WO2016117471A1 - Resin composition, reflector, lead frame provided with reflector, and semiconductor light-emitting apparatus - Google Patents

Abstract

Even with a molded body molded by making use of a resin composition including a large amount of pigments with respect to a polyolefin resin, by using an isocyanurate compound having a specified structure, a resin composition capable of curing even with a low amount of ionizing radiation, a reflector molded from the resin composition, a lead frame provided with the reflector, and a semiconductor light-emitting apparatus making use of the reflector are provided. The resin composition comprises a polyolefin resin, a specified isocyanurate compound, and pigments.

Description

Resin composition, reflector, lead frame with reflector, and semiconductor light emitting device

The present invention relates to a resin composition, a reflector, a lead frame with a reflector, and a semiconductor light emitting device.

Conventionally, as a method of mounting an electronic component on a substrate or the like, after temporarily fixing the electronic component on a substrate on which solder has been previously deposited at a predetermined place, the substrate is heated by means of infrared rays, hot air, etc. A method (reflow method) for melting and fixing electronic components is employed. By this method, the mounting density of electronic components on the substrate surface can be improved.

Also, an LED element, which is one of semiconductor light emitting devices, is widely used as a light source such as an indicator lamp because of its small size, long life, and excellent power saving. In recent years, LED elements with higher brightness have been manufactured at a relatively low cost, and therefore, use as a light source to replace fluorescent lamps and incandescent bulbs has been studied. When applying to such a light source, in order to obtain a large illuminance, a plurality of LED elements are arranged on a surface-mounted LED package, that is, a metal substrate (LED mounting substrate) such as aluminum, and each LED element. A system is often used in which a reflector (reflector) that reflects light in a predetermined direction is disposed around the.

However, since the LED element generates heat during light emission, in such a type of LED lighting device, the reflector deteriorates due to the temperature rise during light emission of the LED element, and the reflectance decreases, thereby reducing the brightness. The life of the element will be shortened. Therefore, heat resistance is required for the reflector.

In order to meet the above heat resistance requirement, Patent Document 1 proposes a polymer composition used for a reflector of a light emitting diode, specifically, polyphthalamide, carbon black, titanium dioxide, glass fiber, and an antioxidant. A polymer composition is disclosed. And the reflectance after heat aging is measured about the said composition, Compared with the polymer composition which does not contain carbon black, the favorable reflectance is obtained with the said composition, and it has shown that there is also little yellowing. However, the heat aging test of the polymer composition described in Patent Document 1 is an evaluation in a short time of 3 hours at 170 ° C., and good results can be obtained with heat resistance and durability under a longer practical condition. Whether it is unknown.
Patent Document 2 discloses a thermosetting light reflecting resin composition used for an optical semiconductor device in which an optical semiconductor element and a wavelength conversion means such as a phosphor are combined. The heat aging test of the thermosetting light reflecting resin composition described in Patent Document 2 has been verified under a more practical condition of 150 hours at 150 ° C., but the molding time is 90 seconds compared to the thermoplastic resin. Since it is long and requires 2 hours as post-cure at 150 ° C., there is a problem in productivity.

In order to solve these problems, Patent Document 3 proposes an electron beam curable resin composition containing polymethylpentene and a crosslinking agent having an allylic substituent having a molecular weight of 1000 or less. In Patent Document 3, the electron beam curable composition containing a white pigment and further containing inorganic particles other than the white pigment has excellent heat resistance in the reflow process, and is used as a molded body such as a reflector. It is described that excellent heat resistance can be obtained. In Patent Document 3, isocyanurate having three allyl groups and isocyanurate having two allyl groups and an epoxy group are used as a crosslinking agent having an allylic substituent. When a crosslinking agent having three allyl groups was used, when the resin composition was cured by irradiating an electron beam, it was necessary to increase the amount of electron beam irradiation in order to react all the allyl groups. . However, if the electron beam irradiation amount increases, the resin deteriorates and the life of the semiconductor light emitting device is shortened. Therefore, it is desired that the electron beam irradiation amount be as small as possible. Moreover, since epoxy group does not react by electron beam irradiation, it remains and changes during product use. As a result, there is a concern that the life of the semiconductor light emitting device may be shortened.

Special Table 2006-503160 JP 2009-149845 A JP 2013-166926 A

The object of the present invention is to reduce the irradiation dose of ionizing radiation by using an isocyanurate compound having a specific structure, even for a molded article formed using a resin composition containing a large amount of pigment with respect to a polyolefin resin. An object of the present invention is to provide a resin composition that can be cured at least, a reflector formed by molding the resin composition, a lead frame with a reflector, and a semiconductor light emitting device using the reflector.

As a result of intensive studies to achieve the above object, the present inventors have found that the object can be achieved by the following invention. That is, the present invention is as follows.

［式中、Ｒ^１はヘテロ原子を含んでいてもよい炭素数４～３０の炭化水素基であり、Ｒ^２及びＲ^３は炭素数３～６のアルケニル基を示し、Ｒ^２及びＲ^３は同一であってもよいし、異なっていてもよい。］
［２］　前記顔料が、白色顔料又は黒色顔料である、［１］に記載の樹脂組成物。
［３］　前記ポリオレフィン樹脂の屈折率が、１．４０～１．６０である、［１］又は［２］に記載の樹脂組成物。
［４］　前記ポリオレフィン樹脂１００質量部に対して、前記イソシアヌレート化合物１～１００質量部、及び顔料１０～１０００質量部を含む、［１］～［３］のいずれかに記載の樹脂組成物。
［５］　前記ポリオレフィン樹脂１００質量部に対して、顔料を除く無機フィラーを１０～５００質量部含む、［４］に記載の樹脂組成物。
［６］　前記ポリオレフィン樹脂１００質量部に対して、流動性向上剤を０．１～５０質量部含む、［４］又は［５］に記載の樹脂組成物。
［７］　［１］～［６］のいずれかに記載の樹脂組成物の硬化物からなる、リフレクター。
［８］　前記硬化物が、前記樹脂組成物を成形した後に、電離放射線を照射してなる、［７］に記載のリフレクター。
［９］　［１］～［６］のいずれかに記載の樹脂組成物の硬化物からなる、リフレクター付きリードフレーム。
［１０］　光半導体素子と、前記光半導体素子の周りに設けられ、該光半導体素子からの光を所定方向に反射させるリフレクターとを基板上に有し、前記リフレクターが［７］又は［８］に記載のリフレクターである、半導体発光装置。 [1] A resin composition comprising a polyolefin resin, an isocyanurate compound, and a pigment, wherein the isocyanurate compound is a compound represented by the following general formula (1).

[Wherein, R ¹ is a hydrocarbon group having 4 to 30 carbon atoms which may contain a hetero atom, R ² and R ³ are alkenyl groups having 3 to 6 carbon atoms, and R ² and R ³ are They may be the same or different. ]
[2] The resin composition according to [1], wherein the pigment is a white pigment or a black pigment.
[3] The resin composition according to [1] or [2], wherein the polyolefin resin has a refractive index of 1.40 to 1.60.
[4] The resin composition according to any one of [1] to [3], comprising 1 to 100 parts by mass of the isocyanurate compound and 10 to 1000 parts by mass of the pigment with respect to 100 parts by mass of the polyolefin resin.
[5] The resin composition according to [4], comprising 10 to 500 parts by mass of an inorganic filler excluding a pigment with respect to 100 parts by mass of the polyolefin resin.
[6] The resin composition according to [4] or [5], comprising 0.1 to 50 parts by mass of a fluidity improver with respect to 100 parts by mass of the polyolefin resin.
[7] A reflector comprising a cured product of the resin composition according to any one of [1] to [6].
[8] The reflector according to [7], wherein the cured product is formed by irradiating ionizing radiation after molding the resin composition.
[9] A lead frame with a reflector, comprising a cured product of the resin composition according to any one of [1] to [6].
[10] An optical semiconductor element and a reflector provided around the optical semiconductor element and reflecting light from the optical semiconductor element in a predetermined direction are provided on the substrate, and the reflector is [7] or [8] The semiconductor light-emitting device which is a reflector as described in.

Since the resin composition obtained according to the present invention can be cured by irradiating with ionizing radiation after molding, the dose of ionizing radiation can be reduced, so that a reflector with little deterioration due to ionizing radiation can be obtained. Moreover, since the resin composition obtained by this invention is excellent in fluidity | liquidity, when making it into a molded object by injection molding etc., workability improves. Therefore, a molded product having excellent shape reproducibility can be obtained.

It is a schematic sectional drawing which shows an example of the semiconductor light-emitting device of this invention. It is a schematic sectional drawing which shows an example of the semiconductor light-emitting device of this invention.

［式中、Ｒ^１はヘテロ原子を含んでいてもよい炭素数４～３０の炭化水素基であり、Ｒ^２及びＲ^３は炭素数３～６のアルケニル基を示し、Ｒ^２及びＲ^３は同一であってもよいし、異なっていてもよい。］
　以下、本発明の樹脂組成物について詳細に説明する。なお、本明細書において、好ましいとされている規定は任意に採用することができ、好ましいもの同士の組み合わせはより好ましいと言える。 [1. Resin composition]
The resin composition of the present invention is a resin composition containing a polyolefin resin, an isocyanurate compound, and a pigment, and the isocyanurate compound is a compound represented by the following general formula (1).

[Wherein, R ¹ is a hydrocarbon group having 4 to 30 carbon atoms which may contain a hetero atom, R ² and R ³ are alkenyl groups having 3 to 6 carbon atoms, and R ² and R ³ are They may be the same or different. ]
Hereinafter, the resin composition of the present invention will be described in detail. In the present specification, it is possible to arbitrarily adopt provisions that are preferable, and it can be said that a combination of preferable ones is more preferable.

<Polyolefin resin>
The polyolefin resin used in the resin composition of the present invention is a polymer of a structural unit whose main chain is composed of a carbon-carbon bond, and the carbon bond may include a cyclic structure. A homopolymer may be sufficient and the copolymer formed by copolymerizing with another monomer may be sufficient. Since the carbon-carbon bond does not cause a hydrolysis reaction, it has excellent water resistance. Examples of the olefin resin include a resin obtained by ring-opening metathesis polymerization of a norbornene derivative or hydrogenation thereof, an olefin homopolymer such as ethylene or propylene, an ethylene-propylene block copolymer, a random copolymer, or Copolymers of ethylene and / or propylene with other olefins such as butene, pentene, hexene, and further copolymers of ethylene and / or propylene with other monomers such as vinyl acetate. It is done. Among these, polyethylene, polypropylene, and polymethylpentene are preferable, and the melting point is as high as 230 to 240 ° C., and they do not decompose even at a molding temperature of about 280 ° C., and have excellent chemical resistance and electrical insulation properties. Polymethylpentene is more preferred.

The polyethylene may be a homopolymer of ethylene, or other comonomer copolymerizable with ethylene (for example, α-olefin such as propylene, 1-butene, 1-hexene, 1-octene). , Vinyl acetate, vinyl alcohol, etc.). Examples of the polyethylene resin include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), and ultra high molecular weight polyethylene ( UHMWPE), cross-linked polyethylene (PEX) and the like. These polyethylenes may be used alone or in combination of two or more.

The polypropylene may be a homopolymer of propylene, or other comonomer copolymerizable with propylene (for example, α-olefin such as ethylene, 1-butene, 1-hexene, 1-octene). , Vinyl acetate, vinyl alcohol, etc.). These polypropylenes may be used alone or in combination of two or more.

The polymethylpentene resin is preferably a homopolymer of 4-methylpentene-1, but 4-methylpentene-1 and other α-olefins such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene. 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, etc. It may be a copolymer with olefin and a copolymer mainly composed of 4-methyl-1-pentene. In the case of the copolymer, from the viewpoint of heat resistance, an alkene having 10 to 18 carbon atoms is preferably copolymerized, and an alkene having 16 or more carbon atoms is more preferable.

By setting the refractive index of the polyolefin resin used in the resin composition of the present invention to 1.40 to 1.60, in particular, a molded body obtained by molding a resin composition using a white pigment as a pigment is used as a reflector. In this case, the light reflectance can be improved. The weight average molecular weight of the polyolefin resin is preferably 220,000 to 800,000. A weight average molecular weight of 220,000 or more is preferable because cracks are less likely to occur in a molded product obtained by molding a resin composition. For example, if a crack is generated in a semiconductor light emitting device, moisture enters and the semiconductor light emitting element breaks down, resulting in an extremely short product life. Moreover, since it becomes difficult to shape | mold a resin composition as a weight average molecular weight is 800,000 or less, it is preferable. The lower limit of the weight average molecular weight of the polyolefin resin is preferably 230,000 or more, more preferably 240,000 or more. Moreover, the upper limit of the weight average molecular weight is preferably 700,000 or less, more preferably 650,000 or less. The weight average molecular weight is preferably a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC), but is not limited to this as long as the method can measure the weight average molecular weight with good reproducibility. For example, the weight average molecular weight can be measured by a method exemplified for a material extracted with an appropriate solvent.

The following conditions can be illustrated as an example of the weight average molecular weight measurement conditions by GPC.
Eluent: o-dichlorobenzene Temperature: 140-160 ° C
Flow rate: 1.0 mL / min
Sample concentration: 1.0 / L
Injection volume: 300 μL

［式中、Ｒ^１はヘテロ原子を含んでいてもよい炭素数４～３０の炭化水素基であり、Ｒ^２及びＲ^３は炭素数３～６のアルケニル基を示し、Ｒ^２及びＲ^３は同一であってもよいし、異なっていてもよい。］ <Isocyanurate compound>
The isocyanurate compound used in the resin composition of the present invention is a compound represented by the following general formula (1).

[Wherein, R ¹ is a hydrocarbon group having 4 to 30 carbon atoms which may contain a hetero atom, R ² and R ³ are alkenyl groups having 3 to 6 carbon atoms, and R ² and R ³ are They may be the same or different. ]

R ¹ is a hydrocarbon group having 4 to 30 carbon atoms which may contain a hetero atom. The hydrocarbon group is preferably a hydrocarbon group having no olefinic unsaturated bond. Examples of these hydrocarbon groups include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Examples of the alkyl group include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl. Examples thereof include a linear alkyl group such as a group and a branched alkyl group. Examples of the cycloalkyl group include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a trityl group, a naphthylmethyl group, and an anthracenylmethyl group. As described above, these hydrocarbon groups may contain a heteroatom, and examples of the heteroatom include heteroatoms such as an oxygen atom, a nitrogen atom, and a sulfur atom. R ¹ is preferably an alkyl group, and particularly preferably an alkyl group having 6 to 20 carbon atoms.

R ² and R ³ represent an alkenyl group having 3 to 6 carbon atoms, and examples thereof include an alkenyl group such as a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. The position of the carbon-carbon double bond in these alkenyl groups may be a terminal position or an internal site. R ² and R ³ may be the same or different. As R ² and R ³ , a propenyl group is particularly preferable, and among all propenyl groups, an allyl group is preferable. R ² and R ³ are preferably allyl groups.

As the isocyanurate compound represented by the general formula (1), for example, specific compounds in the case where both R ² and R ³ are allyl groups are exemplified. 5-Nonyl-1,3-diallyl isocyanurate, 5-decyl-1,3-diallyl isocyanurate, 5-dodecyl-1,3-diallyl isocyanurate, 5-tridecyl-1,3-diallyl isocyanurate, 5-tetradecyl-1,3-diallyl isocyanurate, 5- Examples include cyclohexyl-1,3-diallyl isocyanurate, 5-phenyl-1,3-diallyl isocyanurate, and 5-benzyl-1,3-diallyl isocyanurate.

The resin composition of the present invention can improve moldability and curing treatment of the resin composition by using the isocyanurate compound represented by the general formula (1). In the curing treatment after molding the resin composition, the curing treatment is usually performed by irradiating with ionizing radiation. By using the isocyanurate compound represented by the general formula (1), the conventional trifunctional crosslinking is performed. Compared with the case of using a treating agent, the irradiation amount of ionizing radiation can be reduced. Therefore, deterioration of the material used can be reduced. In addition, the isocyanurate compound represented by the general formula (1) has R ¹ of 4 to 30 carbon atoms and excellent compatibility with the olefin resin, so that the fluidity of the resin composition becomes high, and it is molded by injection molding or the like. Workability is improved when forming a body.

<Pigment>
A pigment is used in the resin composition of the present invention. Although it does not specifically limit as a pigment, When using the cured | curing material of a resin composition as a reflector, as a pigment, a white pigment or a black pigment is used preferably. As the white pigment, titanium oxide, alumina, talc, aluminum hydroxide, mica, calcium carbonate, zinc sulfide, zinc oxide, barium sulfate, potassium titanate and the like can be used alone or in combination. The white pigment is used for imparting a white color tone to the cured product obtained by curing the resin composition of the present invention. In particular, by setting the color tone to a high degree of white, the light ray of the cured product is used. The reflectance can be improved. What improved the light reflectivity of the hardened | cured material obtained by hardening the resin composition of this invention can be used as a reflector. In particular, when a cured product is used as a reflector, a good light reflectance is required. Therefore, as a white pigment, it is preferable to use titanium oxide that is easily available and excellent in light reflectance. The average particle size of the white pigment is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm in the primary particle size distribution from the viewpoint of obtaining moldability and obtaining high reflectance. More preferably, it is 2 to 1 μm. An average particle diameter can be calculated | required as mass average value D50 in the particle size distribution measurement by a laser beam diffraction method.
Further, the black pigment is a powder having a light reflectance of less than 1% at least in the visible light region (400 to 700 nm). The black pigment is added to the cured product obtained by curing the resin composition of the present invention. It can be used to impart the color tone of the cured product to reduce the light reflectance of the cured product. Such a cured product having a reduced light reflectivity is also used as a reflector for LEDs for specific applications. As the black pigment, carbon black or graphite is preferably used.

<Combination ratio>
The resin composition of the present invention contains a polyolefin resin, an isocyanurate compound, and a pigment. The isocyanurate compound is usually 1 to 100 parts by mass, preferably 8 to 60 parts by mass with respect to 100 parts by mass of the polyolefin resin. Part, more preferably 10 to 50 parts by weight. By setting the content of the isocyanurate compound within the above range, the moldability of the resin composition and the curability of the cured product of the resin composition can be made compatible. The pigment is usually 10 to 1000 parts by weight, preferably 50 to 800 parts by weight, and more preferably 100 to 600 parts by weight with respect to 100 parts by weight of the polyolefin resin. By making the content of the pigment within the above range, the effect of the pigment can be sufficiently exhibited in the cured product obtained from the resin composition, and the moldability is ensured when the resin composition is molded. Can do.

<Inorganic filler excluding pigments>
The resin composition of the present invention may further contain an inorganic filler excluding the pigment (hereinafter sometimes referred to as an inorganic filler). By including an inorganic filler, the strength of a cured product obtained by curing the resin composition of the present invention can be improved. As such an inorganic filler, a fibrous inorganic filler, other inorganic fillers such as a plate shape and a particulate shape can be used.

(Fibrous inorganic filler)
Examples of the fibrous inorganic filler include glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, imogolite, sepiolite, slag fiber, zonolite, gypsum fiber And silica fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers and boron fibers.

(Other inorganic fillers)
Other inorganic fillers include silica particles, layered silicates, layered silicates exchanged with organic onium ions, glass flakes, non-swelling mica, graphite, metal foil, ceramic beads, clay, mica, sericite, zeolite, Examples thereof include plate-like and particulate inorganic fillers such as carbon nanoparticles such as bentonite, dolomite, kaolin, powdered silicic acid, feldspar powder, shirasu balloon, gypsum, novaculite, dosonite, and white clay fullerene.

Among the inorganic fillers excluding the pigment, when the resin composition of the present invention is used for a reflector, glass fiber is used from the viewpoint of excellent shape stability due to mechanical strength and temperature when used as a semiconductor light emitting device. It is preferable to use, and it is particularly preferable to use a glass fiber containing 60% by mass or more of silicon dioxide. The ratio of silicon dioxide in the glass fiber is more preferably 65% by mass or more, and further preferably 70% by mass or more.
The cross-sectional shape of the fibrous filler may be a general, substantially circular shape, or an irregular cross-section such as a flat shape. Furthermore, the fiber does not have to have a constant cross-sectional shape and cross-sectional area. The cross-sectional performance in this case is defined as a cross-sectional area obtained by averaging different cross-sectional areas in the length direction. As an example, when the fibrous filler is glass fiber, the size of the cross section satisfies the above-mentioned definition of the cross sectional area, the short axis D1 of the cross section is 0.5 μm or more and 25 μm or less, and the long diameter D2 is 0.5 μm. It is preferable that the ratio D2 / D1 of D2 to D1 is 1.0 to 30 and 300 μm or less. Moreover, it is preferable that the average fiber length of glass fiber is 0.75 micrometer or more and 300 micrometers or less. Such glass fibers are also called milled fibers, and can be obtained by pulverizing long fibers. The inorganic filler excluding the pigment can be used usually in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the polyolefin resin.

<Fluidity improver>
The resin composition of the present invention can further contain a fluidity improver. By including the fluidity improver, when molding the resin composition, it is possible to improve the moldability of the resin composition containing a large amount of the inorganic filler excluding the pigment and the pigment.
Examples of the fluidity improver include polyethylene wax, polypropylene wax, polar wax, liquid paraffin, silane compounds used as silane coupling agents, and metal soap. As for the said fluid improvement agent, only 1 type may be used and 2 or more types may be used together.

In particular, the use of a silane compound used as a silane coupling agent as the fluidity improver is highly dispersible and compatible with inorganic substances in the resin, and reflectivity, mechanical properties, and dimensions when used as a reflector. It is preferable from the viewpoint of improving the stability. Examples of these silane compounds include disilazane such as hexamethyldisilazane; cyclic silazane; trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, trimethoxysilane, benzyldimethylchlorosilane, Methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-butyltrimethoxysilane, n-hexadecyl Trimethoxysilane, n-octadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyl Alkylsilane compounds such as limethoxysilane and vinyltriacetoxysilane; γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane N-phenyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, and N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane And aminosilane compounds such as hexyltrimethoxysilane; and the like.

The fluidity improver can be used usually in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the polyolefin resin.

<Other additives>
In addition, the resin composition of this invention can be made to contain various additives, unless the effect of this invention is impaired. For example, for the purpose of improving the properties of the resin composition, various silicone powders, thermoplastic elastomers, organic synthetic rubbers, fatty acid esters, glycerate esters, zinc stearate, calcium stearate and other internal mold release agents, benzophenone series, Additives such as antioxidants such as salicylic acid, cyanoacrylate, isocyanurate, oxalic anilide, benzoate, hindered amine, benzotriazole, and phenol, and light stabilizers such as hindered amine and benzoate Can be blended.

The resin composition of the present invention is prepared by melting and kneading the above-described polyolefin resin, isocyanurate compound, and inorganic filler, fluidity improver and other additives other than the pigment and the pigment used as necessary, etc. Can be produced as a granulated product. As the melt-kneading method, a known melt-kneading method such as a melt-kneading extruder, a two-roll or three-roll, a stirrer such as a homogenizer or a planetary mixer, or a melt-kneader such as a polylab system or a lab plast mill is used. be able to.

The cured product obtained from the resin composition of the present invention is obtained by converting the resin composition into a molded body having a predetermined shape using various molding methods and curing the molded body. As a molding method, a molding method such as transfer molding, compression molding or injection molding can be used. For example, when an injection molding method is used, it can be obtained by injection molding at a cylinder temperature of 200 to 400 ° C. and a mold temperature of 20 to 150 ° C. As a method for curing the molded body thus obtained, a cured product can be usually obtained by irradiating with ionizing radiation. Examples of the ionizing radiation include an electron beam and ultraviolet rays. From the viewpoint of obtaining a cured product in a relatively short time, it is preferable to use an electron beam.

When an electron beam is used as the ionizing radiation, the acceleration voltage of the electron beam can be appropriately selected according to the size of the resin composition to be used and the thickness of the molded body. For example, in the case of a molded body having a thickness of about 1 mm, the crosslinking agent used can be crosslinked and cured at an acceleration voltage of about 250 to 3000 kV. In addition, in electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the molded body are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress irradiation of an excessive electron beam to the molded body, and to minimize degradation of the molded body due to excess electron beams. The absorbed dose when irradiating with an electron beam is appropriately set depending on the composition of the resin composition, but is preferably an amount at which the crosslink density in the molded body is saturated, and the irradiated dose is preferably 50 to 600 kGy, particularly It is preferably 100 to 250 kGy.
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.

[2. Reflector]
The reflector of the present invention is formed by molding the above-described resin composition of the present invention.
The reflector may be used in combination with a semiconductor light-emitting device to be described later, or may be used in combination with a semiconductor light-emitting device (LED mounting substrate) made of another material.
The reflector of the present invention mainly has an action of reflecting light from the LED element of the semiconductor light emitting device toward the lens (light emitting portion). The details of the reflector are the same as those of the reflector (reflector 12 described later) applied to the semiconductor light emitting device of the present invention, and are omitted here.

[3. Lead frame with reflector]
The lead frame with a reflector of the present invention is formed by molding the above-described resin composition of the present invention. The lead frame indicates a substrate on which the reflector is placed. Any lead frame can be used as long as it is used in the field of semiconductor light emitting devices. Examples of the material of the lead frame include ceramics made of a sintered body such as alumina, aluminum nitride, mullite, and glass. In addition, a resin material having flexibility such as polyimide resin can be used. In particular, a lead frame made of metal is often made of aluminum, copper, or an alloy of copper, and is often plated with a noble metal having a high reflectance such as silver in order to improve the reflectance. In particular, a reflector substrate made of metal is often called a lead frame. Terminal portions and the like formed on the lead frame may be formed by half etching. Specifically, the lead frame with a reflector of the present invention is manufactured by molding the resin composition of the present invention into a desired reflector shape by injection molding the above lead frame.

The thickness of the lead frame with a reflector of the present invention (reflector thickness) is preferably 0.1 to 3.0 mm, more preferably 0.1 to 1.0 mm, and more preferably 0.1 to 0.00 mm. More preferably, it is 8 mm.

The lead frame with a reflector of the present invention can be made into a semiconductor light emitting device by mounting an LED chip on the reflector, further sealing with a known sealing agent, and die bonding to obtain a desired shape. In addition, although the lead frame with a reflector of this invention acts as a reflector, it is functioning also as a frame which supports a semiconductor light-emitting device.

[4. Semiconductor light emitting device]
The semiconductor light emitting device of the present invention is illustrated in FIG. The semiconductor light emitting device according to the present embodiment includes an optical semiconductor element 10 and a reflector 12 provided around the optical semiconductor element 10 and having a light reflecting surface that reflects light from the optical semiconductor element 10 in a predetermined direction. On top. The optical semiconductor element 10 is preferably an LED element or an LED package. In the semiconductor light emitting device, the reflector 12 corresponds to the above-described reflector, and at least a part of the light reflecting surface (all in the case of FIG. 1) is formed of a molded body made of the above-described resin composition for a reflector of the present invention. Become.

The optical semiconductor element 10 emits radiated light (generally UV or blue light in a white light LED), for example, an active layer made of AlGaAs, AlGaInP, GaP or GaN sandwiched between n-type and p-type cladding layers. It is a semiconductor chip (light emitter) having a double heterostructure, and has a hexahedral shape with a side length of about 0.5 mm, for example. In the case of wire bonding mounting, it is connected to an electrode (connection terminal) (not shown) via a lead wire 16.

The shape of the reflector 12 conforms to the shape of the end portion (joint portion) of the lens 18 and is usually a cylindrical shape such as a square shape, a circular shape, or an oval shape, or an annular shape. In the schematic cross-sectional view of FIG. 1, the reflector 12 is a cylindrical body (annular body), and all the end faces of the reflector 12 are in contact with and fixed to the surface of the substrate 14.
In addition, in order to improve the directivity of the light from the optical semiconductor element 10, the inner surface of the reflector 12 may be expanded upward in a tapered shape (see FIG. 1).
The reflector 12 can also function as a lens holder when the end portion on the lens 18 side is processed into a shape corresponding to the shape of the lens 18.

As shown in FIG. 2, the reflector 12 may have only the light reflecting surface side as a light reflecting layer 12b made of the resin composition of the present invention. In this case, the thickness of the light reflection layer 12b is preferably 500 μm or less, and more preferably 300 μm or less, from the viewpoint of reducing the thermal resistance. The member 12a on which the light reflecting layer 12b is formed can be made of a known heat resistant resin.

As described above, the lens 18 is provided on the reflector 12, but this is usually made of resin, and various structures may be adopted and colored depending on the purpose and application.

The space formed by the substrate 14, the reflector 12, and the lens 18 may be a transparent sealing portion, or may be a gap if necessary. This space portion is usually a transparent sealing portion filled with a light-transmitting and insulating material, and the force applied by directly contacting the lead wire 16 in wire bonding mounting and indirectly. Prevents electrical defects caused by the lead wire 16 being disconnected, cut, or short-circuited from the connection portion with the optical semiconductor element 10 and / or the connection portion with the electrode due to applied vibration, impact, etc. can do. At the same time, the optical semiconductor element 10 can be protected from moisture, dust, etc., and the reliability can be maintained over a long period of time.

Examples of the material (transparent sealant composition) that imparts translucency and insulation usually include silicone resins, epoxy silicone resins, epoxy resins, acrylic resins, polyimide resins, polycarbonate resins, and the like. Of these, silicone resins are preferred from the viewpoints of heat resistance, weather resistance, low shrinkage, and discoloration resistance.

Below, an example of the manufacturing method of the semiconductor light-emitting device shown in FIG. 1 is demonstrated.
First, the reflector 12 having a predetermined shape is molded from the reflective resin composition of the present invention by transfer molding, compression molding, injection molding or the like using a mold having a cavity space having a predetermined shape. Thereafter, the separately prepared optical semiconductor element 10 and the electrode are fixed to the substrate 14 with an adhesive or a bonding member, and the LED element and the electrode are connected with the lead wire 16. Next, a transparent sealant composition containing a silicone resin or the like is poured into the recess formed by the substrate 14 and the reflector 12, and cured by heating, drying, or the like to obtain a transparent sealing portion. Thereafter, the lens 18 is disposed on the transparent sealing portion to obtain the semiconductor light emitting device shown in FIG.
In addition, after mounting the lens 18 in a state where the transparent sealant composition is uncured, the composition may be cured.
When the molded body obtained from the resin composition of the present invention is cured by irradiating with ionizing radiation, the amount of ionizing radiation irradiation can be reduced, so that a reflector with little deterioration due to ionizing radiation and a lead frame with a reflector can be obtained. Can do.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the material used in the present Example and the comparative example is as follows.

[Resin component]
Polymethylpentene resin: MX002 (manufactured by Mitsui Chemicals, trademark registration: TPX-MX002, density 0.833 g / cm ³ , melting peak temperature 224 ° C., refractive index 1.42)
Polypropylene resin: J137G [manufactured by Prime Polymer Co., Ltd., Prime Polypro J137G, MI = 30 g / 10 min, refractive index 1.48]
Polyethylene resin: High density polyethylene [manufactured by Prime Polymer Co., Ltd., Hi-Zex 1300J, MI = 12 g / 10 min, refractive index 1.53]

[Isocyanurate compounds]
Compound 1: triallyl isocyanurateCompound 2: 5-dodecyl-1,3-diallyl isocyanurate [in the general formula (1), R ¹ is an n-dodecyl group, R ² and R ³ are allyl groups Some compounds]
Compound 3: monoallyl diglycidyl isocyanurate

[Pigment component]
Titanium oxide: PF691 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.21 μm)
・ Carbon black: # 45 (Mitsubishi Chemical Corporation)

[Inorganic filler components excluding pigments]
Glass fiber: SS05DE-413SP (manufactured by Nittobo Co., Ltd., fiber length 65 μm, average cross-sectional area 41.6 μm ² , cross-sectional shape is round glass fiber)

[Flowability improver]
Silane compound: Hexyltrimethoxysilane [KBM-3063 (manufactured by Shin-Etsu Chemical Co., Ltd.)]

[Other additives]
Release agent: Zinc stearate [SZ-2000 (manufactured by Sakai Chemical Co., Ltd.)]
Antioxidant (1): IRGANOX 1010 (BASF Japan Ltd.)
Antioxidant (2): PEP36 [Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, manufactured by ADEKA Corporation, trade name: ADK STAB PEP36]

[Examples 1 to 10, Comparative Examples 1 to 3]
Various materials were blended and kneaded as shown in Tables 1 and 2 below to obtain resin compositions.
The resin composition was prepared by blending various materials and using an extruder (Nippon Placon Co., Ltd. MAX30: die diameter: 3.0 mm) and a pelletizer (Toyo Seiki Seisakusho MPPEC1). About the obtained resin composition, MVR was evaluated by the method as described below. Moreover, the lead frame molded object with a reflector was produced for the resin composition with the injection molding machine (TR40ER by Sodick Co., Ltd.), and the moldability was evaluated by the method as described below. The heat resistance and tensile properties are as follows: a cured product obtained by irradiating an electron beam with an absorbed voltage of 200 kGy or 340 kGy at an acceleration voltage of 800 kV from a molding machine with a molding size of 750 mm × 750 mm × thickness of 0.5 mm. Evaluation was performed by the method described. The evaluation results are shown in Tables 1 and 2.

(Evaluation 1)
· MVR of MVR ^(cm 3/60 sec) Measurement and formability evaluation resin composition of JIS K 7210: it was measured by a method according to the method described in 1999 MVR thermoplastics. Specifically, the test was performed under the conditions of a test temperature of 280 ° C., a test load of 2.16 kg, and 60 seconds. As a measuring device, a melt flow tester manufactured by Thiast Co. was used. MVR is an index indicating moldability, and the larger the value, the higher the fluidity and the better the moldability.

(Evaluation 2)
Moldability The resin composition obtained above was injection molded onto a 250 μm-thick silver-plated lead frame with an injection molding machine (TR40ER manufactured by Sodick Co., Ltd.) to produce a lead frame molded body with a reflector (resin (Thickness: 700 μm, external dimensions: 35 mm × 35 mm, openings: 2.9 mm × 2.9 mm, number of openings: 36). The injection molding machine conditions were as follows: cylinder temperature: 260 ° C., mold temperature: 70 ° C., injection speed: 200 mm / sec, holding pressure: 100 MPa, holding pressure time: 1 sec, cooling time: 15 sec. As for moldability, the plunger stability during molding was evaluated according to the following criteria.
○: ···· Good formability, stable plunger position △: ··· Moldable but unstable plunger position (possible failure)
×: ··· Molding impossible

(Evaluation 3)
-Heat resistance The storage elastic modulus of each sample of the molded body was measured by RSAG2 (manufactured by TA INSTRUMENTS) under the conditions of a measurement temperature of 25 to 400 ° C, a heating rate of 5 ° C / min, and a strain of 0.1%. The storage elastic moduli at 270 ° C. are shown in Tables 1 and 2 below.

(Evaluation 4)
・ Tensile property Tensile modulus (MPa) of each sample of the molded body is tensed using a tensile compression tester (Tensilon RTF-1350, manufactured by A & D Co., Ltd.) in a temperature environment of 25 ° C. in accordance with JIS K7162. From the first linear portion of the tensile stress-strain curve obtained by measurement under the conditions of a speed of 0.3 mm / min and a distance between chucks of 20 mm, the calculation was performed according to the following formula. The measurement results are shown in Tables 1 and 2 below.
E = Δρ / Δε
E: Tensile modulus Δρ: Stress difference due to the original average cross-sectional area between two points on a straight line Δε: Strain difference between the same two points

As apparent from the results of the above Examples, the resin compositions obtained in Examples 1 to 10, as compared to the resin compositions obtained in Comparative Examples 1 and 2, MVR is 6 cm ^3/60 seconds or more and It is high and shows excellent moldability.
It has been shown that the resin compositions obtained in Examples 1 to 7 have sufficient curability even with a small amount of electron beam irradiation. Further, it is shown that the resin compositions obtained in Examples 8 to 10 have higher storage elastic modulus and higher heat resistance when the electron beam irradiation amount is increased. On the other hand, in comparison with Example 1 and Comparative Example 2, Comparative Example 2 using Compound 3 (monoallyl diglycidyl isocyanurate) as the isocyanurate compound has a low storage elastic modulus and is inferior in heat resistance. From the comparison between Example 2 and Comparative Example 3, Comparative Example 3 using Compound 1 (triallyl isocyanurate) as the isocyanurate compound has poor moldability and the storage elastic modulus is measured. It is shown that you can not.
The resin compositions of Examples 1 and 8, the resin compositions of Examples 2, 7 and 9, and the resin compositions of Examples 3 and 10 have the same blending composition of the resin compositions, respectively. It is the Example which changed irradiation amount. These examples show that even when the electron beam irradiation amount is small, it has a sufficient storage elastic modulus.
The resin compositions obtained in Examples 1 to 10 are shown to have a sufficient tensile modulus even when the electron beam irradiation amount is small.

DESCRIPTION OF SYMBOLS 10 ... Optical semiconductor element 12 ... Reflector 14 ... Board | substrate 16 ... Lead wire 18 ... Lens

Claims (10)

A resin composition comprising a polyolefin resin, an isocyanurate compound, and a pigment, wherein the isocyanurate compound is a compound represented by the following general formula (1).

[Wherein, R ¹ is a hydrocarbon group having 4 to 30 carbon atoms which may contain a hetero atom, R ² and R ³ are alkenyl groups having 3 to 6 carbon atoms, and R ² and R ³ are They may be the same or different. ] The resin composition according to claim 1, wherein the pigment is a white pigment or a black pigment. The resin composition according to claim 1 or 2, wherein the polyolefin resin has a refractive index of 1.40 to 1.60. The resin composition according to any one of claims 1 to 3, comprising 1 to 100 parts by mass of the isocyanurate compound and 10 to 1000 parts by mass of a pigment with respect to 100 parts by mass of the polyolefin resin. The resin composition according to claim 4, comprising 10 to 500 parts by mass of an inorganic filler excluding a pigment with respect to 100 parts by mass of the polyolefin resin. 6. The resin composition according to claim 4, comprising 0.1 to 50 parts by mass of a fluidity improver with respect to 100 parts by mass of the polyolefin resin. A reflector comprising a cured product of the resin composition according to any one of claims 1 to 6. The reflector according to claim 7, wherein the cured product is formed by irradiating ionizing radiation after the resin composition is molded. A lead frame with a reflector, comprising a cured product of the resin composition according to any one of claims 1 to 6. The reflector according to claim 7 or 8, further comprising: an optical semiconductor element; and a reflector provided around the optical semiconductor element and configured to reflect light from the optical semiconductor element in a predetermined direction on the substrate. A semiconductor light emitting device.

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