JP5125681B2 - Curable resin composition, LED package using the same, and manufacturing method thereof - Google Patents

Description

  The present invention relates to a curable resin composition, a light emitting diode (LED) package using the same, and a method for manufacturing the same.

  Conventionally, acrylic resins that are relatively excellent in terms of transparency, light resistance, and heat-resistant coloration have been widely used as optical member resins. However, acrylic resins cannot be said to have sufficient mechanical properties such as breaking strength, and further improvements in properties are required depending on the application. Further, there is a problem that the curing shrinkage is relatively large and the volume is reduced during curing.

  On the other hand, epoxy resins are often used for optical member resins used in the field of optical and electronic equipment because they require high heat resistance and mechanical properties that can withstand mounting processes on electronic boards and high-temperature operations. It was. In recent years, the use of high-intensity laser light, blue light, and near-ultraviolet light has been expanding in the field of optical and electronic equipment. There is a need for resins for optical members.

  However, in general, an optical member formed of an epoxy resin has high transparency in the visible range, but sufficient transparency cannot be obtained in the ultraviolet to near ultraviolet range. Among epoxy resins, alicyclic bisphenol A diglycidyl ether and the like have relatively high transparency in the ultraviolet to near-ultraviolet region, but they have a problem that they are easily colored by heat or light. For example, Patent Documents 1 and 2 disclose a method for reducing impurities that are one of the causes of coloring contained in alicyclic bisphenol A diglycidyl ether, but further improvement in heat resistance and ultraviolet coloring resistance is required. It has been. In addition, a cured product formed from an alicyclic epoxy resin and an acid anhydride is excellent in transparency in the near-ultraviolet region, but its fracture strength and toughness are inferior to those of an aromatic epoxy resin. Interfacial debonding and cracks are considered as problems. Furthermore, there is a problem that the acid anhydride volatilizes and the volume decreases during curing.

  By the way, the optical member (sealing member) for sealing the LED needs to have high transparency, light resistance, and heat resistance in order not to lower the luminance of the LED. In addition, the reliability evaluation of the LED package includes a temperature cycle test and a high-temperature and high-humidity lighting test, and mechanical characteristics and high-temperature and high-humidity resistance to satisfy these requirements are also required.

  The LED sealing member is generally formed by a casting method in which a liquid thermosetting resin is cast into a mold and heat-cured. However, in this method, since the thermosetting resin is slowly cured, the productivity is not sufficient, the problem that it is difficult to control the thickness of the sealing member, and there are voids in the sealing member. There is a problem that it is easy to mix.

In recent years, with the expansion of the LED market, there has been a demand for an LED package manufacturing process that improves mass productivity. Liquid transfer molding is a molding method in which a liquid thermosetting resin is injection-molded into a high-temperature mold and heat-cured, and is useful because of short molding time and high productivity. Moreover, if this shaping | molding method is used, it will also be possible to give arbitrary shapes.
JP 2003-171439 A JP 2004-75894 A

  However, the conventional transparent encapsulating resin for LED can achieve a certain level of high temperature and high humidity resistance, but it is not always satisfactory in terms of liquid transfer moldability. More specifically, when a conventional transparent sealing resin for LED is molded by a liquid transfer molding method, voids or unfilled portions are generated in the molded product, or the molded product is deformed during demolding. There were many cases.

  The present invention has been made in view of such circumstances, and provides a curable resin composition that can maintain high brightness of an LED under high temperature and high humidity and has excellent liquid transfer moldability. With the goal.

  The curable resin composition according to the present invention is derived from a tri- or higher functional polycaprolactone polyol and / or a tri- or higher functional polyol having a structural unit derived therefrom, and a tri- or higher functional aliphatic polyol and / or the same. A polyol component containing a trifunctional or higher functional polyol having a structural unit, a bifunctional or trifunctional alicyclic polyisocyanate having an isocyanate group bonded to a secondary carbon atom, and / or a structural unit derived therefrom And a polyisocyanate component containing a bifunctional or trifunctional polyisocyanate. The curable resin composition according to the present invention preferably forms a cured product having a Shore A hardness of 65 or more at 165 ° C. when heated at 165 ° C. for 5 minutes.

  The curable resin composition according to the present invention forms a cured product by a reaction between a polyol component and a polyisocyanate component. By adopting the above-mentioned specific components as the polyol component and the polyisocyanate component, the curable resin composition according to the present invention has a high brightness of LED under high temperature and high humidity when used as a transparent sealing resin for LED. Can be maintained, and a cured product having high hardness at a high temperature can be formed in a short time. More specifically, for example, when the cured product having a Shore A hardness of 65 or more is formed at 165 ° C. when heated at 65 ° C. for 5 minutes, the curable resin composition according to the present invention is an excellent liquid. Has transfer moldability.

  The polycaprolactone polyol preferably has a weight average molecular weight of 500 or less and a hydroxyl value of 300 mgKOH / g or more. The ratio of the total amount of the polycaprolactone polyol and the polyol having a structural unit derived therefrom to the entire polyol component is preferably 40% by mass or more. The aliphatic polyol preferably has a weight average molecular weight of 350 or less and a hydroxyl value of 1000 mgKOH / g or more. The ratio of the total amount of the aliphatic polyol and the polyol having a structural unit derived therefrom to the entire polyol component is preferably 40% by mass or more. The ratio of the total amount of the alicyclic polyisocyanate and the polyisocyanate having a structural unit derived therefrom to the whole polyisocyanate component is preferably 40% by mass or more. By satisfying these requirements, the crosslink density is increased, and a cured product having high hardness at a high temperature can be easily formed in a short time.

  The aliphatic polyol has trimethylolpropane and a polyol having a hydroxyl value of 1300 mgKOH / g or more, and is derived from the total amount of the aliphatic polyol having trimethylolpropane and a polyol derived from the trimethylolpropane and the polyol. The proportion of the trifunctional or higher functional polyol having a structural unit is 40% by mass or higher, the polyol having a hydroxyl value of 1300 mgKOH / g or higher, and the total amount of the aliphatic polyol having the structural unit derived therefrom, It is preferable that the ratio with respect to the total amount of the trifunctional or higher functional polyol having a structural unit derived therefrom is 10% by mass or more. Thereby, the hardened | cured material which has high hardness at high temperature can be formed more easily in a short time.

  The polyol having a structural unit derived from polycaprolactone polyol is a prepolymer obtained by reacting a polyol containing polycaprolactone polyol with a polyisocyanate having a total number of isocyanate groups smaller than the total number of hydroxyl groups of the polyol. preferable. The polyol having a structural unit derived from an aliphatic polyol may be a prepolymer obtained by reacting a polyol containing an aliphatic polyol with a polyisocyanate having a total number of isocyanate groups smaller than the total number of hydroxyl groups of the polyol. preferable. The polyisocyanate having a structural unit derived from the alicyclic polyisocyanate reacts with a polyisocyanate containing an alicyclic polyisocyanate and a polyol having a total number of hydroxyl groups smaller than the total number of isocyanate groups of the polyisocyanate. It is preferable that it is the prepolymer obtained by making it. By using these prepolymers, the curing rate is increased, and a curable resin composition more suitable for liquid transfer molding can be obtained. Moreover, the compatibility of a polyol component and a polyisocyanate component improves by using a prepolymer rather than the case where only monomers are mixed. Furthermore, curing shrinkage can be reduced by using a prepolymer.

  The curable resin composition according to the present invention preferably further includes a hindered phenolic antioxidant.

  The curable resin composition according to the present invention preferably has a gelation time at 165 ° C. of 25 to 200 seconds. This makes liquid transfer under almost the same molding conditions as conventional solid transfer molding (a molding method in which a solid raw material is melted in a pot at room temperature and then the molten raw material is pressed into a mold cavity and cured). The sealing member of the LED package can be formed by molding, and the efficiency of manufacturing the LED package is improved.

  The curable resin composition according to the present invention is preferably formed by heating a cured product having a glass transition temperature of 110 ° C. or higher. In this case, it is difficult to cause defects such as peeling, cracking, and disconnection in the temperature cycle test, and an LED package having further excellent temperature cycle resistance can be manufactured.

  The manufacturing method of the LED package which concerns on this invention comprises the process of shape | molding the above-mentioned curable resin composition by a liquid transfer molding method, and forming the sealing member of an LED package. According to this manufacturing method, it is possible to manufacture an LED package excellent in high temperature and high humidity resistance and temperature cycle resistance with high productivity.

  The LED package which concerns on this invention is equipped with the sealing member which can be obtained by shape | molding the above-mentioned curable resin composition. The LED package according to the present invention has excellent high temperature and high humidity resistance and temperature cycle resistance.

  The curable resin composition according to the present invention can maintain high brightness of the LED under high temperature and high humidity, and is excellent in liquid transfer moldability. Moreover, according to the curable resin composition which concerns on this invention, the LED package which is excellent also in terms of temperature cycling resistance can be obtained. Furthermore, the curable resin composition according to the present invention has small curing shrinkage and is excellent in optical properties such as transparency, light resistance and heat resistance of the cured product and mechanical properties such as breaking strength.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The curable resin composition according to the present embodiment is a trifunctional or higher functional polycaprolactone polyol and / or a trifunctional or higher functional polyol having a structural unit derived therefrom, and a trifunctional or higher functional aliphatic polyol and / or derived therefrom. A polyol component containing a trifunctional or higher functional polyol having a structural unit, a bifunctional or trifunctional alicyclic polyisocyanate having an isocyanate group bonded to a secondary carbon atom and / or a structural unit derived therefrom And a polyisocyanate component containing a bifunctional or trifunctional polyisocyanate. Each of the polyol component and the polyisocyanate component is in a liquid state, and a cured product is formed by heating the mixture. The curable resin composition according to the present embodiment is a two-component thermosetting resin composition composed of a polyol component (A liquid) and a polyisocyanate component (B liquid).

  The curable resin composition according to the present embodiment forms a cured product having a high hardness at a high temperature by being cured in a short time at a high temperature by using the specific component as a polyol component and a polyisocyanate component. Can do. Thereby, the outstanding liquid transfer moldability is obtained. More specifically, when the curable resin composition is heated at 165 ° C. for 5 minutes, a cured product having a Shore A hardness of 65 or more at 165 ° C. is preferably formed. If the Shore A hardness is less than 65, the molded product may be deformed when the LED package is taken out from the high-temperature mold after molding.

  The polycaprolactone polyol has three or more hydroxyl groups bonded to the terminal of the polycaprolactone skeleton. The polycaprolactone polyol preferably has a weight average molecular weight of 500 or less and a hydroxyl value of 300 mgKOH / g or more. The weight average molecular weight is particularly preferably 300 or less. The hydroxyl value is particularly preferably 500 or more. When the weight average molecular weight exceeds 500, the crosslinking density tends to decrease and the hardness tends to decrease. Similarly, when the hydroxyl value falls below 300 mgKOH / g, the crosslinking density tends to decrease and the hardness tends to decrease.

  The polycaprolactone polyol may be synthesized by a conventional method, or a commercially available product may be obtained. The tri- or higher functional polycaprolactone polyol is used alone or in combination of two or more.

  The trifunctional or higher functional polyol having a structural unit derived from polycaprolactone polyol is preferably a prepolymer obtainable by reaction of a polyol containing polycaprolactone polyol and polyisocyanate, and the structural unit derived from an aliphatic polyol. The trifunctional or higher functional polyol is preferably a prepolymer obtainable by a reaction between a polyol containing an aliphatic polyol and a polyisocyanate. Details of the prepolymer will be described later.

  The total amount of the polycaprolactone polyol and the polyol having a structural unit derived therefrom is preferably 40% by mass or more based on the total polyol component. As a result, the crosslink density at the time of curing becomes sufficiently high, and as a result, the hardness and toughness of the cured product become sufficiently high. From the viewpoint of more effectively exhibiting such an effect, the above ratio is more preferably 50% by mass or more. When the said ratio is less than 40 mass%, there exist problems, such as bridge | crosslinking density becoming low, hardness becoming low, and lacking in toughness.

  The polyol component includes an aliphatic polyol and / or a polyol having a structural unit derived therefrom, which is different from the polyol having a polycaprolactone polyol and / or a structural unit derived therefrom. The aliphatic polyol has a weight average molecular weight of 350 or less, a hydroxyl value of preferably 1000 mgKOH / g or more, and a weight average molecular weight of particularly preferably 250 or less. The hydroxyl value is particularly preferably 1200 or more. When the weight average molecular weight exceeds 350, the crosslinking density tends to decrease and the hardness tends to be low. Similarly, when the hydroxyl value is below 1000 mgKOH / g, the crosslinking density tends to decrease and the hardness tends to decrease.

  The ratio of the total amount of the aliphatic polyol and / or the polyol having a structural unit derived therefrom is preferably 40% by mass or more and more preferably 45% by mass or more with respect to the entire polyol component. When the said ratio is less than 40 mass%, there exist problems, such as bridge | crosslinking density becoming low, hardness becoming low, and lacking in toughness.

  The aliphatic polyol preferably contains trimethylolpropane and a polyol having a hydroxyl value of 1300 mgKOH / g or more. The ratio of the total amount of trimethylolpropane and the polyol having a structural unit derived therefrom is preferably 40% by mass or more with respect to the total amount of the aliphatic polyol and the polyol having a structural unit derived therefrom. 1300 mgKOH The ratio of the total amount of the polyol having a hydroxyl value of / g or more and the polyol having a structural unit derived therefrom is 10% by mass or more based on the total amount of the aliphatic polyol and the polyol having a structural unit derived therefrom. Preferably there is. Examples of the polyol having a hydroxyl value of 1300 mgKOH / g or more include glycerin, pentaerythritol, diglycerin, dipentaerythritol and the like, and glycerin and diglycerin are particularly preferable.

  The polyisocyanate component is a component composed of a bifunctional or higher isocyanate having two or more isocyanate groups in one molecule. This polyisocyanate component is composed of a bifunctional or trifunctional alicyclic polyisocyanate having an isocyanate group bonded to a secondary carbon atom and / or a bifunctional or trifunctional or higher polyfunctional polymer having a structural unit derived therefrom. Contains isocyanate. Here, “secondary carbon atom” means a carbon atom directly bonded to two carbon atoms. Moreover, bifunctional or trifunctional alicyclic isocyanate has two or three isocyanate groups in one molecule.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate), and 4,4'-methylenebis (cyclohexyl isocyanate) is particularly preferable. In addition, isocyanurate type and biuret type polyisocyanates synthesized from the above alicyclic polyisocyanates may be used, and isocyanurate type polyisocyanates synthesized from isophorone diisocyanate as raw materials are particularly preferred. The transition temperature can be increased.

  The alicyclic polyisocyanate may be synthesized by a conventional method, or a commercially available product may be obtained. These may be used alone or as a mixture of plural kinds.

  The polyisocyanate having a structural unit derived from an alicyclic polyisocyanate is preferably a prepolymer that can be obtained by reacting a polyisocyanate containing an alicyclic polyisocyanate with a polyol. Details of the prepolymer will be described later.

  The total amount of the alicyclic polyisocyanate and the polyisocyanate having a structural unit derived therefrom is preferably 40% by mass or more based on the polyisocyanate component. Thereby, the high-temperature high-humidity resistance of the cured product is sufficiently high. From the viewpoint of further effectively exhibiting such effects and further increasing the curing rate, the above ratio is more preferably 40 to 85% by mass. When the said ratio is less than 40 mass%, when it is set as an LED package, there exists a tendency for high-temperature, high-humidity resistance and temperature cycling resistance to fall.

  A prepolymer having a structural unit derived from polycaprolactone polyol is obtained by reacting a polyol containing polycaprolactone polyol with a polyisocyanate so that the hydroxyl groups in the polyol are excessive with respect to the isocyanate groups in the polyisocyanate. It is preferably a prepolymer having a remaining hydroxyl group. A prepolymer having a structural unit derived from an aliphatic polyol is obtained by reacting a polyol containing an aliphatic polyol with a polyisocyanate so that the hydroxyl groups in the polyol are excessive relative to the isocyanate groups in the polyisocyanate. It is preferably a prepolymer having a remaining hydroxyl group. These prepolymers are obtained by reacting the hydroxyl group of the polyol with the isocyanate group of the isocyanate to form a urethane bond. The polyol to be reacted with the polyisocyanate may contain a component other than the tri- or higher functional polycaprolactone polyol or the tri- or higher functional aliphatic polyol.

  In the above reaction, the ratio X / Y of the total number of hydroxyl groups of the polyol (hydroxyl equivalent) X to the total number of isocyanate groups of the polyisocyanate (isocyanate equivalent) Y is preferably 3-20. When X / Y is smaller than 3, there is a problem that the molecular weight of the prepolymer is increased and the viscosity is high and difficult to handle. When X / Y is larger than 20, the effect of prepolymerization tends to be reduced.

  The prepolymer having a structural unit derived from an alicyclic polyisocyanate is prepared by adding a polyisocyanate containing an alicyclic polyisocyanate and a polyol so that the isocyanate group in the polyisocyanate is excessive with respect to the hydroxyl group in the polyol. A prepolymer obtained by reacting and having a remaining isocyanate group is preferred. This prepolymer is obtained by reacting the isocyanate group of the polyisocyanate with the hydroxyl group of the polyol to form a urethane bond. The polyisocyanate to be reacted with the polyol may contain components other than the alicyclic isocyanate.

  In the above reaction, the ratio X / Y of the total number of hydroxyl groups (hydroxyl equivalent) X of polyol and the total number of isocyanate groups (isocyanate equivalent) Y of polyisocyanate is preferably 0.05 to 0.3. When X / Y is larger than 0.3, there is a problem that the molecular weight of the prepolymer becomes large and the viscosity becomes high and difficult to handle. When X / Y is smaller than 0.05, the effect of prepolymerization tends to be small.

  By using the prepolymer as described above, the curing rate is increased as compared with the case where no prepolymer is used. Moreover, the compatibility of a polyol component and a polyisocyanate component improves by using a prepolymer, and it becomes easy to obtain a highly transparent sealing member. Furthermore, curing shrinkage can be reduced by using a prepolymer.

  The polyol component and the polyisocyanate component may contain other polyols or polyisocyanates as monomers or prepolymers in addition to the above components. Other polyols and polyisocyanates are preferably non-aromatic compounds. When an aromatic compound is used, in addition to being inferior in heat resistance and light resistance, the curing rate tends to be too fast, and it tends to be difficult to produce a package by liquid transfer molding.

  Examples of other polyols include ethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-dimethanolcyclohexane, polycarbonate diol, a hydroxyl group-containing acrylic resin having two or more hydroxyl groups in one molecule, and isocyanurate. Examples include skeleton-containing polyols. Two or more of these may be used in combination.

  As other polyisocyanates, compounds having an alicyclic skeleton and an isocyanate and / or isocyanurate skeleton are suitable because they are excellent in light resistance and heat-resistant coloration. Particularly, 1,3-bis (isocyanatomethyl) cyclohexane, hexa Methylene diisocyanate-modified isocyanurate skeleton-containing triisocyanate and norbornene diisocyanate are preferable, and a mixture of a plurality of types of polyisocyanates may be used.

  The mixing ratio of the polyol component and the polyisocyanate component is preferably such that the hydroxyl group of the polyol component and the isocyanate group of the polyisocyanate component are equivalent. If the ratio of the hydroxyl group and the isocyanate group deviates from the equivalent, the cured product tends to deteriorate optical properties such as heat resistance and light resistance, and mechanical properties such as hardness, breaking strength, heat resistance, and moisture resistance.

  In the curable resin composition, a hindered phenolic antioxidant may be used as an antioxidant from the viewpoint of enhancing light resistance and heat-resistant colorability. In particular [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] It is preferable to use undecane.

  The addition amount of the antioxidant is preferably 0.05 to 5% by mass, particularly 0.05 to 0.3% by mass, based on the total mass of the mixture of the polyol component and the polyisocyanate component. Is preferred. When the amount added is less than 0.05% by mass, the effect as an antioxidant tends to be reduced. On the other hand, when the amount exceeds 5% by mass, there are problems such as solubility and precipitation during curing.

  The curable resin composition may contain a polysiloxane-based, polyethylene-based, fluorine-based, fatty acid ester-based, or higher fatty acid salt-based release agent in order to increase the releasability of the molded product from the mold. Good. Fatty acid ester-based and higher fatty acid salt-based release agents are particularly preferred because they exhibit good release properties.

  The addition amount of the release agent in the curable resin composition is preferably 0.01 to 5% by mass, particularly 0.01 to 2% by mass with respect to the total mass of the mixture of the polyol component and the polyisocyanate component. Preferably there is. When the addition amount is less than 0.01% by mass, the effect as a mold release agent is not observed, while when it exceeds 5% by mass, heat-resistant coloring property and solubility are problematic.

  In order to obtain a curing rate necessary for liquid transfer molding, a curing catalyst can be added to the curable resin composition. As the curing catalyst, zirconium-based or aluminum-based organometallic catalyst, tin-based catalyst such as dibutyltin laurate, DBU phenol salt, octylate, amine, imidazole, etc. can be used. The catalyst is suitable because it is excellent in heat resistant colorability.

  The addition amount of the curing catalyst is preferably 1% by mass or less, and more preferably 0.1% by mass or less, based on the total mass of the mixture of the polyol component and the polyisocyanate component. When the addition amount is more than 1% by mass, the curing speed becomes too fast and it becomes difficult to handle the curable resin composition.

  In addition to the above components, a hindered amine light stabilizer, an ultraviolet absorber, an inorganic filler, an organic filler, a coupling agent, a polymerization inhibitor, and the like can be added to the curable resin composition. Further, from the viewpoint of moldability, a plasticizer, an antistatic agent, a flame retardant, and the like may be added. These are preferably liquid from the viewpoint of ensuring the light transmittance of the cured resin, but in the case of a solid, those having a particle size smaller than the wavelength of light to be transmitted are desirable. These are used singly or in combination of two or more.

  The curable resin composition preferably has a gelation time at 165 ° C. of 25 to 200 seconds and more preferably 25 to 150 seconds. This makes it possible to produce an LED package by liquid transfer molding under substantially the same molding conditions (molding temperature and molding time) as in conventional solid transfer molding. If the gelling time is shorter than 25 seconds, the resin solution is cured before it sufficiently flows through the flow path in the molding die, and an unfilled portion is generated in the molding die. It tends to be difficult to obtain. Moreover, there exists a tendency for sufficient hardening in a short time to become difficult that gelation time is 200 second or more. The “gelation time” is measured using a commercially available gelation tester. More specifically, 0.2 g of a liquid curable resin composition is placed on a hot plate heated to 165 ° C. and measured by a hand cure method.

  The gelation time of the curable resin composition can be controlled by adjusting the type and content ratio of the curing catalyst, the prepolymer content ratio, the polyol used as the prepolymer, the type of isocyanate, and the blending ratio.

  The curable resin composition is preferably formed by heating a cured product having a glass transition temperature of 110 ° C. or higher. When the glass transition temperature is high, defects such as peeling, cracking, and disconnection in the temperature cycle test are unlikely to occur, and an LED package having excellent temperature cycle resistance can be manufactured.

  As described above, when the curable resin composition according to the present embodiment is used as an LED sealing resin for forming an LED package sealing member, the LED package is excellent in high temperature and high humidity resistance and temperature cycle resistance. LED package can be suitably produced by liquid transfer molding.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of an LED package. An LED package 10 shown in FIG. 1 includes an insulating substrate 1, a pair of lead frames 2 (2a, 2b) assembled to the substrate 1, an adhesive member 3 provided on one lead frame 2a, and an adhesive Light emitting diode element 4 provided on member 3, wire 5 for electrically connecting light emitting diode element 4 and the other lead frame 2b, a part of a pair of lead frames 2, adhesive member 3, light emitting diode element 4 and a sealing member 6 that seals the wire 5. The LED package 10 is called a surface mount type or a chip type.

  The lead frame 2 includes one lead frame 2a and the other lead frame 2b. The lead frame 2 is a member made of a conductive material such as a metal fitted and attached to the substrate 1, and one lead frame 2a and the other lead frame 2b are separated from each other. The adhesive member 3 is a member for bonding and fixing one lead frame 2a and the light emitting diode element 4 to each other and electrically connecting them. The adhesive member 3 is formed from a silver paste, for example.

  The light emitting diode element 4 is not particularly limited as long as it is a semiconductor element that emits light when a voltage is applied in the forward direction, and may be a known light emitting diode element. The wire 5 may be a conductive wire such as a thin metal wire that can electrically connect the light emitting diode element 4 and the other lead frame 2b.

  The sealing member 6 is formed from the hardened | cured material of the above-mentioned curable resin composition. Since the sealing member 6 protects the light emitting diode element 4 from the outside air and plays a role of taking out light emitted from the light emitting diode element 4 to the outside, the sealing member 6 exhibits high translucency. In this embodiment, the sealing member 6 is formed of a flat plate-like portion 6a on the substrate side and a lens portion 6b on the opposite side of the substrate, and is emitted from the light emitting diode element 4 by the lens portion 6b having a convex lens shape. Light is concentrated.

  Since the LED package 10 of the present embodiment described above employs a cured product of the above-described curable resin composition as a sealing member that is a member that is easily affected by temperature and humidity, the LED package 10 is in a high temperature and high humidity environment. Even if it is exposed for a long time, it is sufficiently excellent in coloring resistance. In addition, liquid transfer molding can be adopted as a part of the manufacturing process, which makes it possible to shorten the molding time and increase the productivity. Furthermore, since the sealing member has good translucency in the initial stage, high luminance can be maintained for a long time. Further, by adopting liquid transfer molding, it is possible to provide a lens shape that improves the light extraction efficiency as shown in FIG.

  FIG. 2 is a schematic cross-sectional view showing another embodiment of the LED package. The surface mount type LED package 20 shown in FIG. 2 includes a light emitting diode element 24 and a light-transmitting sealing member 26 provided so as to seal the light emitting diode element 24. The light emitting diode element 24 is disposed at the bottom of the cavity portion 28 formed by the case member 27. The light emitting diode element 24 is electrically connected to one lead frame 22a via an adhesive member 23, and is electrically connected to the other lead frame 22b via a wire 25. In this LED package 20, the sealing member 26 is formed from a cured product of the above-described curable resin composition. Note that the surface of the sealing member 26 is flat, and does not have a function of concentrating light emitted from the light emitting diode elements 24.

  The pair of lead frames 22 are assembled by being fitted to the case member 27. The pair of lead frames 22, the adhesive member 23, the light emitting diode element 24, and the wire 25 may be made of the same material as the pair of lead frames 2, the adhesive member 3, the light emitting diode element 4, and the wire 5 in the above embodiment. The case member 27 has a shape that can hold the curable resin composition in the cavity portion 28, and the opening portion of the cavity portion 28 is circular.

  The LED package according to the present invention only needs to include a light emitting diode element and a sealing member that seals the light emitting diode element, and may be a shell type instead of the surface mount type as described above.

  Next, a preferred embodiment of a method for manufacturing an LED package will be described by taking the case of manufacturing the LED package 10 of FIG. 1 as an example. The manufacturing method of the LED package 10 according to the present embodiment includes a step of forming the sealing member 6 of the LED package 10 by curing and molding the curable resin composition by liquid transfer molding.

  First, a curable resin composition is prepared and filled in a pot of a molding apparatus. Separately, a structure including one substrate 1 and a plurality of assembly parts assembled to the substrate 1 is prepared. The assembly component includes a pair of lead frames 2 (2a, 2b), an adhesive member 3 provided on one of the lead frames 2a, a light emitting diode element 4 formed on the adhesive member 3, and a light emitting diode element 4 And a wire 5 for electrically connecting the other lead frame 2b. This assembly component is assembled to the substrate 1 by the pair of lead frames 2. This structure is installed at a predetermined position in a cavity formed by a molding die (hereinafter simply referred to as “mold”) included in the molding apparatus. The molding apparatus is used for liquid transfer molding, and is not particularly limited as long as the cavity formed by the mold has the shape of the target cured product.

  Next, the plunger is activated, and the curable resin composition is press-fitted from the pot into a mold cavity heated to a predetermined temperature via a flow path such as a sprue, a runner, and a gate. The mold is usually composed of a separable upper mold and lower mold, and a cavity is formed by connecting them. Thereafter, the curable resin composition filled in the cavity is cured on the structure by holding the curable resin composition in the cavity for a certain period of time. Thereby, the hardened | cured material of a curable resin composition is shape | molded by the target shape, and while sealing a some assembly component, it adheres to a structure.

  The mold temperature is preferably set to a temperature at which the flowability of the curable resin composition is high in the flow path and the curable resin composition can be cured in a short time in the cavity. Although this temperature depends on the composition of the curable resin composition, it is preferably, for example, 120 to 200 ° C. Further, the injection pressure when the curable resin composition is press-fitted into the cavity is preferably set to such a pressure that the curable resin composition can be filled in the entire cavity without any gap. Preferably there is. If the spray pressure is less than 2 MPa, an unfilled portion tends to occur in the cavity, and voids tend to occur in the sealing member 6.

  In order to make it easy to take out the cured product of the curable resin composition (sealing member 6) from the mold, a release agent may be applied to or sprayed on the inner wall surface of the mold that forms the cavity. Furthermore, in order to suppress generation | occurrence | production of the void in hardened | cured material, you may use the well-known vacuuming apparatus which can pressure-reduce the inside of a cavity. An apparatus capable of evacuation is disclosed in a patent document (Japanese Patent Laid-Open No. 2004-160882).

  Subsequently, after the structure and the cured product of the curable resin composition adhered thereto are taken out of the cavity, the substrate and the cured product are cut (diced) so as to separate the plurality of assembly parts individually. Thus, an LED package provided with the cured product of the curable resin composition described above as a sealing member for sealing the assembly component is obtained.

  According to the LED package manufacturing method of the present embodiment described above, since the liquid transfer molding method is employed, the curing time can be set short, leading to improvement in the productivity of the LED package. Moreover, the effect that it is possible to provide arbitrary shapes is acquired by using the said shaping | molding method.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. The present invention can be variously modified without departing from the spirit of the present invention.

  For example, in another embodiment of the method for manufacturing an LED package of the present invention, when forming a sealing member, a casting molding method or a potting method is adopted, although productivity is inferior to liquid transfer molding. May be. In this case, the heating temperature and heating time required for curing the curable resin composition are preferably 60 to 150 ° C. and 1 to 10 hours, although depending on the composition of the curable resin composition, 80 to 150 ° C. More preferably, it is 1 to 10 hours. Moreover, in order to reduce the internal stress in the hardened | cured material which arises with hardening, it is preferable to perform heating by raising temperature gradually or in steps.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.

Example 1
11.5 parts by mass of polycaprolactone triol having a weight average molecular weight of 300 and a hydroxyl value of 540 mgKOH / g (A1: manufactured by Daicel Chemical Industries, trade name “Placcel 303”), 7.2 mass of trimethylolpropane (A2: manufactured by Perstorp) Part, diglycerin (A3: Sakamoto Yakuhin Kogyo Co., Ltd., trade name “diglycerin S”) was added to 4.2 parts by mass, and the mixture was heated and stirred to obtain a polyol component A solution.

1.6 parts by mass of trimethylolpropane (A2), 1,4 parts by mass of 4,4′-methylenebis (cyclohexyl isocyanate) (B4: manufactured by Degussa Japan, trade name “H ₁₂ MDI”) were mixed, and 100 under a nitrogen atmosphere. The mixture was heated and stirred at ° C. for 3 hours to obtain a prepolymer (B1) having a structural unit derived from 4,4′-methylenebis (cyclohexyl isocyanate) and an isocyanate group. 17.4 parts by mass of prepolymer (B1) as a polyisocyanate component, 16.6 parts by mass of norbornene diisocyanate (B2: trade name “Cosmonate NBDI”, manufactured by Mitsui Takeda Chemical Co., Ltd.), isocyanurate which is a trimer of isophorone diisocyanate Type isocyanate 70 mass% butyl acetate solution (B3: manufactured by Degussa Japan, trade name “VESTANAT (R) T1890”) 43.1 parts by mass, as a hindered phenolic antioxidant [2- {3- (3-tert- Butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (C1: manufactured by Sumitomo Chemical Co., Ltd., trade name “Smilizer GA-80 ") After mixing 0.1 parts by mass, butyl acetate was distilled off. . There, 0.025 parts by mass of zinc stearate (D1: Sakai Chemical Industry, trade name “SZ-P”) as an internal mold release agent, organic acid ester release agent (E1: made by AXEL, trade name) "Moldwiz INT-1810") 0.03 part by mass was added, and the mixture was heated and stirred to obtain a polyisocyanate component B liquid.

  A mixed liquid obtained by mixing 22.9 parts by mass of the A liquid and 64.4 parts by mass of the B liquid was degassed under reduced pressure, and poured into a mold in which a 3 mm thick silicone spacer was sandwiched between glass plates. C. for 1 hour, 100.degree. C. for 1 hour, 120.degree. C. for 1 hour, and 150.degree. C. for 3 hours to produce a cured product.

  A case member made of polyphthalimide (external dimensions: width 3.2 mm × depth 2.6 mm × thickness 1.8 mm) having a diameter of 2.4 mm in the opening of the cavity portion was formed in the lead frame. Next, a light emitting diode element (emission wavelength: 470 nm) was mounted on the lead frame exposed at the bottom of the cavity of the case member via a silver paste. Next, the lead frame terminal on which the light emitting diode element was not mounted and the light emitting diode element were connected by wire bonding using a gold wire to obtain an assembly part.

  Next, the liquid mixture of the liquid A and liquid B was poured into the cavity portion of the assembly part and filled. Next, the filled mixture is subjected to heat treatment at 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, and 150 ° C. for 3 hours to obtain a cured product as a sealing member Got. Thus, a surface mount type LED package having the same configuration as that of FIG. 2 was produced.

(Example 2)
Add 13.9 parts by mass of polycaprolactone triol (A1) having a weight average molecular weight of 300, hydroxyl value of 540 mg KOH / g, 8.1 parts by mass of trimethylolpropane (A2), 2.1 parts by mass of diglycerin (A3), and heating. The mixture was stirred to obtain a polyol component A liquid.

  1.6 parts by mass of trimethylolpropane (A2) and 15.6 parts by mass of 4,4′-methylenebis (cyclohexyl isocyanate) (B4) were mixed, and 4,4′-methylenebis (cyclohexyl isocyanate) was obtained in the same manner as in Example 1. The prepolymer (B1) which has a structural unit derived from) and an isocyanate group was obtained. Prepolymer (B1) 17.2 parts by mass, norbornene diisocyanate (B2) 16.4 parts by mass, isocyanurate type isocyanate 70% by mass butyl acetate solution (B3) 42.4 parts by mass, isophorone diisocyanate trimer, hindered type [2- {3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro as a phenolic antioxidant After mixing 0.1 part by mass of [5,5] undecane (C1), butyl acetate was distilled off. Thereto were added 0.025 parts by mass of zinc stearate (D1) and 0.03 parts by mass of an organic acid ester release agent (E1) as internal mold release agents, and the mixture was heated and stirred to obtain a polyisocyanate component B liquid.

  A cured product and an LED package were produced in the same manner as in Example 1 by using a mixed solution obtained by mixing 24.1 parts by mass of the A solution and 63.4 parts by mass of the B solution.

(Example 3)
9.9 parts by mass of polycaprolactone triol (A1) having a weight average molecular weight of 300 and a hydroxyl value of 540 mgKOH / g, 6.5 parts by mass of trimethylolpropane (A2), 4.3 parts by mass of glycerin (A4: manufactured by Sakamoto Pharmaceutical Co., Ltd.) Part was added and heated and stirred to obtain a polyol component A solution.

  1.6 parts by mass of trimethylolpropane (A2) and 16.3 parts by mass of 4,4′-methylenebis (cyclohexylisocyanate) (B4) were mixed, and a prepolymer (B1) was obtained in the same manner as in Example 1. Prepolymer (B1) 17.9 parts by mass, norbornene diisocyanate (B2) 17.1 parts by mass, isophorone diisocyanate trimerized isocyanurate type isocyanate 70% by mass butyl acetate solution (B3) 44.3 parts by mass, hindered type [2- {3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro as a phenolic antioxidant After mixing 0.1 part by mass of [5,5] undecane (C1), butyl acetate was distilled off. Thereto were added 0.025 parts by mass of zinc stearate (D1) and 0.03 parts by mass of an organic acid ester release agent (E1) as internal mold release agents, and the mixture was heated and stirred to obtain a polyisocyanate component B liquid.

  A cured product and an LED package were produced in the same manner as in Example 1 by using a mixed solution obtained by mixing 20.7 parts by mass of the A solution and 66.2 parts by mass of the B solution.

Example 4
13.2 parts by mass of polycaprolactone triol (A1) having a weight average molecular weight of 300 and a hydroxyl value of 540 mgKOH / g, 7.8 parts by mass of trimethylolpropane (A2), 2.1 parts by mass of glycerin (A4: manufactured by Sakamoto Pharmaceutical Co., Ltd.) Part was added and heated and stirred to obtain a polyol component A solution.

  1.6 parts by mass of trimethylolpropane (A2) and 15.8 parts by mass of 4,4′-methylenebis (cyclohexyl isocyanate) (B4) were mixed, and a prepolymer (B1) was obtained in the same manner as in Example 1. Prepolymer (B1) 17.4 parts by mass, norbornene diisocyanate (B2) 16.6 parts by mass, isocyanurate type isocyanate 70% by mass butyl acetate solution (B3) 42.9 parts by mass, isophorone diisocyanate trimer, hindered type [2- {3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro as a phenolic antioxidant After mixing 0.1 part by mass of [5,5] undecane (C1), butyl acetate was distilled off. Thereto were added 0.025 parts by mass of zinc stearate (D1) and 0.03 parts by mass of an organic acid ester release agent (E1) as internal mold release agents, and the mixture was heated and stirred to obtain a polyisocyanate component B liquid.

  A cured product and an LED package were produced in the same manner as in Example 1 by using a mixed solution obtained by mixing 23.1 parts by mass of the A solution and 64.0 parts by mass of the B solution.

(Comparative Example 1)
As the polyol component, 50.2 parts by mass of polycaprolactone triol (A1) having a weight average molecular weight of 300 and a hydroxyl value of 540 mgKOH / g is used. As the isocyanate component, 49.8 parts by mass of norbornene diisocyanate (B2), hindered phenolic antioxidant [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5 A cured product and an LED package were produced in the same manner as in Example 1 using a mixture obtained by mixing 0.1 part by mass of undecane (C1).

(Comparative Example 2)
29.8 parts by mass of polycaprolactone triol (A1) having a weight average molecular weight of 300, a hydroxyl value of 540 mgKOH / g, and 1.9 parts by mass of trimethylolpropane were added and stirred to obtain a polyol component A solution.

  1.4 parts by mass of trimethylolpropane (A2) and 14.1 parts by mass of 4,4′-methylenebis (cyclohexyl isocyanate) (B4) were mixed, and a prepolymer (B1) was obtained in the same manner as in Example 1. Prepolymer (B1) 15.5 parts by mass, norbornene diisocyanate (B2) 14.7 parts by mass, isocyanurate type isocyanate 70% by mass butyl acetate solution (B3) 38.2 parts by mass, isophorone diisocyanate trimer, hindered type [2- {3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro as a phenolic antioxidant After mixing 0.1 part by mass of [5,5] undecane (C1), butyl acetate was distilled off to obtain a polyisocyanate component B liquid.

  A cured product and an LED package were produced in the same manner as in Example 1 by using a mixed solution obtained by mixing 31.7 parts by mass of the A solution and 57.0 parts by mass of the B solution.

(Comparative Example 3)
As the polyol component, 47.7 parts by mass of polycaprolactone triol (A1) having a weight average molecular weight of 300 and a hydroxyl value of 540 mgKOH / g is used. As the isocyanate component, 28.3 parts by mass of norbornene diisocyanate (B2), 4,4′-methylenebis (Cyclohexyl isocyanate) (B4) 15.4 parts by mass, and [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1, as a hindered phenolic antioxidant, 1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (C1) 0.1 part by mass was used. These were mixed and the hardened | cured material and LED package were produced like Example 1. FIG.

  Table 1 shows the compositions of Examples 1 to 4 and Comparative Examples 1 to 3. The numbers in Table 1 indicate parts by mass.

The contents of the components shown in the table are summarized below.
A1: Polycaprolactone triol having a weight average molecular weight of 300 and a hydroxyl value of 540 mgKOH / g A2: Trimethylolpropane A3: Diglycerin A4: Glycerin B1: Prepolymer obtained from trimethylolpropane and 4,4′-methylenebis (cyclohexyl isocyanate) B2: norbornene diisocyanate B3: isocyanurate type isocyanate 70% by mass butyl acetate solution which is a trimer of isophorone diisocyanate B4: 4,4′-methylenebis (cyclohexyl isocyanate)
C1: [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5 ] Undecane D1: Zinc stearate D2: Phosphate ester internal mold release agent

  For the curable resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3, the Shore A hardness and gelation time were measured by the following procedure. Moreover, the glass transition temperature was measured about the hardened | cured material obtained as mentioned above. Using the surface-mount type LED package obtained as described above, a high-temperature and high-humidity lighting test was performed to evaluate the luminance maintenance rate. Moreover, the temperature cycle test was done using the surface mount type LED package, and the external appearance after the test was evaluated. Furthermore, using the curable resin composition, liquid transfer molding was performed under conditions different from the above to produce a cured product, and the moldability was evaluated.

Shore A hardness The liquid mixture of A liquid and B liquid was heated for 5 minutes on the hot plate set to 165 degreeC, and the Shore A hardness in 165 degreeC was measured about the formed hardened | cured material using the spring type hardness meter.

Gelation time 0.2g of liquid mixture of liquid A and liquid B was placed on a hot plate heated to 165 ° C, and the time for the liquid mixture to gel using a gelation tester (SYSTEM, manufactured by SEIKO) Was measured by a hand cure method.

Glass transition temperature A test piece of 19 × 3 × 3 mm was cut out from the cured product obtained as described above, and the heating rate was 5 with a thermomechanical analyzer (product name “TMA-8141BS”, manufactured by TAS-100 Riken Denshi). Measured at ° C / min. The glass transition temperature (hereinafter referred to as “Tg”) was determined from the bent line of the thermal expansion curve.

High temperature and high humidity resistance A current of DC 20 mA was passed through the LED package to light the LED, and the luminance at that time was measured using an instantaneous multi-photometer (Otsuka Electronics Co., Ltd.). Next, the LED package was subjected to a high-temperature and high-humidity lighting test in which a current of DC 20 mA was passed in an environment of 85 ° C. and 85% RH. After the treatment for 1000 hours, the LED package was taken out and its luminance was measured. The luminance maintenance ratio, which is the ratio (L2 / L1) of the luminance (L2) after the test to the luminance (L1) before the test, was 0.8 or more, and “B” was less than 0.7.

Thermal cycle resistance The LED package was repeatedly subjected to a cycle test of -40 ° C / 30 minutes and 85 ° C / 30 minutes as one cycle, and observed for peeling, cracking, wire breakage, etc. after 500 cycles. . When none of them was observed, “A” was indicated, and when any of them was confirmed, “B” was indicated.

Liquid transfer moldability A cured product, which is a sealing member of an LED package, was prepared as follows and liquid transfer moldability was evaluated. First, the liquid mixture of the liquid A and the liquid B was filled in a pot of a molding apparatus for liquid transfer molding. Subsequently, the plunger was started and the mixed solution was press-fitted into the mold cavity heated to 165 to 175 ° C. via the flow path from the pot. The injection pressure was 4 to 15 MPa, and the press-fitting time of the mixed solution into the cavity was 20 to 50 seconds. Next, the mixed solution was held in the cavity for 180 to 300 seconds. Note that the heating temperature, injection pressure, press-fitting time, and holding time of the mold differ depending on the resin used and the mold shape, because the temperature dependency of the curing rate, the ease of entering voids, the ease of filling, etc. differ. Conditions were appropriately set according to the conditions. Thus, the hardened | cured material of the rectangular parallelepiped curable resin composition of external dimensions 5.1mmx3.9mmx4.7mm was obtained. The appearance was observed with a microscope, and “A” was evaluated when no voids and unfilled portions were observed, and “B” was evaluated when any of the voids and unfilled portions were observed.

  Table 2 shows the measurement results of each test.

  In each of Examples 1 to 4, the Shore A hardness after heating at 165 ° C. for 5 minutes was 65 or more and had high hot hardness. On the other hand, in Comparative Examples 1 to 3, the hot hardness was low. In Examples 1 to 4, LED packages excellent in high temperature and high humidity resistance and temperature cycle resistance were obtained. In Examples 1 to 4, the gelation time and glass transition temperature satisfied conditions suitable for liquid transfer molding, and an LED package was actually fabricated with good moldability by liquid transfer molding.

It is a schematic cross section which shows one Embodiment of an LED package. It is a schematic cross section which shows other embodiment of an LED package.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2, 22 ... Lead frame, 3, 23 ... Adhesive member, 4, 24 ... Light emitting diode element 5, 25 ... Wire, 6, 26 ... Sealing member, 10, 20 ... Light emitting diode package, 27 ... Case member.

Claims (9)

Contains a tri- or higher functional polycaprolactone polyol and / or a tri- or higher functional polyol having a structural unit derived therefrom, and a tri- or higher functional aliphatic polyol and / or a tri-functional or higher functional polyol derived therefrom. A polyol component to
A polyisocyanate component containing a bifunctional or trifunctional alicyclic polyisocyanate having an isocyanate group bonded to a secondary carbon atom and / or a bifunctional or trifunctional polyisocyanate having a structural unit derived therefrom; and Including
The aliphatic polyol has trimethylolpropane and a polyol having a hydroxyl value of 1300 mgKOH / g or more,
The ratio of the total amount of the trimethylolpropane and the polyol having a structural unit derived therefrom to the total amount of the trifunctional or higher functional polyol having the aliphatic polyol and the structural unit derived therefrom is 40% by mass or more,
The ratio of the total amount of the polyol having a hydroxyl value of 1300 mgKOH / g or more and the polyol having a structural unit derived therefrom to the total amount of the aliphatic polyol and the trifunctional or higher functional polyol having a structural unit derived therefrom is 10% by mass or more,
A curable resin composition that forms a cured product having a Shore A hardness of 65 or more at 165 ° C when heated at 165 ° C for 5 minutes. The polycaprolactone polyol has a weight average molecular weight of 500 or less and a hydroxyl value of 300 mgKOH / g or more, and the ratio of the total amount of the polycaprolactone polyol and the polyol having a structural unit derived therefrom to the total polyol component is 40. Mass% or more,
The aliphatic polyol has a weight average molecular weight of 350 or less and a hydroxyl value of 1000 mgKOH / g or more, and the ratio of the total amount of the aliphatic polyol and the polyol having a structural unit derived therefrom to the total polyol component is 40. Mass% or more,
The curable resin composition of Claim 1 whose ratio with respect to the whole said polyisocyanate component of the total amount of the said polyisocyanate which has the structural unit derived from the said alicyclic polyisocyanate is 40 mass% or more. The polyol having a structural unit derived from the polycaprolactone polyol is a prepolymer obtained by reacting a polyol containing the polycaprolactone polyol with a polyisocyanate having a total number of isocyanate groups smaller than the total number of hydroxyl groups of the polyol. Yes,
The polyol having a structural unit derived from the aliphatic polyol is a prepolymer obtained by reacting a polyol containing the aliphatic polyol with a polyisocyanate having a total number of isocyanate groups smaller than the total number of hydroxyl groups of the polyol. The curable resin composition according to claim 1 or 2 . The polyisocyanate having a structural unit derived from the alicyclic polyisocyanate reacts with a polyisocyanate containing the alicyclic polyisocyanate and a polyol having a total number of hydroxyl groups smaller than the total number of isocyanate groups of the polyisocyanate. The curable resin composition according to any one of claims 1 to 3 , wherein the curable resin composition is a prepolymer obtained. The curable resin composition according to any one of claims 1 to 4 , further comprising a hindered phenolic antioxidant. The curable resin composition according to any one of claims 1 to 5 , wherein the gelation time at 165 ° C is 25 to 200 seconds. The curable resin composition according to any one of claims 1 to 6 , wherein a cured product having a glass transition temperature of 110 ° C or higher is formed by heating. The curable resin composition according to any one of claims 1 to 7 is molded by liquid transfer molding method, comprising the step of forming a sealing member of the LED package, a manufacturing method of the LED package. Comprising a sealing member which can be obtained by molding the curable resin composition according to any one of claims. 1 to 7, LED package.

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