Thermosetting material, method for producing molded article, and cured product

Abstract

This thermosetting material contains components (A) to (C) and (E). (A) is a substituted or unsubstituted monofunctional or polyfunctional (meth)acrylate compound which has a group having an alicyclic hydrocarbon group with 6 or more ring-forming carbon atoms as an ester substituent group. (B) is a (meth)acrylic acid or a monofunctional (meth)acrylate compound having a polar group as an ester substituent group. (C) is a polyfunctional (meth)acrylate compound having a group other than the ester substituent group in the component (A) as an ester substituent group. (E) is nanoparticles

Description

Thermosetting material, method for manufacturing molded articles, and cured product

[0001] This invention relates to thermosetting materials, methods for manufacturing molded articles, and cured products.

[0002] Light-emitting devices (LED packages, etc.) that utilize light-emitting diodes (LEDs) or other optoelectronic semiconductors are typically manufactured by fixing the optoelectronic semiconductor onto a molded lead frame, which is formed by integrally molding a concave shape onto a lead frame using synthetic resin as a bracket material, and then sealing it with an sealing material such as epoxy resin or silicone resin. By using a reflective material (reflector) in the bracket material, the light from the optoelectronic semiconductor is reflected forward, enabling high brightness on the front.

[0003] One type of backlight for display devices is the edge type, where LED packages are placed at the edges of the display screen and surface illumination is achieved using a light guide plate. In this type, a higher frontal illumination output from the LED package is preferable, so LED packages with the aforementioned reflectors are used.

[0004] On the other hand, in recent years, a direct-lit backlight system has been adopted in which numerous LED packages are placed directly beneath the display screen (LCD panel, etc.), and each LED package lights up to illuminate a designated area. Direct-lit backlights have the advantage of being able to display images with higher brightness and contrast than edge-lit backlights.

[0005] In direct-lit backlit display devices, miniaturization of LED packages is required, and consequently, highly transparent materials are being used for the brackets. By using highly transparent bracket materials, the light from the optical semiconductor is emitted not only in the forward direction but also in a wide range of directions such as the sides, resulting in surface emission with appropriate spread, which enables more precise dimming in images.

[0006] Thermoplastic resins have been used as highly transparent bracket materials, but they have the drawback of low heat resistance. In response to this, the use of thermosetting materials containing thermosetting resins with excellent heat resistance has been considered (see, for example, Patent Document 1). However, the material in Patent Document 1 contains a white pigment and is therefore not transparent. Furthermore, when the molded product is made transparent without incorporating a white pigment, the molded product is susceptible to high temperature and high humidity environments, resulting in cloudiness and a decrease in transparency. In addition, thermosetting materials are required to have good room temperature storage properties so that the composition does not vary from one molded product to another.

[0007] Patent No. 6359889

[0008] The object of the present invention is to provide a thermosetting material that yields molded articles with high transparency and the ability to maintain transparency even under high temperature and high humidity conditions. Furthermore, it is also to provide a thermosetting material with excellent storage properties at room temperature.

[0009] As a result of diligent research, the inventors have found that a composition containing a predetermined thermosetting component and nanoparticles exhibits excellent storage properties at room temperature. Furthermore, they have found that the cured product of this composition has high heat resistance and high transparency, and can maintain its transparency even under high temperature and high humidity conditions, thus completing the present invention.

[0010] The present invention provides the following thermosetting materials, etc. 1. A thermosetting material comprising the following components (A) to (C) and (E): (A) A monofunctional or polyfunctional (meth)acrylate compound having a substituted or unsubstituted alicyclic hydrocarbon group with 6 or more ring-forming carbon atoms as an ester substituent (B) A monofunctional (meth)acrylate compound having (meth)acrylic acid or a group having a polar group as an ester substituent (C) A polyfunctional (meth)acrylate compound having a group other than the ester substituent of component (A) as an ester substituent (E) Nanoparticles 2. The thermosetting material according to 1, further comprising component (F) spherical silica. 3. The thermosetting material according to 2, wherein the content of (F) spherical silica relative to the total major components of the thermosetting material is 40 to 90% by mass. 4. The thermosetting material according to 2 or 3, wherein the average particle size of the (F) spherical silica is 5 μm or more. 5. 10. A thermosetting material according to any one of 1 to 7, wherein the content of spherical silica (F) having an average particle size of 5 μm or less is 75% by mass or less, relative to the total major components of the thermosetting material. 6. A thermosetting material according to any one of 1 to 5, further comprising component (G) a light stabilizer. 7. A thermosetting material according to 6, wherein the light stabilizer is a hindered amine-based light stabilizer. 8. A thermosetting material according to any one of 1 to 7, further comprising the following component (D): (D) a monofunctional (meth)acrylate compound having an ester substituent of component (A) or a group other than the ester substituent of component (B) as an ester substituent. 9. A thermosetting material according to any one of 1 to 8, wherein, based on 100% by mass of the total liquid components in the thermosetting material, the content of component (A) is 1.0 to 50% by mass, the content of component (B) is 1.0 to 50% by mass, and the content of component (C) is 1.0 to 80% by mass. A thermosetting material according to claim 8 or 9, wherein the content of component (D) is 30% by mass or less, based on a total of 100% by mass of liquid components. A cured product of a thermosetting material according to any one of claims 11.1 to 10. A method for manufacturing a molded article, comprising subjecting a thermosetting material according to any one of claims 1 to 10 to injection molding. 13. The method for manufacturing according to claim 12, wherein the molded article is a photoluminescent semiconductor light-emitting device.

[0011] According to the present invention, it is possible to provide a thermosetting material that yields molded articles with high transparency that can maintain transparency even under high temperature and high humidity conditions. Furthermore, it is possible to provide a thermosetting material with excellent room temperature storage properties.

[0012] This is a schematic cross-sectional view of a filling device for a molding machine that can be used in a method for manufacturing a molded article according to one embodiment of the present invention. This is a schematic cross-sectional view of a mold that can be used in a method for manufacturing a molded article according to one embodiment of the present invention. This is a diagram showing the relationship between the viscosity of a thermosetting material and time in one embodiment of a method for manufacturing a molded article according to one embodiment of the present invention. This is a schematic cross-sectional view showing one embodiment of a substrate for mounting an optical semiconductor element and an optical semiconductor light-emitting device using a thermosetting material according to one embodiment of the present invention.

[0013] The thermosetting material, the method for manufacturing the molded article, and the cured product of the present invention will be described in detail below. In this specification, "x to y" represents a numerical range of "x or more, and y or less." The upper and lower limits described for the numerical range can be combined arbitrarily. Furthermore, it is possible to combine two or more non-conflicting embodiments of the embodiments of the present invention described below, and an embodiment that combines two or more embodiments is also an embodiment of the embodiments of the present invention.

[0014] In this specification, the expression "substituted or unsubstituted ZZ group having XX to YY carbon atoms" means that "XX to YY carbon atoms" represents the number of carbon atoms when the ZZ group is unsubstituted, and does not include the number of carbon atoms of substituents when it is substituted. Here, "YY" is greater than "XX", and both "XX" and "YY" represent integers of 1 or more.

[0015] In this specification, the expression "ZZ group with substituted or unsubstituted atoms of XX to YY" means that "atom count XX to YY" represents the number of atoms when the ZZ group is unsubstituted, and does not include the number of substituent atoms when it is substituted. Here, "YY" is greater than "XX", and both "XX" and "YY" represent integers of 1 or more.

[0016] In this specification, when referring to "substituted or unsubstituted," examples of substituents (hereinafter also referred to as "any substituents") include C1-C6 alkyl groups, C1-C6 alkoxy groups, halogen atoms, hydroxyl groups, oxirane groups, methacryloyloxy groups, acryloyloxy groups, and the like. Examples of C1-C6 alkyl groups (preferably linear or branched) include methyl groups, ethyl groups, propyl groups (e.g., n-propyl group, isopropyl group), butyl groups (e.g., n-butyl group, isobutyl group, s-butyl group, t-butyl group), pentyl groups (e.g., n-pentyl), and hexyl groups. Examples of C1-C6 alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentyloxy groups, and hexyloxy groups. Examples of halogen atoms include fluorine atoms, bromine atoms, and iodine atoms.

[0017] In the phrase "substituted or unsubstituted," "unsubstituted" means that the substituent is not substituted and a hydrogen atom is bonded to it.

[0018] In this specification, acrylates and methacrylates are collectively referred to as (meth)acrylates. Acrylic acid and methacrylic acid are collectively referred to as (meth)acrylic acid. Acrylo and methacrylo are collectively referred to as (meth)acrylo. Acrylic and methacrylic are collectively referred to as (meth)acrylics. Methacryloyl groups and acryloyl groups are collectively referred to as (meth)acryloyl groups.

[0019] 1. Thermosetting Material A thermosetting material according to one aspect of the present invention comprises the following components (A) to (C) and (E): (A) A monofunctional or polyfunctional (meth)acrylate compound having a substituted or unsubstituted group having an alicyclic hydrocarbon group with 6 or more ring-forming carbon atoms as an ester substituent (B) A monofunctional (meth)acrylate compound having (meth)acrylic acid or a group having a polar group as an ester substituent (C) A polyfunctional (meth)acrylate compound having a group other than the ester substituent of component (A) as an ester substituent (E) Nanoparticles

[0020] Components (A) to (C) are thermosetting components. By incorporating nanoparticles into the specified thermosetting components, the adhesion between the resin and nanoparticles at the interface in the cured product is improved. This suppresses diffuse reflection of light caused by interfacial delamination, thereby preventing clouding under high temperature and high humidity conditions. Furthermore, since thixotropy can be imparted to the thermosetting material, solid-liquid separation during storage can be suppressed, improving storage at room temperature.

[0021] In one embodiment, the thermosetting material includes the following component (D): (D) A monofunctional (meth)acrylate compound component (D) having an ester substituent of component (A) or a group other than the ester substituent of component (B) as an ester substituent is also a thermosetting component.

[0022] In one embodiment, the thermosetting material contains spherical silica as component (F). This reduces the content of liquid components (mainly thermosetting components) in the thermosetting material, thereby suppressing shrinkage during curing. As a result, defects such as warping and cracking of molded products can be reduced. Furthermore, because the adhesion at the interface between the resin and the spherical silica is high, whitening caused by interfacial delamination can be suppressed. Therefore, the content of spherical silica relative to the entire thermosetting material can be increased. The components of the thermosetting material in this embodiment will be described below.

[0023] <Component (A)> Component (A) is a monofunctional or polyfunctional acrylate compound or a monofunctional or polyfunctional methacrylate compound having a substituted or unsubstituted group having an alicyclic hydrocarbon group with 6 or more ring-forming carbon atoms (preferably 6 to 30, more preferably 7 to 15) as an ester substituent. Since component (A) gives a polymer with a high glass transition temperature, the heat resistance and light resistance of the resulting cured product can be improved.

[0024] From the viewpoint of improving the filling properties of components (E) and (F), component (A) is 10s －１ At a shear rate of 25°C, the viscosity is preferably 1 to 300 mPa·s. More preferably, the viscosity is 2 to 200 mPa·s, and even more preferably 3 to 100 mPa·s.

[0025] The substituted or unsubstituted alicyclic hydrocarbon groups of component (A) having 6 or more ring-forming carbon atoms include substituted or unsubstituted adamantyl groups, substituted or unsubstituted norbornyl groups, substituted or unsubstituted isobornyl groups, substituted or unsubstituted tricyclodecanyl groups, substituted or unsubstituted dicyclopentanyl groups, and cyclohexyl groups, with preferred substituted or unsubstituted adamantyl groups, substituted or unsubstituted norbornyl groups, substituted or unsubstituted isobornyl groups, substituted or unsubstituted tricyclodecanyl groups, and substituted or unsubstituted dicyclopentanyl groups.

[0026] As component (A), compounds represented by the following formulas (I) to (IV) are preferred.

[0027] (In equations (I), (II), (III), and (IV), R １ Each independently represents a hydrogen atom or a methyl group. Each independently represents a single bond, a C1-C4 (preferably C1 or C2) alkylene group, or a C1-C4 (preferably C1 or C2) oxyalkylene group (preferably a single bond). Each independently represents a hydrogen atom, a C1-C4 (preferably C1 or C2) alkyl group, a halogen atom, a hydroxyl group, or an =O group. k represents an integer from 1 to 15. l represents an integer from 1 to 8. m represents an integer from 1 to 11. n represents an integer from 1 to 15. If there are two or more Us, the two or more Us may be the same or different.

[0028] Examples of alkylene groups of X having 1 to 4 carbon atoms include methylene, ethylene, trimethylene, propylene, tetramethylene, butylene, and 2-methyltrimethylene groups. Examples of oxyalkylene groups of X having 1 to 4 carbon atoms include oxymethylene, oxyethylene, oxypropylene, and oxybutylene groups.

[0029] The =O group of U is a double bond group of an oxygen atom, and in the alicyclic hydrocarbon group of the compounds represented by formulas (I) to (IV), it can be bonded to a carbon atom from which two hydrogen atoms can be removed, by removing two hydrogen atoms from the same carbon atom. Examples of C1-C4 alkyl groups of U include methyl, ethyl, propyl (e.g., n-propyl, isopropyl), and butyl (e.g., n-butyl, isobutyl). Examples of halogen atoms of U include fluorine, bromine, and iodine.

[0030] From the viewpoint of heat resistance, a single bond is preferred for X.

[0031] Component (A) is more preferably adamantyl methacrylate, adamantyl acrylate, cyclohexyl methacrylate, 1-norbornyl methacrylate, 1-isobornyl methacrylate, 1-isobornyl acrylate, 1-dicyclopentanyl methacrylate, adamantyl dimethacrylate, adamantyl diacrylate, tricyclodecanedimethanol dimethacrylate, or tricyclodecanedimethanol diacrylate, and even more preferably 1-adamantyl methacrylate, 1-norbornyl methacrylate, or 1-isobornyl methacrylate.

[0032] Based on a total of 100% by mass of liquid components in a thermosetting material, the content of component (A) may be 1.0 to 50% by mass, 1.0 to 30% by mass, 5.0 to 27% by mass, or 7.0 to 26% by mass. Note that liquid components refer to components that are liquid at room temperature (25°C). Examples include thermosetting components such as components (A) to (D) and liquid additives (polymerization initiators, etc.). In one embodiment, liquid components refer to the total of thermosetting components. Since the majority of liquid components are thermosetting components, there is no significant difference even if liquid additives are not included in the calculation. Furthermore, based on a total of 100% by mass of components (A) to (F), the content of component (A) may be 0.5 to 20% by mass, 0.5 to 15% by mass, 1.0 to 13% by mass, or 1.5 to 10% by mass. When the content of component (A) is within the above range, the resulting cured product has excellent heat resistance, light resistance, and moderate flexibility. Specifically, the higher the content of component (A), the higher the heat resistance and light resistance obtained in the cured product. Conversely, the lower the content of component (A), the less the hardness of the resulting cured product becomes excessively high, and moderate flexibility is obtained.

[0033] <Component (B)> Component (B) is a monofunctional acrylate compound having acrylic acid, methacrylic acid, or a group having a polar group (other than the ester substituent of component (A)) as an ester substituent, or a monofunctional methacrylate compound having a group having a polar group (other than the ester substituent of component (A)) as an ester substituent. Because component (B) has a polar group, it can improve the adhesion and wettability of the resulting cured product.

[0034] Examples of polar groups include hydroxyl groups, epoxy groups, glycidyl groups, tetrahydrofurfuryl groups, isocyanate groups, carboxyl groups, alkoxysilyl groups, phosphate ester groups, lactone groups, oxetane groups, tetrahydropyranyl groups, and amino groups. Among these, glycidyl groups, phosphate ester groups, carboxyl groups, glycidyl groups, and lactone groups are preferred because they provide higher adhesion and wettability.

[0035] Specific examples of the monofunctional (meth)acrylate compound having a group with a polar group as an ester substituent include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate (for example, trade name: 4-HBA, manufactured by Nippon Kasei Co., Ltd.), cyclohexanedimethanol mono (meth)acrylate (for example, trade name: CHMMA, manufactured by Nippon Kasei Co., Ltd.), glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether (for example, trade name: 4-HBAGE, manufactured by Nippon Kasei Co., Ltd.), tetrahydrofurfuryl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 2-(meth)acryloyloxyethyl phosphate, bis(2-(meth)acryloyloxyethyl) phosphate, KAYAMER PM-2 (trade name, manufactured by Nippon Kayaku Co., Ltd.), KAYAMER PM-21 (trade name, manufactured by Nippon Kayaku Co., Ltd.), γ-butyllactone (meth)acrylate, (meth)acrylic acid (3-methyl-3-oxetanyl), (meth)acrylic acid (3-ethyl-3-oxetanyl), tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and the like.

[0036] Component (B) may be used alone or in combination of two or more.

[0037] Based on 100% by mass of the total liquid components in the thermosetting material, the content of component (B) may be 1.0 to 50% by mass, 1.0 to 35% by mass, 3.0 to 30% by mass, 5.0 to 25% by mass, or 6.0 to 23% by mass. Also, based on 100% by mass of the total of components (A) to (F), the content of component (B) may be 0.5 to 10% by mass, 1.0 to 8% by mass, or 1.0 to 5.0% by mass. By having a component (B) content within the above range, a cured product with excellent adhesion and appropriate flexibility can be obtained.

[0038] <Component (C)> Component (C) is a polyfunctional (preferably containing 2 to 5 functional groups) acrylate compound or methacrylate compound having groups other than the ester substituent of component (A) as ester substituents. By including component (C), high mechanical strength and excellent heat deformation suppression can be obtained in the resulting cured product.

[0039] Examples of component (C) include tricyclodecanedimethanol di(meth)acrylate, 1,6-hexanediol diacrylate, 1,10-decanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipropylene glycol di(meth)acrylate, alkoxylated hexanediol di(meth)acrylate, alkoxylated aliphatic di(meth)acrylate, polyethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and polyester di(meth)acrylate (for example, commercially available products such as CN2203, CN2270, CN2271, CN2272, CN2273, CN2274, and CN2283 (all manufactured by Arkema)). Among these, 1,6-hexanediol diacrylate, 1,10-decanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate are preferred because they easily provide heat deformation suppression, and 1,10-decanediol di(meth)acrylate and 1,9-nonanediol di(meth)acrylate are more preferred.

[0040] From the viewpoint of heat resistance, component (C) preferably does not contain an aliphatic urethane structure (for example, -NH-C(=O)-O-).

[0041] Examples of component (α) which is a component contained in component (C) and has a melting point of -5°C or higher include 1,10-decanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and the like.

[0042] Component (C) may be used alone or in combination of two or more.

[0043] Based on 100% by mass of the total liquid components in the thermosetting material, the content of component (C) may be 80% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, and may also be 1.0% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more. Also, based on 100% by mass of the total of components (A) to (F), the content of component (C) may be 5.0 to 50% by mass, 5.0 to 30% by mass, or 7.0 to 20% by mass. When the content of component (C) is within the above range, a cured product excellent in mechanical strength, heat deformation suppression, and having appropriate flexibility can be obtained. Also, when the content of component (C) is within the above range, the curing rate of the thermosetting material can be adjusted to an appropriate range, and the curing reaction can proceed smoothly.

[0044] <Component (D)> Component (D) is a monofunctional acrylate compound or a monofunctional methacrylate compound having a group other than the ester substituent of component (A) or the ester substituent of component (B) as an ester substituent. By containing component (D), the viscosity of the thermosetting material can be adjusted, and the hardness of the obtained cured product can be adjusted and burrs can be suppressed.

[0045] Examples of component (D) include ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl methacrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, methyl (meth)acrylate, butoxyethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, butoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, urethane (meth)acrylate, etc. Among these, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl methacrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate are preferred in terms of ease of viscosity adjustment, and 2-ethylhexyl methacrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate are more preferred.

[0046] Component (D) is preferably free from an aliphatic urethane structure (e.g., -NH-C(=O)-O-) from the viewpoint of suppressing discoloration to yellow or the like during thermal curing.

[0047] Examples of component (α) that are included in component (D) and have a melting point of -5°C or higher include stearyl methacrylate and lauryl acrylate.

[0048] Component (D) may be used alone or in combination of two or more types.

[0049] Based on 100% by mass of the total liquid components in the thermosetting material, the content of component (D) may be 30% by mass or less, 10% by mass or less, 7.0% by mass or less, 5.0% by mass or less, or 0% by mass or more, 1.0% by mass or more, 2.0% by mass or more, or 4.0% by mass or more. Furthermore, based on 100% by mass of the total of components (A) to (F), the content of component (D) may be 0 to 20% by mass, 0 to 15% by mass, 1.0 to 10% by mass, or 1.0 to 5% by mass. By having a component (D) content within the above range, a cured product with excellent toughness and adhesion, and appropriate flexibility can be obtained.

[0050] <Component (E)> Component (E) is nanoparticles. By including component (E), the nanoparticles aggregate in a static state, forming a cross-linked structure that makes the material less fluid, thus significantly increasing the viscosity of the material. Therefore, even if the amount of liquid component is increased, solid-liquid separation does not occur in a static state, and the ability to store at room temperature can be maintained. Examples of nanoparticle materials include silver, gold, silicon, silicon carbide, silica, aluminum oxide, copper oxide, iron oxide, cobalt oxide, titanium oxide, titanium nitride, titanium oxynitride, titanium carbide, zinc oxide, zirconium oxide, cerium oxide, ITO (indium tin oxide), ATO (antimony trioxide), hydroxyapatite, graphene, graphene oxide, single-walled carbon nanotubes, multi-walled carbon nanotubes, fullerenes, diamond, mesoporous carbon, etc. Nanoparticles can be manufactured using known technologies such as nanoparticle pulverizers and high-temperature hydrolysis. Commercially available nanoparticles can also be used. The diameter (average primary particle size) of the nanoparticles is, for example, 1 nm or more and 100 nm or less.

[0051] In one embodiment, the average particle size (D50) of component (E) is, for example, 1 to 1000 nm, from the viewpoint of maintaining viscosity in a static state for storage at room temperature. The average particle size (D50) is preferably 2 to 500 nm, more preferably 3 to 300 nm, and particularly preferably 5 to 100 nm.

[0052] The average particle size (D50) of component (E) is measured using a laser diffraction particle size distribution analyzer. The average particle size (D50) refers to the median diameter of the cumulative distribution, which is the diameter at which the larger and smaller portions are equal when the distribution is divided into two parts.

[0053] Component (E) is preferably surface-treated spherical silica from the viewpoint of improving wettability and cured product strength. More preferably, it is spherical silica surface-treated with acrylic silane or methacrylic silane. The acrylic silane or methacrylic silane surface treatment can be performed using a silane coupling agent. Examples of silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. The time for the acrylic silane or methacrylic silane surface treatment is, for example, 30 to 120 minutes.

[0054] In one embodiment, the nanoparticles are nanosilica. Examples of nanosilica include fumed silica (AEROSIL®, Aerosil Japan Co., Ltd.), Rheoroseal (registered trademark, Tokuyama Corporation), HDK (registered trademark, Asahi Kasei Wacker Silicone Co., Ltd.), etc.

[0055] The content of component (E), based on 100% by mass of the total main components (components (A) to (F)) of the thermosetting material, may be 0.1 to 30% by mass, 0.5 to 25% by mass, or 1.0 to 20% by mass. By having the content of component (E) within the above range, the fluidity and storage properties at room temperature of the thermosetting material can be improved.

[0056] <Component (F)> Component (F) is spherical silica (SiO ２ The inclusion of component (F) reduces the liquid component content in the thermosetting material, thereby suppressing shrinkage during curing. As a result, defects such as warping and cracking of molded products can be reduced. Furthermore, the fluidity of the thermosetting material is maintained, improving the filling properties during molding.

[0057] The average particle size (D50) of component (F) is, for example, 1 to 100 μm, preferably 3 to 70 μm, more preferably 5 to 50 μm, and particularly preferably 10 to 20 μm, from the viewpoint of improving filling performance, suppressing blockage of the molding channel, and ensuring the flexibility of the cured product. In one embodiment, the average particle size (D50) of component (F) is 5 μm or more. Furthermore, the content of component (F) with an average particle size (D50) of 5 μm or less relative to the total thermosetting material is 75% by mass or less. This further improves the transparency of the cured product.

[0058] The average particle size (D50) of component (F) is measured using a laser diffraction particle size distribution analyzer. The average particle size (D50) refers to the median diameter of the cumulative distribution, which is the diameter at which the larger and smaller portions are equal when the distribution is divided into two parts.

[0059] Component (F) is preferably surface-treated spherical silica, and more preferably surface-treated spherical silica with acrylic silane or methacrylic silane, from the viewpoint of improving wettability and cured product strength. The acrylic silane or methacrylic silane surface treatment can be performed using a silane coupling agent. Examples of silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. The duration of the acrylic silane or methacrylic silane surface treatment is, for example, 30 to 120 minutes.

[0060] Examples of component (F) include CRS1085-SF630 (manufactured by Ryumori Co., Ltd.), CRS1035-LER4: spherical silica with an average particle size (D50) of 2 μm (manufactured by Ryumori Co., Ltd.), S430-5PHM (manufactured by Nippon Steel Chemical & Material Co., Ltd.), SP40HM (manufactured by Nippon Steel Chemical & Material Co., Ltd.), FB-304HM (manufactured by Denka Co., Ltd.), etc.

[0061] Component (F) may be used alone or in combination of two or more types.

[0062] The content of component (F) when the total mass of all major components (components (A) to (F)) of the thermosetting material is based on 100% by mass may be 40 to 90% by mass, 55 to 85% by mass, or 60 to 85% by mass.

[0063] By keeping the content of component (F) within the above range, the content of liquid components (mainly thermosetting components) in the thermosetting material can be reduced, thereby suppressing shrinkage during curing. As a result, defects such as warping and cracking of molded products can be reduced. When two or more types of component (F) are combined, the content of component (B) is the sum of the two or more types.

[0064] (Additives) In one embodiment, the thermosetting material contains a light stabilizer as component (G). This results in a cured product with excellent light resistance. <Component (G)> Any light stabilizer can be used, such as an ultraviolet absorber or a hindered amine light stabilizer. A hindered amine light stabilizer is preferred. Specific examples of hindered amine-based light stabilizers include ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-68, LA-77, LA-81, LA-82, LA-87, LA-94 (all manufactured by ADEKA Corporation), Tinuvin 123, 144, 440, 662, 765, 770DF, Tinuvin XT 850 FF, Tinuvin XT 855 FF, Chimassorb 2020, 119, 944 (all manufactured by BASF), Hostavin N30 (manufactured by Hoechst), JF-95 (manufactured by Johoku Chemical Industry Co., Ltd.), and Cyasorb. Examples include UV-3346, UV-3526 (manufactured by Cytec), Uval 299 (manufactured by GLC), and Sanduvor PR-31 (manufactured by Clariant) (all are trade names). Among these, LA-72, LA-81, JF-95, and Tinuvin770DF are particularly preferred.

[0065] The light stabilizer may be used alone or in combination of two or more types. When a light stabilizer is included, the amount of the light stabilizer is preferably 0.001 to 20 parts by mass, relative to 100 parts by mass of the total liquid components in the thermosetting material, from the viewpoint of not hindering the effects of the present invention. More preferably, it is 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass.

[0066] When using the NOR type, which has the lowest basicity among the hindered amine light stabilizers, it can be combined with any antioxidant. Among these, phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred. ３ When using the NH type, which has the highest basicity, it is better to combine it with phenolic antioxidants or phosphorus-based antioxidants.

[0067] The thermosetting material of one embodiment may further contain additives, to the extent that they do not impair the effects of the present invention. Examples of additives include polymerization initiators, antioxidants, ultraviolet absorbers, plasticizers, inorganic fillers, colorants, antistatic agents, lubricants, mold release agents, flame retardants, leveling agents, and defoaming agents. Known additives can be used.

[0068] A polymerization initiator may be included to promote the polymerization reaction. The polymerization initiator is not particularly limited, but examples include radical polymerization initiators. Examples of radical polymerization initiators are not particularly limited, but include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, alkyl peresters (peroxyesters), peroxycarbonates, etc. Examples of commercially available products include Pertible E and Perhexa HC.

[0069] The polymerization initiator may be used alone or in combination of two or more. When a polymerization initiator is included, the content of the radical polymerization initiator is preferably 0.001 to 20 parts by mass, based on 100 parts by mass of the total thermosetting material.

[0070] Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, vitamin-based antioxidants, lactone-based antioxidants, and amine-based antioxidants.

[0071] Examples of phenolic antioxidants include tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, β-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, and tris[(3,5-di-t- Examples include butyl-4-hydroxyphenyl)propionyloxyethyl isocyanurate, 2,6-di-t-butyl-4-methylphenol, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, and for example, IRGANOX Commercially available products such as 1010, IRGANOX 1076, IRGANOX 1330, IRGANOX 3114, IRGANOX 3125, IRGANOX 3790 (all manufactured by BASF), CYANOX 1790 (manufactured by Cyanamide Corporation), SUMILIZER BHT, SUMILIZER GA-80 (both manufactured by Sumitomo Chemical Co., Ltd.), and ADEKA stab AO-80 (manufactured by ADEKA Corporation) can be used (all are brand names).

[0072] Examples of phosphorus-based antioxidants include tris(2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]-N,N-bis[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]-ethyl]ethanamine, cyclic neopentanetetraylbis(2,6-di-t-butyl-4-methylphenyl) phosphite, distearyl pentaerythritol diphosphite, etc., for example, IRGAFOS 168, IRGAFOS 12, IRGAFOS 38 (all manufactured by BASF), ADK STAB2112, ADK Commercially available products such as STAB 329K, ADK STAB PEP36, ADK STAB PEP-8, ADEKA STAB 2112 (all manufactured by ADEKA Corporation), Sandstab P-EPQ (manufactured by Clariant), Weston 618, Weston 619G, and Weston 624 (all manufactured by GE) can be used (all are brand names).

[0073] Examples of sulfur-based antioxidants include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, lauryl stearyl thiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), and pentaerythritol tetrakis(3-lauryl thiopropionate). Commercially available products such as DSTP "Yoshitomi", DLTP "Yoshitomi", DLTOIB, DMTP "Yoshitomi" (all manufactured by API Corporation), Seenox 412S (manufactured by Cipro Chemical Co., Ltd.), Cyanox 1212 (manufactured by Cyanamide Corporation), and SUMILIZER TP-D (manufactured by Sumitomo Chemical Co., Ltd.) can be used (all are brand names).

[0074] Examples of vitamin-based antioxidants include tocopherol and 2,5,7,8-tetramethyl-2(4',8',12'-trimethyltridecyl)coumarone-6-ol, and commercially available products such as IRGANOX E201 (manufactured by BASF) can be used. As for lactone-based antioxidants, those described in Japanese Patent Publication No. 7-233160 and Japanese Patent Publication No. 7-247278 can be used. In addition, HP-136 (trade name, manufactured by BASF, compound name: 5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one) can also be used.

[0075] Examples of commercially available amine-based antioxidants include IRGASTAB FS 042 (manufactured by BASF) and GENOX EP (manufactured by Crompton, compound name: dialkyl-N-methylamine oxide) (both are trade names).

[0076] The antioxidant may be used alone or in combination of two or more. When an antioxidant is included, the amount of the antioxidant is preferably 0.001 to 20 parts by mass, per 100 parts by mass of the total liquid components in the thermosetting material, from the viewpoint of not hindering the effects of the present invention. More preferably, it is 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass.

[0077] In one embodiment, the thermosetting material essentially consists of components (A) to (F) and optionally additives such as component (G), and may contain other unavoidable impurities as long as they do not impair the effects of the present invention. In one embodiment, for example, 85% or more by mass, 95% or more by mass, or 99% or more by mass or 100% by mass of the thermosetting material may consist of components (A) to (F), or components (A) to (F) and optionally additives.

[0078] The thermosetting material according to this embodiment can be prepared by mixing the above components in a predetermined ratio. The mixing method is not particularly limited, and any known means such as a stirrer (mixer) can be used. Furthermore, the mixing can be done at room temperature, under cooling, or under heating, and under atmospheric pressure, reduced pressure, or increased pressure.

[0079] According to one embodiment, the thermosetting material is heated to 25°C for 10 seconds. －１ The viscosity at the shear rate is 1 Pa·s to 50 Pa·s, more preferably 2 Pa·s to 30 Pa·s. The viscosity of the thermosetting material being within this range provides excellent fluidity and high filling properties, as well as excellent flexibility in the resulting cured product. Note: 10s at 25°C. －１ The viscosity at the shear rate is determined by the method described in the examples.

[0080] According to the thermosetting material of this embodiment, warping is suppressed in the cured product of the thermosetting material (for example, the bracket material of an LED package) after it has been thermoset in a state where it has been integrally molded with other materials such as metal materials. As a result, the rate of defective products in molded products having the cured product (for example, an integrally molded product of the bracket material and lead frame of an LED package) can be reduced, and high production stability can be achieved.

[0081] Furthermore, the thermosetting material of this embodiment maintains a solidified state at cooling temperatures achievable with general cooling equipment, thus exhibiting excellent storage stability. Moreover, the thermosetting material of this embodiment is suitable, for example, as a bracket material for optical semiconductor light-emitting devices, as the resulting cured product has excellent flexibility, suppressing the occurrence of cracks and chips due to slight impacts, thereby reducing the rate of defective products in molded items. Additionally, the resulting cured product of this embodiment possesses excellent flexibility, heat resistance, and light resistance, suppressing the occurrence of defects such as discoloration after prolonged exposure to light and heat, such as when used for extended periods as a bracket material for optical semiconductors. Furthermore, the resulting cured product of this embodiment exhibits excellent flexibility and suppresses warping, resulting in a cured product that combines flexibility with an excellent appearance.

[0082] 2. Method for Manufacturing Molded Articles A method for manufacturing molded articles according to one aspect of the present invention includes subjecting the above-mentioned thermosetting material to injection molding. For example, it includes a step of supplying the thermosetting material into a plunger (supply step), a step of filling the supplied thermosetting material into the molded part of a mold having a molded part (cavity) using the plunger (filling step), a step of thermosetting the filled thermosetting material within the molded part (curing step), and a step of extruding the thermoset resin that has been thermoset (release step).

[0083] In the method of one embodiment, transfer molding such as LTM (Liquid Transfer Molding), compression molding, or injection molding such as LIM (Liquid Injection Molding) is preferred from the viewpoint of preventing only the resin component from being filled. Prepolymerization may also be performed.

[0084] By using the thermosetting material described above, even when filling a mold under pressure, or when excessive holding pressure is applied after filling, the thermosetting material can fill gaps as small as 1 μm.

[0085] In transfer molding, a transfer molding machine (e.g., a liquid transfer molding machine G-Line) can be used to mold the product for a period of 30 to 500 seconds, preferably with a clamping force of 5 to 20 kN, a molding temperature of 100 to 190°C, and a molding time of 30 to 180 seconds. Post-curing may be performed for 0.5 to 24 hours at, for example, 150 to 185°C.

[0086] In compression molding, a compression molding machine can be used to mold the product for, for example, 30 to 600 seconds at a molding temperature of 100 to 190°C, preferably 30 to 300 seconds at a molding temperature of 110 to 170°C. Post-curing may be carried out for, for example, 0.5 to 24 hours at 150 to 185°C.

[0087] In liquid injection molding, for example, using a liquid thermosetting resin injection molding machine LA-40S, molding can be performed, for example, with a clamping force of 10kN to 40kN, a molding temperature of 100 to 190°C, and a molding time of 30 to 500 seconds, preferably with a molding temperature of 100 to 180°C and a molding time of 20 to 180 seconds.

[0088] The molding machine described above preferably includes a plunger and a mold having a molded product section. The molding machine described above preferably further includes a shut-off nozzle.

[0089] Figure 1 shows an embodiment of a filling device for a molding machine capable of carrying out an injection molding method according to one embodiment of the present invention. The molding machine in Figure 1 is an injection molding machine having a plunger mechanism for extruding the thermosetting material of this embodiment into a mold, and comprises a filling device 10 having a plunger 11 as shown in Figure 1, and a mold 20 having a cavity 21 as shown in Figure 2(A). Although not shown, it comprises a degassing device as a degassing means connected to a pore for degassing the cavity 21 in the mold 20, a heating device as a heating means connected to the mold 20, and a cooling device. The molding material is the thermosetting material of this embodiment.

[0090] As the filling device 10, a known filling device having a plunger can be used. Normally, as shown in Figure 1, a filling device 10 having a plunger 11 is equipped with a feed section and a check valve, and by moving the check valve 12 (the check valve may be screw-shaped) back and forth, the material introduced from an inlet (not shown) is fed, stirred, and mixed. However, in this embodiment, since a thermosetting material, which is a uniform liquid, is introduced, stirring and mixing are not necessary.

[0091] In the step of filling the cavity with a plunger, it is preferable to fill the cavity in the mold with thermosetting material via a flow path whose temperature is controlled to 50°C or lower. When carrying out the molding method of one embodiment of the present invention using the apparatus shown in Figure 2, the flow path corresponds to the flow path of the thermosetting material in the filling apparatus 10 (not shown) and the introduction path in the mold 20.

[0092] In a method according to one embodiment of the present invention, preferably in the step of filling a cavity in a mold with a thermosetting material filled in a plunger, the flow path between the plunger and the cavity is provided with a gate system that blocks the flow of the curing liquid and the exchange of heat. The molding method according to one embodiment of the present invention will be described below with reference to Figure 2. When carrying out the method according to one embodiment of the present invention using the apparatus shown in Figure 2, for example, the needle 223 and the opening 222 correspond to the gate system. As described above, when the needle 223 moves toward the movable mold 23 and closes the opening 222, the introduction passage 221 is divided before the heating section 22A, the thermosetting material introduced into the introduction passage 221 remains in the cooling section 22B, and the flow of the thermosetting material and the exchange of heat can be blocked. Examples of systems that can block the flow of the thermosetting material and the exchange of heat include a valve gate system and a shut-off nozzle system. The heating device is a device that heats the heating section 22A and the movable mold 23. These heating methods allow the temperature inside the cavity (also called the "cavity temperature") to be set to a predetermined temperature. In the method of one embodiment of the present invention, the temperature of the mold 23 constituting the cavity is preferably set to 100°C or higher and 180°C or lower. The cooling device is a device for cooling the flow path of the thermosetting material. Specifically, it is preferable to cool the cooling section 22B of the filling device 10 and the mold 20 to 10°C or higher and 50°C or lower. In the case of injection molding, the needle (not shown) in Figure 1 corresponds to the needle 223 in Figure 2, and the flow path (not shown) in Figure 1 corresponds to the introduction path 221 in Figure 2.

[0093] Figure 1 shows the supply process. In the case of transfer molding or compression molding, the material can be measured by inserting an appropriate amount into the plunger 11 using a supply device (not shown), such as a syringe. In the case of injection molding, the thermosetting material is injected into the filling device 10 shown in Figure 1 through an inlet (not shown). The injected thermosetting material is pushed out by the check valve 12, and then a predetermined amount is measured by the plunger 11. After measuring is complete or before injection, the check valve 12 moves forward and functions as a check valve when the plunger 11 operates. During this time, the flow path is cooled by the cooling device, so the thermosetting material flows smoothly without hardening.

[0094] The filling process is shown, for example, in Figure 2(B). When injecting the thermosetting material into the cavity, it is preferable to depressurize the cavity by using a vent to release air from inside the cavity or by using a vacuum device such as the vacuum tube 240 in Figure 2, which is connected to a vacuum device with pores that allow for depressurization of the cavity. The reason is that in the process of injecting the thermosetting material into the cavity and completely filling it, the vent releases air from inside the cavity, and depressurizing the cavity ensures that it is completely filled by eliminating air. If this mechanism is not available, it is preferable to have a mechanism that allows air to escape from inside the cavity when the material is filled (for example, a vent mechanism). To mold the thermosetting material, first, the movable mold 23 is brought close to the fixed mold 22 and clamped (Figure 2(A)). The movement of the movable mold 23 is temporarily stopped when the elastic member 238 of the movable mold 23 comes into contact with the elastic member 224 of the fixed mold 22.

[0095] Filling the cavity with thermosetting material is preferably done by opening the gate of the gate system (moving the needle 223 towards the fixed mold 22) and filling the cavity 21 in the mold with thermosetting material. The heating sections 22A provided in the movable mold 23 and the fixed mold 22 are kept constantly heated and set so that the cavity temperature is, for example, 60°C or higher, preferably 100°C to 180°C, and particularly preferably 110°C to 170°C. When using an injection molding machine, when injecting from the injection section into the cavity begins, the nozzle of the shut-off nozzle (or valve gate in some cases) is opened, the plunger of the injection section is moved, and the thermosetting component is injected into the cavity. When using a transfer molding machine, since the entire material from the plunger to the cavity is cured, it is sufficient that the material can flow into the cavity, and it is not necessary to block the transfer of heat.

[0096] The curing process is shown, for example, in Figure 2(C). Once the filling of the cavity 21 with the thermosetting material is complete, the curing of the thermosetting material begins simultaneously. However, in order to improve the transferability of the molded product, it is preferable to cure it by applying a predetermined pressure. That is, it is preferable to pressurize the plunger 11 to 1.0 MPa or more and 30 MPa or less. This pressure applied to the thermosetting material to improve transferability is called holding pressure. In the curing process, it is preferable to perform holding pressure (increasing the pressure applied to the thermosetting material) after the start of thermosetting and before the completion of curing, and after holding pressure, the gate of the gate system is closed and thermosetting is performed. Specifically, the gate is closed by advancing the needle 223 to close the opening 222. During the molding process, the cooling device is activated to cool the entire flow path of the thermosetting material, that is, the cooling section 22B provided in the filling device 10 of the molding machine and the fixed mold 22 of the mold 20. At this time, it is preferable to maintain the entire flow path temperature between 10°C and 50°C, and particularly preferably set to 30°C or less.

[0097] The holding pressure in the plunger 11 and the timing of the start of holding pressure will be explained below. Figure 3 shows the relationship between the viscosity of the thermosetting material and time in this embodiment. In Figure 3, the period P1 from when the material is injected into the cavity until filling is completed corresponds to the induction period until heat is applied to the material and hardening begins. The hardening process is divided into two stages: the initial hardening period P2, from when heat is applied and the material begins to harden until hardening is complete, and the late hardening period P3, when hardening is complete. The viscosity of the thermosetting material remains low and unchanged during the induction period P1, shows a significant viscosity change from low to high during the initial hardening period P2, and slowly increases while remaining at a high viscosity during the late hardening period P3.

[0098] In the initial curing stage P2, the thermosetting material shrinks not only due to a viscosity change as it transforms from liquid to solid, but also due to a volume change. Therefore, in actual molding, if pressure is not applied to the thermosetting material, the molded product will have poor transferability. To improve transferability, it is preferable to apply pressure to the thermosetting material (holding pressure) to make the thermosetting material adhere tightly to the mold 20 and to replenish the thermosetting material from the gate area. However, in the thermosetting material of this embodiment, if pressure is applied in a low viscosity state, there is a risk of defects such as material leaking out and hardening (burring) from the gap between the fixed mold 22 and the movable mold 23, or malfunction of the ejector pins due to the thermosetting material penetrating into gaps around the ejector pins. On the other hand, even if pressure is applied when the viscosity is high in the initial curing stage P2, or in the later curing stage P3, the high viscosity of the thermosetting material prevents compressive deformation, and therefore the transferability cannot be improved. Therefore, in order to obtain a molded product with high transferability, it is preferable to align the timing of the start of holding pressure (holding pressure start time T) with the timing of the transition from the induction phase P1 to the initial curing phase P2 of the curing process.

[0099] Here, if the viscosity of the thermosetting material in the cavity 21 can be detected, the holding pressure start time T can be determined. In this embodiment, the thermosetting material thickens and simultaneously begins to shrink during the initial curing stage P2, so it is preferable to detect the time when shrinkage begins. This allows for an appropriate determination of the holding pressure start time T.

[0100] During the curing process, holding pressure under the above-described conditions prevents shrinkage and distortion of the molded product and improves transferability. After holding pressure for a certain period of time, as shown in Figure 2(C), the needle 223 is advanced to close the opening 222, and the thermosetting material is heated for a certain period of time to completely cure it, ensuring that no uncured areas remain. At this point, the plunger 11 is advanced to fill the cavity 21 of the mold 20 with the thermosetting material, and the time required for filling t １Let's assume that. When the filling is completed, the plunger 11 stops. Also, when the curing of the thermosetting material starts, at the same time, shrinkage of the thermosetting material occurs, so the plunger 11 that had stopped after the filling process starts to advance again. The time t required from the completion of the filling process until the plunger 11 starts to advance again due to shrinkage ２ Let's assume that. Further, the time required to heat further to completely cure the thermosetting material is t ３ In the case of １ +t ２ +t ３ (The total time required for the filling process and the thermosetting process) is preferably 0.2 minutes to 3 minutes. More preferably, it is 0.2 minutes to 2 minutes. If it is less than 0.2 minutes, there is a risk of uncured occurrence, and if it is more than 3 minutes, it is not preferable from the viewpoint of mass productivity.

[0101] The mold release process is shown, for example, in Fig. 2(D). By separating the movable mold 23 from the fixed mold 22, the cured product in the cavity can be taken out. When the mold release property is poor, an ejector mechanism may be provided in the mold as appropriate.

[0102] 3. Cured Product The cured product according to one aspect of the present invention can be produced using the above-described thermosetting material. The cured product of one embodiment is preferably a molded product.

[0103] The cured product of one embodiment can be suitably used, for example, as a bracket material for an optical semiconductor light-emitting device. The bracket material of this embodiment has a high total light transmittance even after long-term use, excellent heat resistance and weather resistance, and excellent adhesion to peripheral members.

[0104] The above-described bracket material has a high total light transmittance and little clouding or yellowing even after long-term use. The total light transmittance of the bracket material is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more as an initial value.

[0105] The above-described optical semiconductor light-emitting device includes the bracket material described above. Other components of the optical semiconductor light-emitting device can be known. The substrate for mounting the optical semiconductor element and the optical semiconductor light-emitting device will be further described with reference to the drawings. Figure 4 is a schematic cross-sectional view showing one embodiment of the substrate for mounting the optical semiconductor element and the optical semiconductor light-emitting device. Figure 4(a) shows the lead frame 510.

[0106] Figure 4(b) shows a substrate 520 for mounting an optical semiconductor element, in which a cured material is formed as a bracket material 521 on the lead frame 510 of Figure 4(a). The substrate 520 for mounting an optical semiconductor element has a bottom surface made up of the lead frame 510 and the bracket material 521, and a recess made up of the inner circumferential surface made up of the bracket material 521. The cured material constituting the bracket material 521 is obtained by curing the thermosetting material of this embodiment.

[0107] Figure 4(c) shows an optical semiconductor light-emitting device 530 in which an optical semiconductor element 531 is mounted on the lead frame of the optical semiconductor element mounting substrate shown in Figure 4(b), the optical semiconductor element 531 and the other lead frame on which the optical semiconductor element 531 is not mounted are bonded with a wire 532, and the recess is sealed with a transparent resin (sealing resin) 533. The sealing resin may contain a phosphor 534 for converting light emission, such as blue, to white.

[0108] The dimensions and shapes of each part of the substrate for mounting the optical semiconductor element are not particularly limited and can be set as appropriate. Furthermore, the sealing resin (sealing material) can be made from, for example, epoxy resin, silicone resin, acrylate resin, etc.

[0109] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0110] Examples 1-14 and Comparative Examples 1-3 [Preparation of Thermosetting Materials] Components (A) to (D) shown in Tables 1-3 were weighed, mixed, and stirred. Next, components (E) and (F) were weighed and added in that order, and finally stirred to prepare a thermosetting material. A stirring device capable of stirring by rotation and revolution was used. The rotation speed was set to 1000 rpm for rotation and 2000 rpm for revolution. The rotation time was 1 minute.

[0111] The following items were evaluated for the thermosetting materials. The results are shown in Tables 1 to 3. (1) Viscosity of thermosetting materials The melt viscosity of each example of thermosetting material was measured using a viscoelasticity measuring device under the following conditions. Device name: Anton Paar Physica MCR301 Measurement method: Plate-to-plate Plate diameter: 25 mmφ Temperature: 25°C Plate, plate spacing: 0.6 mm Shear rate: 0.5 to 200 s －１ Measurement conditions: 10s －１ After applying shear for 15 minutes, the material was left to stand for 1 hour, and then measured at the above shear rate. 10s in this shear rate range －１ The shear viscosity was defined as viscosity.

[0112] (2) Storage at room temperature for thermosetting materials: Each example of thermosetting material was left at 25°C for two days. After storage, if no solid-liquid separation occurred, it was evaluated as "○", and if it occurred, it was evaluated as "×".

[0113] [Molded product] (A) Molded product 1 The above-mentioned thermosetting material was subjected to LIM molding under the following conditions to obtain molded product (cured product) 1. The mold was 10 mm wide, 50 mm long, and 1 mm thick, and the mold used had a vent section at the flow end with a width of 5 mm, a length of 10 mm, and a thickness of 0.03 mm.

[0114] LIM molding was performed under the following conditions: Molding machine: Liquid thermosetting resin injection molding machine LA-40S (manufactured by Sodick Co., Ltd.) Measuring by the plunger of the molding machine: 1 cm ３ Low-temperature section flow path temperature: 15°C Flow path and heat shielding method: Shut-off nozzle used High-temperature section flow path temperature and cavity temperature: 145°C Filling time: 5 seconds Pressure during filling: 10 MPa or less (filling time takes priority) Holding pressure time: 15 seconds Pressure during holding pressure: 15 MPa Curing time: 90 seconds

[0115] (Evaluation of Filling Properties) In the filling of the thermosetting material for the manufacture of molded product 1 described above, the filling properties were visually confirmed. ○ was used when no voids occurred and no unfilled areas occurred. △ was used when voids or unfilled areas occurred. × was used when voids occurred and unfilled areas occurred.

[0116] (B) Molded product 2 A thermosetting material was poured into a mold measuring 30 mm in width x 30 mm in length x 0.3 mm in thickness, and cured in an oven set to 150°C under a nitrogen atmosphere for 1 hour to obtain molded product 2. (C) Molded product 3 A thermosetting material was poured into a mold measuring 10 mm in width x 30 mm in length x 0.4 mm in thickness, and cured in an oven set to 150°C under a nitrogen atmosphere for 1 hour to obtain molded product 3.

[0117] The following items were evaluated for the molded product. The results are shown in Tables 1 to 3. (1) Presence or absence of burrs on the molded product The mold for molded product 1 was set to a predetermined temperature, and during the filling process between 10 and 15 seconds, if burrs were found visually in the molded product that extended beyond the end of the vent section or from parts other than the vent section, it was evaluated as "×", if burrs were found in either one of the parts, it was evaluated as "△", and if neither was found, it was evaluated as "○".

[0118] (2) The 85°C 85% RH durable molded product 1 was left for 20 hours under conditions of 85°C and 85% RH using a constant temperature and humidity chamber (manufactured by ESPEC Corporation, product name: PR-2J). After that, the cloudiness of molded product 1 was visually observed and evaluated according to the following criteria. ○: No change ×: Cloudiness present in the molded product

[0119] (3) Total light transmittance The total light transmittance of molded product 2 was measured using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: NDH2000).

[0120] (4) After measuring the initial total light transmittance of the heat-resistant molded product 2, it was heated in an oven at 180°C for 100 hours. The total light transmittance of the molded product 2 after heating was measured, and if the difference between the initial and post-heating total light transmittances was less than 10%, it was marked as "○", and if it was 10% or more, it was marked as "×".

[0121] (5) The light-resistant molded product 3 was fixed directly above the LED (UV-A) chip and lit at an output of 0.3W under conditions of 85°C and 85%RH using a constant temperature and humidity chamber (manufactured by ESPEC Corporation, product name: PR-2J). If the time until the molded product became cloudy was 50 hours or more, it was marked as "○", and if it was less than 50 hours, it was marked as "×".

[0122]

[0123]

[0124]

[0125] The components listed in Tables 1-3 are as follows. Of the components of the thermosetting material, components (A) to (D) and the polymerization initiator (perhexa HC) are liquid components. Component (A) Adamantyl methacrylate (AM, manufactured by Osaka Organic Chemical Industry Co., Ltd., viscosity at 25°C: 5 mPa·s, melting point (Tm) < -15°C) 1-Isobornyl methacrylate (IBMA, manufactured by Kyoeisha Chemical Co., Ltd., viscosity at 25°C: 5 mPa·s, Tm < -15°C) Tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin Nakamura Chemical Industry Co., Ltd., viscosity at 25°C: 135 mPa·s, Tm < -15°C)

[0126] • Component (B): Glycidyl methacrylate (GMA, manufactured by Kyoeisha Chemical Co., Ltd., Tm < -15°C) • Component (C): 1,9ND-A: 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., Tm = 20°C) A-DON-N: 1,10-decanediol diacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., Tm = 20°C) BPE-80N: Bifunctional ethoxylated bisphenol A-diacrylate represented by the following formula (manufactured by Shin Nakamura Chemical Industry Co., Ltd., average value of e + f is 2.3, Tm < -18°C)

[0127]

[0128] CN2283: Polyester acrylate oligomer (manufactured by Arkema, Tm < -15°C) 3000MK: Epoxy ester compound represented by the following formula (i) (manufactured by Kyoeisha Chemical Co., Ltd., Tm < -15°C).

[0129]

[0130] • Ingredients (D): Lauryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., Tm = 4°C), Stearyl methacrylate (S, manufactured by Kyoeisha Chemical Co., Ltd., Tm = 20°C) • Ingredients (E): R972: Fumed silica (manufactured by Nippon Aerosil Co., Ltd.), average primary particle size 16 nm; R974: Fumed silica (manufactured by Nippon Aerosil Co., Ltd.), average primary particle size 12 nm; R976: Fumed silica (manufactured by Nippon Aerosil Co., Ltd.), average primary particle size 7 nm

[0131] ・Component (F) FB-304HM: Spherical silica with an average particle size (D50) of 11 μm (methacrylic silane surface treatment) (manufactured by Denka Co., Ltd.) FB-4DFD: Spherical silica with an average particle size (D50) of 5 μm (methacrylic silane surface treatment) (manufactured by Denka Co., Ltd.) CRS1085-SF630: Spherical silica with an average particle size (D50) of 15 μm (manufactured by Ryumori Co., Ltd.) FB-15D: Spherical silica with an average particle size (D50) of 15 μm (methacrylic silane surface treatment) (manufactured by Denka Co., Ltd.) The methacrylic silane surface treatment of FB-304HM, FB-4DFD and FB-15D was carried out using KBM-503 (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) while stirring to ensure that the silica surface was uniformly coated.

[0132] The average particle size (D50) was measured using a laser diffraction particle size distribution analyzer, SALD-300V (manufactured by Shimadzu Corporation). Component (F) was dispersed in toluene solvent, and the amount was gradually increased from a small amount until the scattering intensity was measurable. The concentration was then adjusted appropriately to a level where particle size measurement was possible, and the weight of the added particles was determined.

[0133] • Components (G) LA-81: ADK STAB LA-81 (manufactured by ADEKA Corporation) JF-95: ADK STAB JF-95 (manufactured by ADEKA Corporation) Tinuvin770DF (manufactured by BASF Japan Ltd.) The amounts of components (G) and antioxidants in the table are parts by mass (phr) per 100 parts by mass of the total liquid components in the thermosetting material.

[0134] Other polymerization initiators: Perhexa HC (manufactured by NOF Corporation) Antioxidant: Adekastab AO-80 (manufactured by ADEKA Corporation), 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane

[0135] As shown in Tables 1-3, all of the thermosetting materials in the examples were confirmed to have excellent storage properties at room temperature. Furthermore, it was confirmed that the molded products in the examples could maintain their transparency without clouding even under high temperature and high humidity conditions.

[0136] A thermosetting material and cured product according to one aspect of the present invention can be suitably used, for example, as a bracket material for optical semiconductors. A method for manufacturing a molded article according to one aspect of the present invention can be suitably used, for example, for molding a bracket material for optical semiconductors.

[0137] Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will find it easy to make many modifications to these exemplary embodiments and / or examples without substantially departing from the novel teachings and effects of the present invention. Accordingly, many of these modifications fall within the scope of the present invention. All references to the documents described in this specification and the contents of the application on which the priority claim under the Paris Convention of this application is based are incorporated herein by reference.

Claims

1. A thermosetting material comprising the following components (A) to (C) and (E): (A) Monofunctional or polyfunctional (meth)acrylate compound having a substituted or unsubstituted alicyclic hydrocarbon group with 6 or more ring-forming carbon atoms as an ester substituent; (B) Monofunctional (meth)acrylate compound having (meth)acrylic acid or a group having a polar group as an ester substituent; (C) Polyfunctional (meth)acrylate compound having a group other than the ester substituent of component (A) as an ester substituent; (E) Nanoparticles 2. The thermosetting material according to claim 1, further comprising component (F) spherical silica.

3. The thermosetting material according to claim 2, wherein the content of (F) spherical silica relative to the total major components of the thermosetting material is 40 to 90% by mass.

4. The thermosetting material according to claim 2 or 3, wherein the average particle size of the spherical silica (F) is 5 μm or more.

5. The thermosetting material according to claim 2 or 3, wherein the content of (F) spherical silica having an average particle size of 5 μm or less relative to the total major components of the thermosetting material is 75% by mass or less.

6. The thermosetting material according to any one of claims 1 to 5, further comprising component (G) a light stabilizer.

7. The thermosetting material according to claim 6, wherein the light stabilizer is a hindered amine-based light stabilizer.

8. A thermosetting material according to any one of claims 1 to 7, further comprising the following component (D): (D) A monofunctional (meth)acrylate compound having an ester substituent of component (A) or a group other than the ester substituent of component (B) as an ester substituent.

9. A thermosetting material according to any one of claims 1 to 8, wherein, based on 100% by mass of the total liquid components in the thermosetting material, the content of component (A) is 1.0 to 50% by mass, the content of component (B) is 1.0 to 50% by mass, and the content of component (C) is 1.0 to 80% by mass.

10. The thermosetting material according to claim 8 or 9, wherein the content of component (D) is 30% by mass or less, based on 100% by mass of the total liquid components.

11. A cured product of a thermosetting material according to any one of claims 1 to 10.

12. A method for manufacturing a molded article, comprising subjecting a thermosetting material according to any one of claims 1 to 10 to injection molding.

13. The manufacturing method according to claim 12, wherein the molded product is a photosemiconductor light-emitting device.

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