, in order to show a smooth mold releasability, silicone oil (NB-500 Southern CNC Precision Electronic Component Release Agent) was applied to the surface of the mold prior to transfer molding.

Using the package thus prepared, each package subjected to moisture absorption conditions of 30°C/60RH%Х192 hours (10 samples each) was provided to the infrared (IR) reflow, respectively, and the percentage of peeling and cracking in the package itself was individually determined. Measured and evaluated.

A case where the probability of occurrence of package peeling and cracking is less than 0 to 34% is indicated as "good", and a case where the probability of occurrence of package peeling and cracking is less than 34 to 67% is indicated as "suitable", and occurrence of package peeling and cracking When the probability was 67 to 100%, it was expressed as "poor".

Referring to [Table 1] and [Table 2], the optical semiconductor package using the epoxy resin composition for sealing an optical semiconductor device according to Examples 1 to 4 of the present invention exhibits “good” properties, but Comparative Example 1 and It can be seen that the optical semiconductor package using the epoxy resin composition for sealing an optical semiconductor element according to 2 cannot be molded, and the probability of occurrence of package peeling and cracking increases.

Temperature cycle test is a TC (-40 ~ 105 ℃, Ramp time 10 min, Soak time 20 min, 1 Cycle 60 min, 1000 cycles) temperature cycle test chamber (JT) -5GT JEOTTECH (JEIO TECH CO., LTD.) and inspect the electrical characteristics. If there is no abnormality in electrical characteristics, it is evaluated as "suitable". In the case of defective electricity, it is evaluated as "bad".

Referring to [Table 1] and [Table 2], the optical semiconductor package using the epoxy resin composition for sealing an optical semiconductor device according to Examples 1 to 4 of the present invention has electrical properties of "suitable", but in Comparative Examples 1 and 2 The optical semiconductor package using the epoxy resin composition for sealing an optical semiconductor device according to the invention cannot be molded, so a package sample cannot be obtained, and the optical semiconductor package using the epoxy resin composition for sealing an optical semiconductor device according to Comparative Examples 3 and 4 is generally electric. It can be seen that defective electricity is generated. In the case of Comparative Example 5, it was judged that there was no problem in electric conduction, but it was found that peeling defects occurred at the interface between the package inner substrate and the encapsulant in the solder resistance evaluation after the moisture absorption condition of 30° C./60RH% Х 192 hours.

Example 2

Acid anhydride curing agent (MH-700G) 16 parts by weight and carboxyl terminal curing agent (HF-08) in a container containing 49 parts by weight ratio of liquid epoxy resin YD-128W 16 parts by weight and solid epoxy resin YD-011H 84 parts by weight Then, the reaction mixture was raised to 120°C and maintained for 60 minutes to react. After the reaction, the mixture was placed in a cooling tray and cooled to room temperature of 28°C to prepare a semi-cured epoxy resin precursor having a softening point of 60°C to 84°C. At this time, the ratio of the number of carboxyl groups and acid anhydride groups of the curing agent including 49 parts by weight of the curing agent HF-08 at the end of the carboxyl group and 16 parts by weight of the acid anhydride curing agent MH-700G is 60:40.

The solid-state semi-cured epoxy resin precursor prepared in this way is pulverized through a high-speed rotary grinder and then passed through an iron net having a diameter of 3 mm to form a powder having a size of 3 mm or less. As a powdered epoxy resin precursor and an additive, imidazole 2E4MZ, a curing accelerator, is mixed at 1,000 rpm using a high-speed mixer at a ratio of 1.2 parts by weight, and then finished mixing the dough using an extruder maintained at 80 to 120°C.

The product passed through the extruder is cooled to room temperature of 28°C. Then, it is crushed again using a high-speed grinder, and the powdered product is stored in a plastic container. Prepare a tablet in the form of a cylinder by applying a certain pressure on a predetermined powder phase for convenient handling before use in the transfer molding equipment.

Example 5

When the curing accelerator was added, a polyether-modified silicone oil (KF353, refractive index 1.438) was prepared in the same manner as in Example 2, except that 1 part by weight was added.

Example 6

When the curing accelerator was added, it was prepared in the same manner as in Example 2, except that 5 parts by weight of polyether-modified silicone oil (KF615A, refractive index 1.451) was added.

Example 7

When the curing accelerator was added, methylphenyl silicone oil (KF54, refractive index 1.505) was prepared in the same manner as in Example 2, except that 6 parts by weight was added.

Example 8

When the curing accelerator was added, methylphenyl silicone oil (PMM0025, refractive index 1.533) was prepared in the same manner as in Example 2, except that 7 parts by weight was added.

Comparative Example 6

When the curing accelerator was added, carbinol-modified silicone oil (KF6001, refractive index 1.413) was prepared in the same manner as in Example 2, except that 0.2 parts by weight was added.

Comparative Example 7

When the curing accelerator was added, it was prepared in the same manner as in Example 2, except that 2 parts by weight of polyether-modified silicone oil (KF353, refractive index 1.438) was added.

Comparative Example 8

When the curing accelerator was added, a polyether-modified silicone oil (KF615A, refractive index 1.451) was prepared in the same manner as in Example 2, except that 7 parts by weight was added.

[Table 3] is a table showing the properties of the epoxy resin composition for optical semiconductor device sealing according to Examples 5 to 9 of the present invention.

[Table 3]

[Table 4] is a table showing the properties of the epoxy resin sealant for optical semiconductor device sealing according to Comparative Examples 6 to 8.

[Table 4]

The light transmittance (%) was measured from 300 nm to 1100 nm using an ultraviolet-spectrometer (UV-spectormeter) (measured by placing a specimen having a thickness of 1 mm into a quartz cell containing a paraffin solution). As measured by an ultraviolet-spectrometer (V-670, JASCO Corporation), the light transmittance at a room temperature of 1 mm and a wavelength of 650 nm is 75 to 99%. When the light transmittance was 75% or more, it was evaluated as "transparent", and when it was less than 75%, it was evaluated as "opaque".

However, the light transmittance when the filler, colorant or phosphor described above is used is not limited to the above.

Referring to [Table 3] and [Table 4], the epoxy resin composition for sealing an optical semiconductor device according to Examples 5 to 8 of the present invention exhibits “transparent” properties, but an optical semiconductor according to Comparative Examples 6 and 8 It can be seen that the epoxy resin composition for device sealing was "opaque".

The releasability is compounded by melting each component shown in [Table 3] to [Table 4], melted, kneaded with a mixing extruder (80°C to 120°C), aged, cooled at room temperature, and pulverized to obtain a desired powdery form. An epoxy resin composition is obtained.

Using each of the powdered epoxy resin compositions thus obtained, the optical semiconductor device was sealed by transfer molding (forming condition: 4 minutes at 150° C.) (encapsulation of the epoxy resin composition on a printed circuit board size: length 20 mm x width 5.9 mm x When the thickness is 0.7 mm x 12 lines), it is cured for 4 minutes, and then its release properties from the transfer molding mold are evaluated.

Printing obtained in the fourth attempt when continuous transfer molding is performed after cleaning molding with a cleaning rubber sheet (SC-4000 NARA CHEM), a cleaning wax sheet (SW-8000 NARA CHEM) The epoxy resin composition molded on the circuit board and its releasability from the mold are evaluated.

When the epoxy resin composition molded on the printed circuit board can be separated from the mold (cavity) only by the operation of the eject pin, releasability is evaluated as "good". When the optical semiconductor package can be separated from the mold by the operation of the eject pin and air blowing, the releasability is evaluated as "good". When the optical semiconductor package cannot be separated by the operation of the eject pin and air blow, and is separated from the mold by applying mechanical force to cause deformation of the package and cracks are generated inside, the releasability is evaluated as "poor".

Referring to [Table 3] and [Table 4], the optical semiconductor package using the epoxy resin composition for sealing an optical semiconductor device according to Examples 5 to 8 of the present invention has excellent releasability, but the light according to Comparative Example 6 It can be seen that the optical semiconductor package using the epoxy resin composition for sealing a semiconductor device is "poor". From this, it can be seen that when using the silicone release agent having a refractive index of 1.438 or more, the release property can be improved without inhibiting the light transmittance of the encapsulant while increasing the ?t amount.

However, the optical semiconductor package using the epoxy resin composition for sealing an optical semiconductor element according to Comparative Examples 7 and 8 exhibits relatively “good” characteristics, but since the light transmittance is “opaque”, it can be used for sealing an optical semiconductor element. none.

As described above, although the present invention has been described with limited embodiments and drawings, the present invention is not limited to the above embodiments, and various modifications and variations from these descriptions will be made by those skilled in the art to which the present invention pertains. This is possible.

Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined not only by the following claims, but also by the claims and equivalents.

110: lead frame 120: optical semiconductor element
130: gold wire 140: encapsulant

Claims (18)

It contains an epoxy resin, a curing agent and a curing accelerator,
The curing agent includes a curing agent at the end of the carboxyl group represented by Formula 1 and an acid anhydride curing agent,
[Formula 1]

(R ₁ is

And R ₂ is

, R'is a hydrocarbon having 1 to 4 carbon atoms, and is an integer of n 1 to 7.)
The curing agent at the end of the carboxyl group includes 54 parts to 82 parts by weight compared to 100 parts by weight of the curing agent,
The acid anhydride curing agent comprises 18 parts by weight to 46 parts by weight compared to 100 parts by weight of the curing agent,
The ratio of the number of carboxyl groups of the curing agent at the end of the carboxyl group and the number of acid anhydride groups of the acid anhydride curing agent is 52:48 to 75:25.
delete According to claim 1,
The curing agent at the terminal of the carboxyl group includes the following Chemical Formula 2 or Chemical Formula 3
[Formula 2]

(m is an integer of 6 or 7.)
[Formula 3]

Epoxy resin composition for sealing an optical semiconductor device, characterized in that.
According to claim 1,
The acid anhydride curing agent is hexahydro phthalic anhydride, tetrahydro phthalic anhydride, methylhexahydro phthalic anhydride, methyltetrahydro anhydride and methyltetrahydrophthalic anhydride and cyclohexane anhydride Epoxy for sealing an optical semiconductor device, characterized in that it contains at least one of 1,2,4-tricarboxylic-1,2-acid (cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride) Resin composition.
According to claim 1,
The epoxy resin is an epoxy resin composition for sealing an optical semiconductor device, characterized in that it comprises a solid state epoxy resin having a softening point of 55°C to 125°C and a liquid state epoxy resin having a viscosity of 100 cps to 20,000 cps at 25°C.
According to claim 1,
The epoxy resin includes a solid state epoxy resin,
The solid state epoxy resin is at least one of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, cresol novolac epoxy resin, bisphenol A type novolac epoxy resin and triglycidyl isocyanurate containing two or more epoxy groups in the molecule. Epoxy resin composition for sealing an optical semiconductor device comprising any one.
According to claim 1,
The epoxy resin includes a liquid epoxy resin,
The liquid epoxy resin is at least one of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, acid anhydride modified epoxy (Haxa-hydrophtalic acid Diglycidyl ether) and aliphatic epoxy resin It characterized in that it comprises an epoxy resin composition for sealing an optical semiconductor device.
According to claim 1,
The epoxy resin composition for sealing an optical semiconductor element further comprises a release agent having a refractive index value of 1.438 to 1.533.
The method of claim 8,
The release agent comprises a silicone oil containing a methylphenyl siloxane backbone, the epoxy resin composition for sealing an optical semiconductor device.
According to claim 1,
The epoxy resin composition for sealing an optical semiconductor device further comprises at least one of a colorant, a coupling agent, an antioxidant, carbon black, an inorganic filler, and a phosphor, the epoxy resin composition for sealing an optical semiconductor device.
The method of claim 10,
The colorant is an epoxy resin composition for sealing an optical semiconductor device, characterized in that it blocks light in the visible light region of 380 nm to 700 nm and transmits light in the near infrared region of 700 nm or more.
According to claim 1,
The epoxy resin composition for sealing an optical semiconductor element is a semi-cured (B-STAGE) state at 20 ℃ to 30 ℃ epoxy resin composition for sealing an optical semiconductor element.
An optical semiconductor element encapsulating material comprising the epoxy resin composition for sealing an optical semiconductor element according to any one of claims 1 to 3 to 12.
Preparing a semi-cured epoxy resin precursor by melt mixing to include a curing agent in the epoxy resin; And
Melting and mixing by adding a curing accelerator to the semi-cured epoxy resin precursor
Including,
The curing agent includes a curing agent at the end of the carboxyl group represented by Formula 1 and an acid anhydride curing agent,
[Formula 1]

(R ₁ is

And R ₂ is

, R'is a hydrocarbon having 1 to 4 carbon atoms, and is an integer of n 1 to 7.)
The curing agent at the end of the carboxyl group includes 54 parts to 82 parts by weight compared to 100 parts by weight of the curing agent,
The acid anhydride curing agent comprises 18 parts by weight to 46 parts by weight compared to 100 parts by weight of the curing agent,
A method of manufacturing an epoxy resin composition for sealing an optical semiconductor device, wherein the ratio of the number of carboxyl groups of the curing agent at the terminal of the carboxyl group and the number of acid anhydride groups of the acid anhydride curing agent is 52:48 to 75:25.
The method of claim 14,
The epoxy resin is a method for producing an optical resin device sealing epoxy resin composition comprising a solid state epoxy resin having a softening point of 55°C to 125°C and a liquid state epoxy resin having a viscosity of 100cps to 20,000cps at 25°C.
The method of claim 14,
The step of preparing a semi-cured epoxy resin precursor by melt mixing to include a curing agent in the epoxy resin,
A method of manufacturing an epoxy resin composition for sealing an optical semiconductor device, characterized in that the epoxy resin and the curing agent are melt-mixed at a temperature of 90°C to 140°C.
The method of claim 14,
The step of melt mixing by adding a curing accelerator to the semi-cured epoxy resin precursor,
Method for producing an epoxy resin composition for optical semiconductor device sealing, characterized in that the mixture is melt-mixed at a temperature of 80 ℃ to 120 ℃.
The method of claim 14,
The step of melt mixing by adding a curing accelerator to the semi-cured epoxy resin precursor,
A method of manufacturing an epoxy resin composition for sealing an optical semiconductor device, characterized in that a mold release agent is further added to the semi-cured epoxy resin precursor.

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