JP2016222761A - Resin composition, reflector, lead frame with reflector, semiconductor light emitting device, isocyanurate compound for crosslinking agent, and glycoluril compound for crosslinking agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in heat resistance and moldability and capable of forming a reflector exhibiting stable heat resistance and moldability.SOLUTION: The resin composition is an isocyanurate compound containing a polyolefin resin, a crosslinking agent and a reinforcement filler, where the crosslinking agent is represented by the chemical formula (1), where R is an alkylene group having 1 to 16 carbon atoms or an alkylene group having 1 to 16 carbon atoms and an ester bond, an ether bond, a thioether bond, an amino bond, an amide bond, an urethane bond, an urea bond, a carbamate bond, a thiocarbamate bond and a carbonate bond is selected as single, a plurality of or a combination thereof.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a reflector, a lead frame with a reflector, a semiconductor light emitting device, an isocyanurate compound for a crosslinking agent, and a glycoluril compound for a crosslinking agent.

  An LED element, which is one of semiconductor light emitting devices, is widely used as a light source for an indicator lamp or the like because it is small and has a long lifetime and is excellent in 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 method of forming a surface-mounted LED package, that is, a plurality of LED elements are arranged on a metal substrate (LED mounting substrate) such as aluminum. A method of arranging a reflector (hereinafter referred to as a reflector) that reflects light in a predetermined direction around each LED element is frequently used.

  Since the LED element generates heat during light emission, in such a type of LED lighting apparatus, the deterioration of the reflector may be accelerated due to a temperature rise during light emission of the LED element. The deterioration of the reflector leads to a decrease in reflectance, leading to a shortened life of the LED element. For this reason, the reflector is required to have heat resistance against the heat generated by the LED element. Moreover, since the curvature and dimensional change which arise in a reflector also cause the reflectance of a reflector to fall, dimensional stability is also requested | required of a reflector.

  In response to these requirements, Patent Document 1 discloses a thermosetting light reflecting resin composition containing an epoxy resin, a curing agent, a curing catalyst, an inorganic filler, a white pigment, an additive, and a release agent, The light which specified the surface free energy in the mold release surface of the molded product obtained by transfer molding the product and releasing it from the molding die, and the light diffuse reflectance at the light wavelength of 400 nm after curing of the resin composition A reflective resin composition, and an optical semiconductor element mounting substrate manufactured using the composition have been proposed. According to this technology, the thermosetting light reflecting resin composition is excellent in various properties such as optical properties and heat-resistant coloring properties required for a substrate for mounting an optical semiconductor element, and excellent in molding processability by a transfer molding method or the like. It is said that can be provided.

  Patent Document 2 discloses a white resin molded product obtained by irradiating a specific amount of an electron beam onto a molded product comprising a resin composition containing a fluororesin having a carbon-hydrogen bond and a predetermined amount of titanium oxide. LED reflectors have been proposed. According to this technology, the reflector part has a high heat deterioration resistance and light deterioration resistance that are not easily discolored even when exposed to light at a high temperature of 150 ° C. or higher for a long time, and is easy to process and excellent in productivity. It is said that it is possible to provide a white resin molded article and an LED reflector having characteristics suitable as a constituent material.

  Patent Document 3 includes a thermoplastic resin, a filler, and a melt viscosity reducing agent, and the melt viscosity reducing agent is a polyfunctional alkyl compound containing a predetermined amount or a dimer acid-based thermoplastic resin containing a predetermined amount. A certain resin composition and a molded body comprising the same have been proposed. According to this technique, it is said that a resin composition excellent in melt fluidity during processing and a molded body comprising the same can be provided.

In particular, recently, in order to further increase the light emission intensity of the LED element, a large current is applied to the LED element. For this reason, the LED element easily generates heat, and the reflector is required to have higher levels of heat resistance and dimensional stability.
Therefore, from the viewpoint of heat resistance, it has been proposed to use a crosslinking agent having a thermogravimetric reduction temperature higher than a specific value (see Patent Document 4). Patent Document 4 discloses that if a crosslinking agent having a temperature of 169 ° C. or higher can be used, high heat resistance can be imparted and it can be produced with good moldability.
Usually, in order to improve heat resistance, it is considered good to increase the addition amount of a crosslinking agent. However, a compound having a high thermogravimetric decrease temperature that is effective in improving heat resistance has a high molecular weight. Therefore, when the amount is increased, the compatibility further decreases. In addition, a compound having a high thermogravimetry temperature often contains an aromatic ring structure.
Since the crosslinking agent disclosed in Patent Document 4 contains an aromatic ring structure, the thermogravimetric reduction temperature is high, but the compatibility with a polyolefin resin excellent in transparency is lowered.
As described above, when the polyolefin resin is used, the distribution of the cross-linking agent in the resin composition becomes non-uniform, and the characteristics of the resulting resin composition and the molded body made of the resin composition vary greatly. For this reason, there existed a subject that it was difficult to apply to the use for which high transparency is requested | required. For this reason, it was difficult to select a crosslinking agent having a high thermogravimetric reduction temperature and good compatibility.

JP 2009-149845 A JP 2011-195709 A International Publication WO2010 / 084845 Japanese Patent Laid-Open No. 2015-23100

  In view of the above problems, the present invention provides a resin composition that is excellent in heat resistance and moldability and that can form a reflector that exhibits stable heat resistance and moldability, a reflector molded from the resin composition, and a lead with reflector An object is to provide a frame and a semiconductor light emitting device. The present invention also provides an isocyanurate compound for a crosslinking agent and a glycoluril compound for a crosslinking agent that can be used in a resin composition capable of forming the reflector, have excellent heat resistance, and have good compatibility with a polyolefin resin. For the purpose.

The present inventors solved the above problems by using a polyolefin resin and an isocyanurate compound having a specific structure, or a polyolefin resin and a glycoluril compound having a specific structure as a crosslinking agent. That is, the present invention
[1] A resin composition comprising a polyolefin resin, a crosslinking agent, and a reinforcing filler, wherein the crosslinking agent is an isocyanurate compound represented by the chemical formula (1).

In the formula, R is an alkylene group having 1 to 16 carbon atoms or an alkylene group having 1 to 16 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, and a carbamate. One selected from a bond, a thiocarbamate bond, and a carbonate bond, or a combination thereof.

[2] A resin composition comprising a polyolefin resin, a crosslinking agent, and a reinforcing filler, wherein the crosslinking agent is a glycoluril compound represented by the chemical formula (2).

In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an allyl group.

[3] The resin composition according to [1] or [2], further including a white pigment or a black pigment.
[4] The resin composition according to any one of [1] to [3], which is cured by ionizing radiation.
[5] The resin composition according to any one of [1] to [4], which is for a reflector.
[6] A reflector comprising a cured product obtained by curing the resin composition according to [5].
[7] A lead frame with a reflector having the reflector according to [6].
[8] A semiconductor light emitting device having the reflector according to [6] or the lead frame with reflector according to claim 7.
[9] An isocyanurate compound for a crosslinking agent represented by the chemical formula (1).

In the formula, R is an alkylene group having 1 to 16 carbon atoms or an alkylene group having 1 to 16 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, and a carbamate. One selected from a bond, a thiocarbamate bond, and a carbonate bond, or a combination thereof.

[10] A glycoluril compound for a crosslinking agent represented by the chemical formula (2).

In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an allyl group.

[11] The isocyanurate compound for a crosslinking agent according to [9], which is for a reflector.
[12] The glycoluril compound for a crosslinking agent according to [10], which is for a reflector.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can form the reflector which is excellent in heat resistance and moldability, and exhibits stable heat resistance and moldability, the reflector shape | molded from this resin composition, a lead frame with a reflector, a semiconductor A light emitting device can be provided. Further, it can be used in a resin composition capable of forming the reflector, and can provide an isocyanurate compound for a crosslinking agent and a glycoluril compound for a crosslinking agent that have excellent heat resistance and good compatibility with a polyolefin resin. .

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

[Resin composition]
Hereinafter, the resin composition according to the embodiment of the present invention will be described in detail. In the present specification, it is possible to arbitrarily adopt a prescription that is preferable, and it can be said that a combination of preferable ones is more preferable.
The resin composition according to the first embodiment contains a polyolefin resin, a crosslinking agent, and a reinforcing filler, and the crosslinking agent is an isocyanurate compound represented by the chemical formula (1).

In the formula, R is an alkylene group having 1 to 16 carbon atoms or an alkylene group having 1 to 16 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, and a carbamate. One selected from a bond, a thiocarbamate bond, and a carbonate bond, or a combination thereof.

  The resin composition according to the second embodiment contains a polyolefin resin, a crosslinking agent, and a reinforcing filler, and the crosslinking agent is a glycoluril compound represented by the chemical formula (2).

In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an allyl group. Here, the lower alkyl group refers to an alkyl group having 1 to 4 carbon atoms.

<Polyolefin resin>
Next, the polyolefin resin applicable to the resin composition according to the first embodiment and the second embodiment will be described. The polyolefin resin 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, for example, 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 them, polyethylene, polypropylene, and polymethylpentene are preferable, 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 ethylene and another comonomer copolymerizable with ethylene (for example, α-olefin such as propylene, 1-butene, 1-hexene, 1-octene, Copolymers with vinyl acetate, vinyl alcohol, etc.) may also be used. 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.

  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, Copolymers with vinyl acetate, vinyl alcohol, etc.) may also be used. 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, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, etc. And a copolymer mainly composed of 4-methyl-1-pentene. In the case of the copolymer, from the viewpoint of heat resistance, those obtained by copolymerizing alkenes having 10 to 18 carbon atoms are preferred, and those obtained by copolymerizing alkenes having 16 or more carbon atoms are more preferred.

  The refractive index of the polyolefin resin is preferably 1.40 to 1.60. Thereby, especially when the molded object obtained by shape | molding a resin composition using a white pigment as a pigment is made into a reflector, light reflectivity can be improved. Moreover, it is preferable that the weight average molecular weights of polyolefin resin are 220,000-800,000. 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 g / L
Injection volume: 300 μL

<Isocyanurate compound>
Next, the crosslinking agent in 1st Embodiment is demonstrated. The cross-linking agent used in the first embodiment is an isocyanurate compound represented by the above chemical formula (1).
The carbon number of R in the chemical formula (1) is preferably 2 to 8 carbon atoms from the viewpoint of obtaining the mixing property with the polyolefin resin, good storage elastic modulus at high temperature, and good dimensional stability. R in the chemical formula (1) may further have an organic group having 1 to 4 carbon atoms as a substituent.
Among the isocyanurate compounds represented by the chemical formula (1), R is an alkylene group,
Ethylene bis (diallyl isocyanurate),
Trimethylene bis (diallyl isocyanurate),
Tetramethylene bis (diallyl isocyanurate),
Pentamethylene bis (diallyl isocyanurate),
Hexamethylene bis (diallyl isocyanurate),
Heptamethylenebis (diallyl isocyanurate),
Octamethylene bis (diallyl isocyanurate),
Nonamethylene bis (diallyl isocyanurate),
Decamethylene bis (diallyl isocyanurate) and dodecamethylene bis (diallyl isocyanurate) can be used.
Among the isocyanurate compounds represented by the chemical formula (1), those in which R has an ether bond include oxydiethylene bis (diallyl isocyanurate) and 1,2-bis (3,5-diallyl isocyanurethoxy) ethane. Is mentioned.

  Furthermore, as the isocyanurate compound represented by the chemical formula (1), those represented by the following chemical formula can be used.

That is, (3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -acetic acid 2- (3,5-diallyl-2,4,6-trioxo- [ 1,3,5] triazinan-1-yl) -ethyl ester,
(3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -propionic acid 2- (3,5-diallyl-2,4,6-trioxo- [1 , 3,5] triazinan-1-yl) -ethyl ester,
(3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -propionic acid 3- (3,5-diallyl-2,4,6-trioxo- [1 , 3,5] triazinan-1-yl) -propyl ester,
Dimethylene bis (diallyl isocyanur) sulfide,
Diethylenebis (diallyl isocyanuric) sulfide,
1,2-bis (3,5-diallyl isocyanurethylthio) ethane,
2- (3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -N- [2- (3,5-diallyl-2,4,6-trioxo -[1,3,5] triazinan-1-yl) -ethyl] -acetamide,
3- (3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -N- [2- (3,5-diallyl-2,4,6-trioxo -[1,3,5] triazinan-1-yl) -ethyl] -propionamide,
3- (3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -N- [3- (3,5-diallyl-2,4,6-trioxo -[1,3,5] triazinan-1-yl) -propyl] -propionamide,
[2- (3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -ethyl] -carbamic acid 2- (3,5-diallyl-2,4, 6-trioxo- [1,3,5] triazinan-1-yl) -ethyl ester,
[2- (3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -ethyl] -carbamic acid 3- (3,5-diallyl-2,4, 6-trioxo- [1,3,5] triazinan-1-yl) -propyl ester,
[3- (3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -propyl] -carbamic acid 2- (3,5-diallyl-2,4, 6-trioxo- [1,3,5] triazinan-1-yl) -ethyl ester,
1,3-bis- [2- (3,5-diallyl isocyanur) -ethyl] -urea,
1- [2- (3,5-diallyl isocyanur) -ethyl] -3- [3- (3,5-diallyl isocyanur) -propyl] -urea,
1,3-bis- [3- (3,5-diallyl isocyanur) -propyl] -urea,
[2- (3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -ethyl] -thiocarbamic acid O- [2- (3,5-diallyl- 2,4,6-trioxo- [1,3,5] triazinan-1-yl) -ethyl] ester,
[2- (3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -ethyl] -thiocarbamic acid O- [3- (3,5-diallyl- 2,4,6-trioxo- [1,3,5] triazinan-1-yl) -propyl] ester,
[3- (3,5-diallyl-2,4,6-trioxo- [1,3,5] triazinan-1-yl) -propyl] -thiocarbamic acid O- [2- (3,5-diallyl- 2,4,6-trioxo- [1,3,5] triazinan-1-yl) -ethyl] ester,
Carbonic acid bis [2- (3,5-diallyl isocyanur) -ethyl] ester,
Carbonic acid bis [3- (3,5-diallyl isocyanur) -propyl] ester and carbonic acid bis [4- (3,5-diallyl isocyanuric) -butyl] ester can be used.
The above-mentioned isocyanurate compounds may be used alone or in combination of two or more.

The purity of the isocyanurate compound is preferably 90% or more, and more preferably 95% or more. The purity of the isocyanurate compound is largely governed by the content of by-products at the time of production. The main component of this by-product is an amine compound formed by ring opening by imide bond cleavage in the isocyanuric ring. . This amine compound is known to inhibit the crosslinking function of the isocyanurate compound and cause coloration of the cured product.
The isocyanurate compound can be produced by various synthetic methods, but generally, during a synthesis reaction using a strong base such as sodium hydroxide as a base, the isocyanuric ring is easy to open, resulting in a decrease in yield. There's a problem. In addition, since this amine compound is similar in polarity to the isocyanurate compound, such an amine compound cannot be easily separated (removed) from the isocyanurate compound.
In addition, when an isocyanuric ring is opened, an amine compound is generated as a by-product, and when this amine compound is contained (mixed) as an impurity of the isocyanurate compound, the curing characteristics of the resin are obtained when used as a resin crosslinking agent. Decreases and causes coloration of the cured product.

Under such circumstances, the isocyanurate compound is preferably produced by a synthesis method in which the production of an amine compound is suppressed as a by-product.
More specifically, in the production of the isocyanurate compound, a carbonate that is a weak base is used as a base when 1,3-diallyl isocyanurate is reacted with a dihalogen compound.
That is, the isocyanurate compound is preferably produced by reacting 1,3-diallyl isocyanurate with a dihalogen compound using a carbonate.
Since a weak base carbonate is used as the base, the opening of the isocyanuric ring during production is suppressed, and purification of the isocyanurate compound as a reaction product is easy. And since the purity is raised, when the said isocyanurate compound is added to resin, the crosslinking function which the said isocyanurate compound originally has can be exhibited.

  The isocyanurate compound represented by the chemical formula (1) is excellent in compatibility with the polyolefin resin contained as another component of the resin composition. Moreover, the favorable storage elastic modulus under high temperature can be provided to the hardened | cured material obtained by hardening the said resin composition. Furthermore, since it is excellent also in dimensional stability, it is suitable as a crosslinking agent for forming the reflector mounted in a semiconductor light-emitting device. That is, the isocyanurate compound represented by the chemical formula (1) can be said to be an isocyanurate compound for a crosslinking agent.

<Glycoluril compound>
Next, the crosslinking agent in 2nd Embodiment is demonstrated. The crosslinking agent used in the second embodiment is a glycoluril compound represented by the above chemical formula (2).
Examples of the glycoluril compound represented by the chemical formula (2) include 1-allylglycoluril, 1,3-diallylglycoluril, 1,4-diallylglycoluril, 1,6-diallylglycoluril, 1,3,4-tril. Allyl glycoluril, 1,3,4,6-tetraallylglycoluril, 1-allyl-3a-methylglycoluril, 1,3-diallyl-3a-methylglycoluril, 1,4-diallyl-3a-methylglycoluril 1,6-diallyl-3a-methylglycoluril, 1,3,4-triallyl-3a-methylglycoluril, 1,3,4,6-tetraallyl-3a-methylglycoluril, 1-allyl-3a, 6a -Dimethyl glycoluril, 1,3-diallyl-3a, 6a-dimethylglycol Uril, 1,4-diallyl-3a, 6a-dimethylglycoluril, 1,6-diallyl-3a, 6a-dimethylglycoluril, 1,3,4-triallyl-3a, 6a-dimethylglycoluril, 1,3, 4,6-tetraallyl-3a, 6a-dimethylglycoluril, 1-allyl-3a, 6a-diphenylglycoluril, 1,3-diallyl-3a, 6a-diphenylglycoluril, 1,4-diallyl-3a, 6a- Diphenylglycoluril, 1,6-diallyl-3a, 6a-diphenylglycoluril, 1,3,4-triallyl-3a, 6a-diphenylglycoluril, 1,3,4,6-tetraallyl-3a, 6a-diphenylglycol And uril. The glycoluril compounds described above may be used alone or in combination of two or more.
The glycoluril compound represented by the chemical formula (2) includes 1,3,4,4, from the viewpoint of obtaining a mixing property with a polyolefin resin, a good storage elastic modulus at a high temperature, and a good dimensional stability. 6-tetraallylglycoluril is particularly preferred.
The glycoluril compound represented by the chemical formula (2) can impart a good storage elastic modulus at a high temperature to a cured product obtained by curing the resin composition. Furthermore, in order to show favorable dimensional stability, it is suitable as a crosslinking agent for forming the reflector mounted in a semiconductor light-emitting device. That is, the glycoluril compound represented by the chemical formula (2) can be referred to as a glycoluril compound for a crosslinking agent.

<Reinforcing filler>
In both the first embodiment and the second embodiment, the resin composition needs to contain a reinforcing filler. By including the reinforcing filler, the strength of the cured product obtained by curing the resin composition can be improved.
The reinforcing filler is contained in the resin composition and its cured product. Moreover, it is contained in the reflector with the resin composition and the white material. That is, the reinforcing filler is included in the reflector forming composition for forming the reflector, and is included in the reflector formed of the reflector forming composition together with the cured product of the resin composition and the white material. Yes. As the reinforcing filler, glass fibers can be preferably mentioned, but fibers made of other materials may be used. For example, fibers such as wollastonite, acicular titanium oxide, acicular potassium titanate, talc, carbon fiber, boron fiber, aramid fiber, polyethylene fiber, and fibrous xylon may be used. These reinforcing fillers can be used alone or in combination of two or more.

The reinforcing filler preferably has an average length (fiber length) in the range of 40 μm to 100 μm. By setting the fiber length within this range, a large amount of reinforcing filler is filled in the cured product, and the strength of the obtained reflector can be increased. In addition, long glass fibers as in the prior art rarely jump out of the reflector surface and inhibit light reflectivity.
Moreover, if it is in the said range, the injection moldability at the time of reflector formation is possible, without preventing the fluidity | liquidity of a resin composition.
Furthermore, a relatively long glass fiber is broken by a mechanical mixing means at the time of preparing the resin composition to generate a mechano radical, and the mechano radical tends to deteriorate the electron beam curable material. This fibrous material is less likely to generate such mechano radicals and can suppress deterioration of the resin composition and its cured product according to this embodiment.

  The cross-sectional form of the reinforcing filler is not particularly limited, and may be a circular cross section or an irregular cross section. The average diameter of the cross section is preferably in the range of 5 μm to 50 μm. The average length and diameter of the reinforcing filler can be measured with an optical microscope, X-ray CT or the like on the surface or cross section of the molded body obtained from the resin composition.

  By adding a reinforcing filler, the coefficient of thermal expansion (CTE) can be reduced. In general, since the difference between the coefficient of thermal expansion (CTE) and a lead frame made of copper (CTE = 18 ppm / ° C.) can be reduced, warping can be suppressed when the reflector and the lead frame are integrated by insert molding. In addition, by making the linear expansion coefficient of the reflector close to that of the lead frame in this way, the difference in dimensional change in an environment where the temperature changes rapidly, such as in a heat cycle test, is reduced. As a result, the reflector and the lead frame Adhesion with is improved. The linear expansion coefficient of the resin composition of the present invention and its cured product is preferably 5 to 40 ppm / ° C, more preferably 10 to 30 ppm / ° C.

In the present embodiment, the reinforcing filler that can be used in the resin composition is preferably a fibrous filler. The radial cross-sectional area of the fibrous filler is preferably 1 μm ² or more and 100 μm ² or less.
If the cross-sectional area in the radial direction of the fibrous filler is 1 μm ² or more, it is difficult to break in the fiber length direction during processing, it is difficult to break, a sufficient reinforcing effect can be obtained, and the heat resistance of the molded body can be increased.
If the cross-sectional area in the radial direction of the fibrous filler is 100 μm ² or less, good fluidity is obtained, it can be uniformly filled to the vicinity of the interface between the reflector and the substrate, and sufficient strength near the interface is obtained, When used in a semiconductor light emitting device or the like, the adhesion between the reflector and the substrate can be enhanced.
From the above viewpoint, the lower limit value of the cross-sectional area in the radial direction of the fibrous filler is preferably 30 μm ² , and more preferably 35 μm ² . The upper limit of the cross-sectional area in the radial direction of the fibrous filler is preferably a 85 .mu.m ^2, more preferably 50 [mu] m ^2.
As the fibrous filler, asbestos fiber, carbon fiber, graphite fiber, metal fiber, slag fiber, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, glass fiber, etc. Can be mentioned.
Among these, from the viewpoint of forming the light reflecting surface of the reflector and improving the light reflectivity, it is preferable to use glass fibers in which the fibrous filler contains 60% by mass or more of silicon dioxide. The ratio of silicon dioxide in the fibrous filler 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 fibers need not have 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.

  Plate-like or particulate reinforcing 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 It is preferable to use carbon nanoparticles such as sericite, zeolite, bentonite, dolomite, kaolin, powdered silicic acid, feldspar powder, shirasu balloon, gypsum, novaculite, dosonite, and white clay fullerene.

<Pigment>
In both the first embodiment and the second embodiment, the resin composition may contain a white pigment or a black pigment. By including a white pigment or a black pigment, the light reflectance of the cured product obtained by curing the resin composition can be increased or decreased.
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 can give a white color tone to the cured product obtained by curing the resin composition according to the present embodiment, and particularly when the color tone is highly white, the light reflection of the cured product. The rate can be improved.
What improved the light reflectivity of the hardened | cured material obtained by hardening the resin composition which concerns on this embodiment 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 diameter of the white pigment can be obtained as a mass average value D50 in particle size distribution measurement by a laser light diffraction method. The average particle size of the white pigment is preferably 0.05 to 100 μm, and preferably 0.1 to 10 μm in the primary particle size distribution from the viewpoint of obtaining the moldability of the resin composition and obtaining high reflectance. Is more preferable, and it is still more preferable that it is 0.2-1 micrometer.
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), and a black product is obtained by curing the resin composition according to this embodiment. Color tone can be imparted, and the light reflectance of the cured product can be reduced.
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.

<Fluidity improver>
When the resin composition according to the present embodiment includes the above-described pigment and reinforcing filler, it is preferable to include a fluidity improver. Thereby, the moldability of a resin composition can be improved.
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 this embodiment, it is used as a silane coupling agent from the viewpoint that the dispersibility and compatibility of the inorganic substance with respect to the resin are high, and the reflectance, mechanical characteristics, and dimensional stability when used as a reflector can be improved. It is preferable to use a silane compound.
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.

<Other additives>
Any resin composition of the first embodiment and the second embodiment can contain various additives other than the above-described compounds as long as the effects of the present invention are not 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.

<Combination ratio of each component>
(Crosslinking agent)
The amount of the crosslinking agent (isocyanurate compound represented by chemical formula (1)) in the resin composition according to the first embodiment and the crosslinking agent (glycol represented by chemical formula (2) in the resin composition according to the second embodiment. The blending amount of (uril compound) is preferably 0.1 to 50 parts by mass, and preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyolefin resin.
By setting the blending amount of the isocyanurate compound represented by the chemical formula (1) and the blending amount of the glycoluril compound represented by the chemical formula (2) within the above ranges, the moldability of the resin composition and the resin composition are cured. It is possible to achieve both the heat resistance of the cured product.
(Reinforcing filler)
In both the resin composition according to the first embodiment and the resin composition according to the second embodiment, the compounding amount of the reinforcing filler may be 60 to 200 parts by mass with respect to 100 parts by mass of the polyolefin resin. Preferably, it is more preferable to set it as 80-150 mass parts. By making the compounding quantity of a reinforcing filler into the said range, sufficient intensity | strength can be provided to the hardened | cured material obtained by hardening a resin composition. Moreover, by setting it as the said range, a molded object can be obtained by injection molding using the said resin composition.
(Pigment)
In both the resin composition according to the first embodiment and the resin composition according to the second embodiment, the blending amount of the white pigment or the black pigment is 10 to 1000 parts by mass with respect to 100 parts by mass of the polyolefin resin. Is preferable, it is more preferable to set it as 50-800 mass parts, and it is more preferable to set it as 100-600 mass parts. By making the blending amount of the pigment within the above range, in the cured product obtained from the resin composition, the effect of the pigment can be sufficiently exhibited, and the moldability is ensured when the resin composition is molded. Can do.
(Fluidity improver)
When both the resin composition according to the first embodiment and the resin composition according to the second embodiment use a fluidity improver, the blending amount is 0.1 with respect to 100 parts by mass of the polyolefin resin. It is preferable to set it as -50 mass parts.

[Resin composition for reflector]
The resin composition described above is suitable as a reflector resin composition for forming a reflector of a semiconductor light emitting device.

[Reflector]
A reflector of a semiconductor light emitting device can be formed from the resin composition according to this embodiment described above. The reflector mainly has an action of reflecting light from the LED element of the semiconductor light emitting device toward the lens (light emitting portion). Details of the reflector will be described together with a semiconductor light emitting device described later. The reflector may be incorporated in the semiconductor light emitting device, or may be used in combination with a semiconductor light emitting device (LED mounting substrate) made of another material.
In order to manufacture the reflector according to the present embodiment, first, a granulated product such as a pellet is formed by melt-kneading the above resin composition. 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.
Furthermore, the resin composition is formed into a predetermined shape using various molding methods. 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, a molded body can be obtained by injection molding at a cylinder temperature of 200 to 400 ° C. and a mold temperature of 20 to 150 ° C.
A cured product of the resin composition can be obtained by curing the molded body thus obtained. As a curing method, a method of irradiating with ionizing radiation can be used. As the ionizing radiation, an electron beam or an ultraviolet ray can be used. 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 used crosslinking agent 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. Further, the absorbed dose when irradiating with an electron beam is appropriately set depending on the composition of the resin composition, but an amount at which the crosslinking density in the molded body is saturated is preferable, and the irradiated dose is preferably 50 to 600 kGy, particularly It is preferable that it is 100-250 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.
The reflector can be formed from a cured product obtained by curing the resin composition with ionizing radiation as described above.

[Lead frame with reflector]
In the lead frame with reflector according to the embodiment of the present invention, the lead frame refers to a substrate on which the reflector is placed. The lead frame with a reflector according to the embodiment of the present invention can be formed using a reflector made of a cured product of the resin composition described above.
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 described above on the above-described lead frame into a desired reflector shape and curing it.
The thickness of the lead frame with reflector according to the present embodiment (reflector thickness) is preferably 0.02 to 3.0 mm, more preferably 0.05 to 1.0 mm, and 0.05 to More preferably, it is 0.8 mm.
The lead frame with a reflector according to the present embodiment can be made into a semiconductor light emitting device by mounting an LED element on the reflector, further sealing with a known sealant, and die bonding to obtain a desired shape. it can.
In addition, although the lead frame with a reflector which concerns on this embodiment acts as a reflector, it is functioning also as a frame which supports a semiconductor light-emitting device. In particular, the strength of the semiconductor light emitting device can be increased by forming the reflector including the reinforcing filler so as to surround the periphery of the semiconductor light emitting device.

[Semiconductor light-emitting device]
The semiconductor light emitting device according to this embodiment will be described with reference to the drawings. As shown in FIG. 1, the semiconductor light emitting device according to this embodiment includes an optical semiconductor element 10 and a light reflecting surface that is provided around the optical semiconductor element 10 and reflects light from the optical semiconductor element 10 in a predetermined direction. And a reflector 12 having the above structure on the substrate 14. The optical semiconductor element 10 is preferably an LED element or an LED package. In the semiconductor light emitting device, the reflector 12 is formed of a molded body made of the resin composition described above, at least a part of the light reflecting surface (in the case of FIG. 1, all).
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). In the case of the semiconductor light emitting device shown in FIG. 1, the thickness at the upper end surface of the reflector 12 is smaller than the thickness at the end surface on the fixed side with respect to the substrate. It is possible to increase the strength of the upper side end surface of.
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 be formed only on the light reflecting surface side as a light reflecting layer 12b made of the resin composition described above. 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. The lens 18 is made of a 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 encapsulant composition) that imparts light-transmitting properties and insulating properties 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 a resin composition described later 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.

The present invention will be described in detail using examples. The present invention is not limited to these examples.
[Production example of crosslinking agent]
<Production Example 1>
4.18 g (20.0 mmol) of 1,3-diallyl isocyanurate, 1.27 g (10.0 mmol) of 1,4-dichlorobutane and 166 mg (1.0 mmol) of potassium iodide were mixed with N, N-dimethylformamide. While stirring at room temperature with 10 mL, 4.15 g (30.0 mmol) of potassium carbonate was added thereto and stirred at 110 ° C. for 6 hours.
The resulting reaction mixture was then filtered to remove solids and the resulting filtrate was concentrated under reduced pressure. To the obtained concentrate, 30 mL of toluene and 10 mL of water were added and stirred at room temperature for 1 hour, and then the aqueous layer was removed. After concentrating the organic layer thus obtained under reduced pressure, 30 mL of hexane was added, and the precipitated crystals were separated by filtration and dried to obtain 4.63 g of tetramethylenebis (diallyl isocyanurate). The yield was 98%.
The NMR spectrum of the crystal of the obtained reaction product was measured, and compared with the NMR spectrum of the sample, it was confirmed that it was tetramethylene bis (diallyl isocyanurate) represented by the following chemical formula. Further, HPLC analysis confirmed that the purity was 97%. Hereinafter, tetramethylene bis (diallyl isocyanurate) may be referred to as a crosslinking agent 1.

<Production Example 2>
1.18 g (20.0 mmol) of 1,3-diallyl isocyanurate, 1.87 g (10.0 mmol) of 1,2-bis (2-chloroethoxy) ethane and 166 mg (1.0 mmol) of potassium iodide were added. While stirring at room temperature with 10 mL of N, N-dimethylformamide, 4.15 g (30.0 mmol) of potassium carbonate was added thereto, and the mixture was stirred at 110 ° C. for 6 hours.
The resulting reaction mixture was then filtered to remove solids and the resulting filtrate was concentrated under reduced pressure. To the obtained concentrate, 30 mL of toluene and 10 mL of water were added and stirred at room temperature for 1 hour, and then the aqueous layer was removed. The obtained organic layer was concentrated under reduced pressure to obtain 4.80 g of 1,2-bis (3,5-diallyl isocyanurethoxy) ethane. The yield was 90%.
The NMR spectrum of the crystal of the obtained reaction product was measured, and compared with the NMR spectrum of the sample, it was confirmed that it was 1,2-bis (3,5-diallyl isocyanurethoxy) ethane represented by the following chemical formula. . Further, HPLC analysis confirmed that the purity was 97%. Hereinafter, 1,2-bis (3,5-diallyl isocyanurethoxy) ethane may be referred to as the crosslinking agent 2.

<Production Example 3>
4.18 g (20.0 mmol) of 1,3-diallyl isocyanurate, 1.43 g (10.0 mmol) of bis (2-chloroethyl) ether and 166 mg (1.0 mmol) of potassium iodide were mixed with N, N-dimethyl. While stirring at room temperature with 10 mL of formamide, 4.15 g (30.0 mmol) of potassium carbonate was added thereto, and the mixture was stirred at 110 ° C. for 6 hours.
The resulting reaction mixture was then filtered to remove solids and the resulting filtrate was concentrated under reduced pressure. To the obtained concentrate, 30 mL of toluene and 10 mL of water were added and stirred at room temperature for 1 hour, and then the aqueous layer was removed. The obtained organic layer was concentrated under reduced pressure to obtain 4.78 g of oxydiethylenebis (diallyl isocyanurate). The yield was 98%.
The NMR spectrum of the crystal of the obtained reaction product was measured, and compared with the NMR spectrum of the sample, it was confirmed that it was oxydiethylenebis (diallyl isocyanurate) represented by the following chemical formula. Further, HPLC analysis confirmed that the purity was 95%. Hereinafter, oxydiethylenebis (diallyl isocyanurate) may be referred to as the crosslinking agent 3.

<Production Example 4>
The compound was synthesized according to the method described in JP-A-11-171887. That is, 14.2 g (100 mmol) of glycoluril, 16.0 g (400 mmol) of sodium hydroxide and 140 mL of dimethyl sulfoxide were mixed, heated and stirred at 40 ° C. for 1 hour, and then 34.4 g (400 mmol) of allyl chloride was added at the same temperature. It was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was further heated and stirred at 40 ° C. for 2 hours to complete the reaction.
The resulting reaction mixture was evaporated to dryness. The obtained dried product was subjected to liquid separation extraction with 400 mL of ethyl acetate and 400 mL of water. The ethyl acetate layer was washed with 100 mL of water and then with 100 mL of saturated brine, and then dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and 1,3,4,6-tetraallylglycoluril 27. 4 g were obtained as a colorless oil. The yield was 90%.
The liquid NMR spectrum of the obtained reaction product was measured, and compared with the NMR spectrum of the sample, it was confirmed that it was 1,3,4,6-tetraallylglycoluril represented by the following chemical formula. Further, HPLC analysis confirmed that the purity was 95%. Hereinafter, 1,2,4,6-tetraallylglycoluril may be referred to as a crosslinking agent 4 in some cases.

<Comparison cross-linking agent 1>
As a comparative crosslinking agent, diallyl isophthalate represented by the following chemical formula (Daiso Corporation, Daiso Dup 100 monomer) was used.

<Comparison crosslinking agent 2>
As a comparative crosslinking agent, triallyl isocyanurate represented by the following chemical formula (manufactured by Nippon Kasei Co., Ltd., TAIC) was used.

[Evaluation of 2% weight loss temperature]
The 2% weight reduction temperatures of the crosslinking agents 1 to 4 and the comparative crosslinking agents 1 and 2 were measured with TG-DTA (type name: TG8120, manufactured by Rigaku Corporation). In accordance with JIS K7120, the temperature was raised from room temperature to 750 ° C., and the temperature was 2% lower than the total weight.

  From these results, it was confirmed that the crosslinking materials 1 to 4 according to the present invention had a high 2% weight loss temperature of 212 ° C. or higher and good thermal stability.

[Evaluation of polyolefin mixing properties]
To 100 parts by mass of polymethylpentene resin (manufactured by Mitsui Chemicals, TPX RT18), 8 parts by mass of the crosslinking agent 1 was added and kneaded to obtain a resin composition 1. Similarly, resin compositions 2 to 4 were obtained using each of the crosslinking agents 2 to 4. Similarly, comparative resin compositions 1 and 2 were obtained from comparative crosslinking agents 1 and 2. Further, the obtained resin compositions 1 to 4 and comparative resin compositions 1 and 2 were pressed at 260 ° C. and 30 MPa using a hydraulic press machine, and press plates 1 to 4 of the resin composition for mixing evaluation. And comparative press plates 1 and 2 were obtained. The appearance of the press plate made of the specimen resin composition was evaluated based on the following indices.
Transparent: A
Cloudiness (translucent): B
Bleed-out or partially opaque part was observed: C
Those that are transparent have high compatibility and are presumed to be uniformly mixed. Moreover, it is estimated that the thing which is cloudy has low compatibility, and the thing which has bleed out or a partially opaque part has very bad compatibility.

  From these results, it was confirmed that the crosslinking materials 1 to 4 according to the present invention have good compatibility with polymethylpentene.

[Adjustment of resin composition]
The cross-linking agent 1, polyolefin resin and various materials obtained by the above production examples were kneaded with the formulation shown in Table 3 to obtain a resin composition 5. Similarly, using each of the crosslinking agents 2 to 4 and the comparative crosslinking agents 1 and 2, the compositions shown in Table 3 were kneaded to obtain resin compositions 6 to 8 and comparative resin compositions 3 and 4.

In Table 3,
* 1 Polymethylpentene resin TPX RT18 (Mitsui Chemicals)
* 2 Titanium oxide PF-691 (Ishihara Sangyo Co., Ltd. Rutile structure average particle size 0.21 μm)
* 3 Inorganic filler Glass fiber: PF70E-001 (manufactured by Nittobo Co., Ltd., fiber length 70 μm, average cross-sectional area 95.0 μm ² , cross-sectional shape is round)
* 4 Dispersant KBM-3063 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 5 Antioxidant IRGANOX 1010 (BASF Japan Ltd.)
* 6 Antioxidant ADK STAB PEP36 [Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, manufactured by ADEKA Corporation]
* 7 Zinc stearate SZ-2000 (manufactured by Sakai Chemical Co., Ltd.)

[Evaluation of light reflectance]
Using the resin composition 5 described above, a molded body 1 was obtained by the following method. Similarly, moldings 2 to 4 were obtained using the resin compositions 6 to 8, respectively. Similarly, comparative molded bodies 1 and 2 were obtained using the comparative resin compositions 3 and 4, respectively.
A specimen for light reflectance measurement was produced under the following molding conditions. That is, press molding was performed at 750 mm × 750 mm × thickness 0.2 mm under the conditions of 250 ° C., 30 seconds, and 20 MPa. These molded bodies were irradiated with an electron beam at an acceleration voltage of 250 kV and an absorbed dose of 340 kGy to obtain a cured product for testing. About the obtained hardened | cured material for a test, the reflectance of the wavelength range 230-780 nm was measured with the spectrophotometer (Shimadzu Corporation make, UV-2550). The light reflectance (%) at a wavelength of 450 nm was evaluated. The results are shown in Table 4.

[Evaluation of storage modulus]
Each of the above-mentioned resin compositions 5-8 and comparative resin compositions 3-4 is 700 μm thick on a silver plating frame (thickness 250 μm) using an injection molding machine (Sodick Corporation TR55EH, pre-plastic type), Molded to have an outer dimension of 35 mm × 35 mm and an opening of 2.9 mm × 2.9 mm, and molded bodies 5 to 8 and comparative molded bodies 3 and 4 were obtained.
The conditions of the injection molding machine were as follows: cylinder temperature: 260 ° C., mold temperature: 70 ° C., injection speed: 200 mm / second, holding pressure: 100 MPa, holding pressure time: 1 second, cooling time: 15 seconds.
These molded bodies were irradiated with an electron beam at an acceleration voltage of 800 kV and an absorbed dose of 340 Gy to obtain a cured product. The storage elastic modulus of the obtained cured product 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 modulus at 270 ° C. is shown in Table 5 below.

As is clear from the results in Tables 1 and 2, the crosslinking agents 1 to 4 had good mixing properties with the polyolefin resin. This is presumably because the structure has an alkyl chain and an alkyl ether chain, so the compatibility with the olefin chain of the polyolefin resin is high. Moreover, since the crosslinking agents 1 to 4 have a high 2% weight loss temperature, they are excellent in heat resistance.
Also, from Tables 4 and 5, the molded products using the comparative crosslinking agents 1 and 2 had poor compatibility with the polyolefin resin, although the storage elastic modulus at 270 ° C. satisfied the required performance. Since the comparative crosslinking agent 1 has a low 2% weight loss temperature, it was found that the molded body using the comparative crosslinking agents 1 and 2 lacks heat resistance.
From the above, by using the crosslinking agents 1 to 4, it is possible to obtain a resin composition having not only heat resistance and moldability but also uniformity, a reflector, a lead frame with a reflector, and a semiconductor light emitting device.

  DESCRIPTION OF SYMBOLS 10 ... Optical semiconductor element, 12 ... Reflector, 12a ... Member, 12b ... Light reflection layer, 14 ... Board | substrate, 16 ... Lead wire, 18 ... Lens

Claims (12)

Containing a polyolefin resin, a crosslinking agent, and a reinforcing filler,
A resin composition in which the crosslinking agent is an isocyanurate compound represented by the chemical formula (1).

(In the formula, R is an alkylene group having 1 to 16 carbon atoms or an alkylene group having 1 to 16 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, It is selected from any one of carbamate bond, thiocarbamate bond, and carbonate bond, or a combination thereof. Containing a polyolefin resin, a crosslinking agent, and a reinforcing filler,
A resin composition in which the crosslinking agent is a glycoluril compound represented by the chemical formula (2).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an allyl group.)   Furthermore, the resin composition of Claim 1 or 2 containing a white pigment or a black pigment.   The resin composition according to any one of claims 1 to 3, which is cured by ionizing radiation.   It is for reflectors, The resin composition of any one of Claims 1-4.   A reflector comprising a cured product obtained by curing the resin composition according to claim 5.   A lead frame with a reflector having the reflector according to claim 6.   The semiconductor light-emitting device which has the reflector of Claim 6, or the lead frame with a reflector of Claim 7. An isocyanurate compound for a crosslinking agent represented by the chemical formula (1).

(In the formula, R is an alkylene group having 1 to 16 carbon atoms or an alkylene group having 1 to 16 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, It is selected from any one of carbamate bond, thiocarbamate bond, and carbonate bond, or a combination thereof. A glycoluril compound for a crosslinking agent represented by the chemical formula (2).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an allyl group.)   The isocyanurate compound for a crosslinking agent according to claim 9, which is used for a reflector.   The glycoluril compound for a crosslinking agent according to claim 10, which is used for a reflector.