JP6680132B2 - Resin composition, method for producing resin composition, and light emitting device - Google Patents

Description

  The present invention relates to a resin composition, a method for producing the resin composition, and a light emitting device.

  BACKGROUND ART Conventionally, a surface mount type light emitting device including a resin package and a light emitting element provided in a recess of the package has been widely used. In this light emitting device, the light emitting element is mounted on the lead exposed on the bottom surface of the recess. In the light emitting device configured as described above, the light emitted from the light emitting element is emitted from the opening of the concave portion. For example, the light emitting element such as a light emitting diode emits a large amount of light not only in the upward direction but also in the lateral direction. Therefore, in order to increase the light extraction efficiency of the light emitting device, it is necessary to effectively extract the light emitted laterally from the light emitting element through the opening of the recess. Therefore, the light extraction efficiency is improved by inclining the side wall around the recess of the package so that the opening area increases toward the opening and increasing the reflectance of the bottom surface and side wall of the recess.

  In the resin package, as a method of increasing the reflectance of the bottom surface and the side wall of the recess, which is the surface of the resin, there is a method of manufacturing the package by adding a reflecting material to the resin and, for example, injection molding. The package formed by this method can have higher reflectance as the content of the reflective material increases, but when the filling amount of the reflective material in the resin increases, the fluidity of the resin deteriorates and the package is molded. Becomes difficult.

  In view of this, attempts have been made to prevent the deterioration of the fluidity of the resin by adding the surface-reflecting material to the resin in advance. For example, Patent Literature 1 discloses a resin in which a white pigment as a reflector is subjected to a hydrophobic treatment with a coupling agent such as a silane coupling agent or a titanium coupling agent, and then included in a resin. Further, in Patent Document 2, titanium oxide as a reflecting material is surface-treated with a surface treatment agent such as a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or an organic substance such as silicone, and then contained in a resin. It is disclosed.

JP 2012-124428 A JP, 2013-032539, A

  However, even if the members described in Patent Documents 1 and 2 are used, the fluidity of the reflective material is insufficient, and it is difficult to highly fill the reflective material.

  Therefore, an object of the present embodiment is to provide a resin composition for a package, which improves the fluidity of a reflecting material and improves the light extraction efficiency, a method for producing the same, and a light emitting device.

The resin composition of one embodiment according to the present invention,
A resin composition comprising a polyamide (A) and a reflecting material (C) treated with a phosphorous acid type titanate coupling agent (B) represented by the following general formula 1.
(R'-O) _6-a- Ti- [P- (OR ") _m (OH) _3-m ] _a ... General formula 1
R'is an alkyl group,
a is an integer of 1 to 6,
R ″ is an alkyl group represented by CnH _{n + 1 in} which _n is an integer of 1 to 30,
m is an integer of 0 to 3,
Is.

A light emitting device according to an embodiment of the present invention is
A package including a resin molding part made of the resin composition according to the embodiment of the present invention and a lead electrode embedded in the resin molding part, and a light emitting element connected to the lead electrode.

The method for producing a resin composition according to one embodiment of the present invention,
A treatment step of treating the reflecting material (C) with the phosphorous acid titanate coupling agent (B) represented by the following general formula 1,
(R'-O) _6-a- Ti- [P- (OR ") _m (OH) _3-m ] _a ... General formula 1
R ′ is an alkyl group a is an integer of 1 to 6 R ″ is an alkyl group represented by CnH _{n + 1} where _n is an integer of 1 to 30 is an integer of 0 to 3 Polyamide (A), and A mixing step of mixing the phosphorous acid-type titanate-based coupling agent (B) and the reflecting material (C),
including.

  According to the resin composition, the method for producing the same, and the light emitting device of the embodiment of the present invention, it is possible to provide a light emitting device with good light extraction efficiency.

It is a perspective view which shows the structure of the light-emitting device of Embodiment 2 which concerns on this invention.

Hereinafter, the resin composition of the embodiment according to the present invention will be described.
As described above, the light emitting device package is manufactured using, for example, a resin containing a reflective material such as titanium oxide particles in order to increase the light extraction efficiency. However, if the resin contains a reflective material, the fluidity of the resin deteriorates. Therefore, the surface-treated reflective material is contained in the resin to suppress the deterioration of the fluidity of the resin.

  For example, when a light emitting device was manufactured using a package in which titanium oxide surface-treated with a phosphorous acid type titanate coupling agent was molded with polyamide, the light extraction efficiency was improved. On the other hand, a light emitting device using a package formed of polyamide containing titanium oxide surface-treated with an amine titanate coupling agent, a pyrophosphoric acid type titanate coupling agent and a carboxylic acid type titanate coupling agent is used. When manufactured, the titanate coupling agent itself undergoes thermal discoloration during manufacturing of the light-emitting device, and the reflectance of the side wall is decreased, and the light extraction efficiency is decreased.

Therefore, each surface treatment agent of the phosphorous acid type titanate coupling agent, the amine type titanate coupling agent, the pyrophosphoric acid type titanate coupling agent and the carboxylic acid type titanate coupling agent is dropped onto a glass plate with a pipette and dried. It was heated at a temperature of 320 ° C. for 30 seconds, and the degree of discoloration was visually confirmed.
As a result, no discoloration was observed for the diphosphite type titanate coupling agent, but any discoloration was observed for the amine titanate coupling agent, the pyrophosphoric acid type titanate coupling agent and the carboxylic acid type titanate coupling agent. confirmed.

Specifically, in the color change confirmation experiment,
Regarding the phosphorous acid-type titanate coupling agent, two types of tetraoctylbis (ditridecylphosphite) titanate and tetraisopropylbis (dioctylphosphite) titanate were confirmed, and no discoloration was observed.
Further, as the amine titanate coupling agent, isopropyl tri (N-amidoethyl aminoethyl) titanate,
Pyrophosphate-type titanate coupling agent, bis (dioctyl pyrophosphate) oxyacetate titanate,
Isopropyltriisostearoyl titanate was confirmed as a carboxylic acid type titanate coupling agent, and discoloration was confirmed in all cases.

Here, tetraoctyl bis (ditridecyl phosphite) titanate is
Chemical _{Formula: (C 8 H 17 -O)} 4 -Ti- [P- (O-C 13 H 27) 2 OH] 2
Is represented by
Tetraisopropyl bis (dioctyl phosphite) titanate is
Chemical _{formula: [(CH 3) 2 CH} -O] 4 -Ti- [P- (O-C 8 H 17) 2 OH] 2
It is represented by.

  Hereinafter, each configuration of the embodiment according to the present invention will be described in detail.

Embodiment 1.
The resin composition of Embodiment 1 is a resin composition suitable for producing a package of an optical semiconductor device such as a light emitting device,
A resin composition comprising a polyamide (A) and a reflecting material (C) treated with a phosphorous acid type titanate coupling agent (B) represented by the following formula 1.
(R'-O) _6-a- Ti- [P- (OR ") _m (OH) _3-m ] _a ... General formula 1
Here, in Formula 1, R ′ is an alkyl group,
a is an integer of 1 to 6,
R ″ is an alkyl group represented by C _n H _{n + 1} where _n is an integer of 1 to 30,
m is an integer of 0-3.

  Hereinafter, each component will be specifically described.

<Polyamide (A)>
The polyamide used in the first embodiment is not particularly limited, but it is preferable to use a polyamide having a high melting point and high heat resistance. As the polyamide having a high melting point and high heat resistance, a semi-aromatic polyamide, a semi-fat Examples include cyclic polyamides. Among the semi-aromatic amides and semi-alicyclic polyamides, polyhexamethylene terephthalamide (PA6T), polynonamethylene terephthalamide (PA9T), polydecamethylene terephthalamide (PA10T), polyhexamethylene cyclohexanedicarboxamide (PA6C), polynonamethylenecyclohexanedicarboxamide (PA9C), polydecamethylenecyclohexanedicarboxamide (PA10C) and the like are particularly desirable. Regarding the above polyamide, one kind of polyamide may be used alone, or two or more kinds of polyamide may be used in combination.

<Titanate coupling agent (B)>
The titanate coupling agent used in the first embodiment is a phosphorous acid type titanate coupling agent represented by the following formula 1.
(R'-O) _6-a- Ti- [P- (OR ") _m (OH) _3-m ] _a ... Formula 1
Here, in the formula 1, R ′ is an alkyl group containing an isopropyl group or an octyl group, and may be an alkyl group having a smaller number of carbon atoms than the isopropyl group, or an alkyl group having a larger number of carbon atoms than the octyl group. May be.
In addition, a is an integer of 1 to 6.

R ″ is an alkyl group represented by C _n H _{n + 1} where _n is an integer of 1 to 30, and n is preferably an integer of 4 to 20 and more preferably an integer of 6 to 18. is there.
Specific examples of the alkyl group having 4 to 20 carbon atoms include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group. Group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, respectively, saturated or unsaturated straight-chain, saturated or unsaturated branched chain, saturated or unsaturated cyclic Any thing can be used.

  m is an integer of 0 to 3, preferably m is 2, that is, the titanate coupling agent of Embodiment 1 is preferably a diphosphite type titanate coupling agent.

  As the coupling agent, one type of coupling agent may be used alone, or two or more types of coupling agent may be used in combination.

The amount of the titanate coupling agent used in the surface treatment of the reflecting material is not particularly limited and may be appropriately set. For example, with respect to 100 parts by weight of the reflecting material (C),
For example, it is set in the range of 0.1 to 3.0 parts by weight, preferably 0.2 to 2.0 parts by weight, and more preferably 0.3 to 1.5 parts by weight.

  The method of treating the reflective material with the coupling agent is not particularly limited, and a wet method, a dry method, an integral blend method, or the like can be used. The wet method is a method in which the reflecting material is previously charged into a solvent to form a slurry, and then the above titanate coupling agent is added and treated. The dry method is a method in which the reflecting material is charged into a mixer or the like in the absence of a solvent in advance, and the above titanate coupling agent is added thereto for treatment. The integral blending method is a method in which the titanate coupling agent is added at the same time when the reflecting material is added to the resin.

<Reflective material (C)>
Examples of the reflective material used in the first embodiment include metal compounds such as metal oxides such as magnesium oxide, aluminum oxide, zinc oxide, titanium oxide, zirconium oxide, niobium oxide, yttrium oxide, boron nitride, and magnesium hydroxide. To be Alternatively, a metal sulfide such as zinc sulfide or magnesium sulfide or a metal nitride may be used and can be appropriately selected in consideration of properties such as refractive index and reflectance. The metal compound is relatively chemically stable, is less likely to undergo discoloration due to a chemical reaction such as oxidation or sulfurization, and can be highly reliable as a light emitting device. Further, among the metal compounds, metal oxides are preferable because they are relatively inexpensive.

  Among them, titanium oxide is preferable because it is chemically stable and has high light reflectivity to visible light. As titanium oxide, any one of anatase type, rutile type, monoclinic type and the like can be used, and two or more types having different crystal forms can be used in combination. Titanium oxide is preferably a rutile type. This is because rutile type titanium oxide has a high refractive index, good light stability, and lower activity as a photocatalyst than anatase type titanium oxide.

  Titanium oxide as a reflecting material is preferably contained in an amount of 0.1% by weight to 50% by weight of the total amount of the resin molded body composition. It is more preferably 0.2% by weight to 45% by weight. Thereby, the light emission output of the light emitting device can be maintained high. There is also no particular limitation on the shape of the titanium oxide, and any of various shapes such as a particle shape, a fiber shape, a plate shape (including a flake shape, a scale shape, a mica shape, etc.) can be used. More than one species may be used in combination. The size of the titanium oxide is not particularly limited, but is preferably 0.1 μm to 0.5 μm in average particle diameter. When using titanium oxide, the photocatalytic effect is suppressed by the surface treatment.

  The resin composition of Embodiment 1 may contain the following inorganic minerals in order to improve properties such as mechanical strength of the obtained resin molded product.

<Inorganic mineral (D)>
As the inorganic mineral (D), glass fiber, potassium titanate fiber, wollastonite, zinc oxide fiber, sodium titanate fiber, aluminum borate fiber, magnesium borate fiber, magnesium oxide fiber, aluminum silicate fiber, silicon nitride fiber , And inorganic fibers such as carbon fibers. Among them, it is preferable to use one or more selected from the group consisting of potassium titanate fiber and wollastonite for its hiding power.

  As the potassium titanate fiber, various potassium titanate fibers can be used. For example, potassium tetratitanate fiber, potassium hexatitanate fiber, potassium octatitanate fiber and the like can be used. The size of the potassium titanate fiber is not particularly limited, but the average fiber diameter is usually 0.01 μm to 1 μm, preferably 0.1 μm to 0.5 μm, and the average fiber length is 1 μm to 50 μm, preferably 3 μm to 30 μm. Wollastonite is an inorganic fiber made of calcium metasilicate. The size of wollastonite is not particularly limited, but usually, the average fiber diameter is 0.1 μm to 15 μm, preferably 2.0 μm to 7.0 μm, the average fiber length is 3 μm to 100 μm, preferably 20 μm to 50 μm, and the average aspect ratio is 3. The above is preferably 3 to 50, and more preferably 5 to 30.

  In order to further improve the properties such as mechanical strength of the obtained resin molded body, the potassium titanate fiber and wollastonite may be subjected to a surface treatment. For the surface treatment, a silane coupling agent, a titanium coupling agent or the like may be used according to a known method. The amount of potassium titanate fiber and / or wollastonite is usually 5% by weight to 70% by weight, preferably 10% by weight to 70% by weight (30 to 90% by weight of resin component) of the total amount of the resin molded composition. It is good to say

  The resin composition of Embodiment 1 may contain the following additives in order to prevent discoloration of the obtained resin molded product and prevent a decrease in light reflectance.

<Additive (E)>
The resin composition of Embodiment 1 is, for example, a hindered phenol-based compound, a hindered-based amine compound, phosphorus in order to prevent discoloration and prevent a decrease in light reflectance when used as a package for an optical semiconductor device. A system compound and a sulfur system compound can be contained. Others Further, the resin composition of the present invention may be blended with one or more of various additives conventionally used for synthetic resins so long as the preferable physical properties are not impaired. Examples of the additives include inorganic fillers such as talc, silica, zinc oxide (including those in the tetrapot form), flame retardants, plasticizers, nucleating agents, dyes, pigments, release agents, ultraviolet absorbers, etc. Can be mentioned.

The method for producing the resin composition of Embodiment 1 includes a treatment step of treating the reflecting material (C) with the phosphorous acid type titanate coupling agent (B) given by the above formula 1,
A mixing step of mixing the polyamide (A) and the reflecting material (C) treated with the phosphorous acid titanate coupling agent (B);
including.
Here, in the treatment step of treating the reflecting material (C), 100 parts by weight of the reflecting material (C) is treated with 0.1 part by weight to 10 parts by weight of the phosphorous acid titanate coupling agent (B). It is preferable to treat 100 parts by weight of the reflecting material (C) with 0.3 to 1.5 parts by weight of the phosphorous acid type titanate coupling agent (B).

  Since the resin composition of Embodiment 1 configured as described above contains the reflecting material (C) surface-treated with the phosphorous acid type titanate coupling agent (B), deterioration of fluidity can be suppressed. Therefore, as a result, a package having a thin side wall can be easily formed, and the reflectance of the side wall does not decrease due to discoloration due to heat received when the light emitting device is manufactured.

Embodiment 2.
The light emitting device of the second embodiment according to the present invention is a light emitting device including a package molded using the resin composition of the first embodiment. FIG. 1 is a perspective view showing the configuration of a light emitting device according to a second embodiment of the present invention.

  The light emitting device 100 of the second embodiment includes (1) the light emitting element 10, and (2) the recess 60 having the bottom surface 20a and the side wall 20b, and the package 20 molded using the resin composition of the first embodiment. , (3) a lead electrode 30 integrally formed with the package 20, and (4) a sealing member 40 for covering the light emitting element 10.

In the light emitting device 100, the light emitting element 10 is mounted on the lead electrode 30 exposed on the bottom surface 20 a of the recess 60 of the package 20. The electrode of the light emitting element 10 and the lead electrode 30 exposed on the bottom surface 20a are electrically connected by a conductive wire. Further, in order to change the color tone from the light emitting device 100, the sealing member 40 may contain a fluorescent substance 50. As described in the first embodiment, the package 20 is configured to include polyamide, a reflective material, an inorganic fiber and the like. The material of the sealing resin 40 is silicone.
Hereinafter, each component of the second embodiment will be described.

<Light emitting element 10>
The light emitting element 10 has, for example, a semiconductor laminated structure including a light emitting layer on a substrate. The semiconductor laminated structure can be formed, for example, by growing a semiconductor such as GaAlN, InGaN, GaN, AlInGaN, ZnS, ZnSe, SiC, GaP, GaAlAs, AlN, InN, AlInGaP. Among these semiconductors, by using a nitride-based compound semiconductor such as GaAlN, InGaN, GaN, and AlInGaN, the light intensity having a peak emission wavelength in the near-ultraviolet region or the short wavelength region of visible light (360 nm to 550 nm) is high. A light emitting element can be manufactured. Note that a light-emitting element having an emission peak wavelength in the long wavelength region of visible light (551 nm to 780 nm) can also be used.

  The light emitting device 100 may include a plurality of light emitting elements 10. By combining a plurality of light emitting elements 10, it is possible to provide the light emitting device 100 capable of emitting white light having high color rendering properties. The combination of the light emitting elements 10 for emitting white light is, for example, a combination of two light emitting elements 10 capable of emitting green light and one light emitting element 10 capable of emitting blue light and red light. .

  Further, for example, in the case of configuring a light emitting device for full color display, for example, a red light emitting element having an emission wavelength of 610 nm to 700 nm, a green light emitting element having an emission wavelength of 495 nm to 565 nm, and an emission wavelength of 430 nm A blue light emitting element having a wavelength of 490 nm is also used. In the light emitting device 100, when white light is emitted by mixing the light of the light emitting element and the light of the phosphor, the peak wavelength of the light emitting element is set in consideration of the complementary color relationship between the light emitting element 10 and the fluorescent material 50 in the emission wavelength. And select phosphors. In this case, considering further the deterioration of the sealing member 40 due to the light output of the light emitting element 10, the emission wavelength of the light emitting element 10 is preferably 400 nm or more and 530 nm or less, and more preferably 420 nm or more and 490 nm or less. In order to further improve the excitation efficiency and the emission efficiency of the light emitting element 10 and the fluorescent substance 50, 450 nm or more and 475 nm or less are more preferable.

<Package 20>
The package 20 has a recess 60 defined by a bottom surface 20a and a side surface 20b. As described in Embodiment 1, by surface-treating the reflecting material contained in the package 20 with the phosphorous acid-type titanate coupling agent, the viscosity of the package resin can be reduced without discoloring due to heat during manufacturing of the light emitting device. Highly filling reflective material while suppressing. As a result, it is possible to mold even a package having a thin side wall 20b of, for example, 200 μm or less, further 100 μm or less, using the resin composition in which the reflective material is highly filled. Even with such a thin side wall, since the light reflectance on the side wall can be increased, light leakage from the side wall can be reduced, and a light emitting device with high light extraction efficiency can be provided. Further, the package 20 has a form having a longitudinal direction and a lateral direction when observed from the side where the recess 60 is open. At this time, if the thickness of the side wall 20b formed along the longitudinal direction of the side walls 20b of the recess 60 is reduced, the outer dimension of the package in the lateral direction can be reduced without changing the size of the recess 60. Therefore, it is possible to provide the light emitting device 100 having a small thickness by using the same light emitting element 10. As described above, the thin light emitting device 100 is suitable for use as a side view.

<Sealing member 40>
The material of the sealing member 40 is not particularly limited, but a translucent resin such as silicone resin or epoxy resin can be used, for example. It is also possible to use an inorganic material such as glass.

<Fluorescent substance 50>
The fluorescent substance 50 absorbs light from the light emitting element 10 and emits light of different wavelengths. Specifically, for example, an aluminum garnet-based phosphor, a nitride-based phosphor / an oxynitride-based phosphor / a sialon-based phosphor that is mainly activated by a lanthanoid-based element such as Eu, Ce, or a lanthanoid-based such as Eu. , Mn and other transition metal-based elements are mainly activated, alkaline earth halogen apatite phosphors, alkaline earth metal borate halogen phosphors, alkaline earth metal aluminate phosphors, alkaline earth silicates , Alkaline earth sulfides, alkaline earth thiogallates, alkaline earth silicon nitrides, germanates, or rare earth aluminates, rare earth silicates or Eu, which are mainly activated by lanthanoid series elements such as Ce. It is at least any one or two or more selected from organic compounds and organic complexes that are mainly activated by lanthanoid elements.

  The light emitting device of the second embodiment configured as described above includes a package including a large amount of the reflecting material (C) surface-treated with the phosphorous acid-type titanate coupling agent (B), and therefore the light extraction efficiency is improved. Has improved.

Hereinafter, examples according to the present invention will be described. However, the present invention is not limited to the following examples. As Examples 1 to 5, resin compositions having the compositions shown in Table 1 were prepared.

As shown in Table 1, the resin compositions of Examples 1 to 5 contained titanium oxide surface-treated with a titanate coupling agent, and thus Comparative Examples 1 and 2 containing titanium oxide not surface-treated. It is different from the resin composition.
Here, regarding the type of titanate coupling agent, B1 is tetraisopropyl bis (dioctyl phosphite) titanate, and is simply referred to as titanate coupling agent (B1). B2 is tetraoctyl bis (ditridecyl phosphite) titanate, which is also simply referred to as a titanate coupling agent (B2).
In the examples, tetraisopropyl bis (dioctyl phosphite) titanate uses a trade name of Ajinomoto Fine-Techno Co., Inc .: Plane Act 41B, and tetraoctyl bis (ditridecyl phosphite) titanate is Ajinomoto Fine techno ( Brand name: Plenact 46B manufactured by K.K.

In addition, in Examples 1 to 5 and Comparative Examples 1 and 2, the following were used except for the surface treatment agent.
Polyamide (A): poly nonamethylene terephthalamide _{(- [- CO-C 6} H 4 -CONH- (C 9 H 18) -NH -] -),
Reflector (C): Titanium oxide (Product name of Ishihara Sangyo Co., Ltd .: CR-90)
Fibrous mineral (D): Wollastonite (trade name: SH-1800 manufactured by Kinsei Matec Co., Ltd.)
Additive (E): Hindered phenolic compound (trade name of BASF: Irganox 1098 (registered trademark))

  Further, calcium diphosphite manufactured by Daido Pharmaceutical Co., Ltd. was used as the phosphorus compound, and Nylostab S-EED (registered trademark) manufactured by Clariant Japan Co., Ltd. was used as the hindered amine compound.

Treatment method for reflectors To the predetermined amount of titanium dioxide shown in Table 1, NH ₃ water, which is twice the theoretical amount of water required for hydrolysis of the surface treatment agent, was added and mixed, and the titanate coupling agent was added to the titanium dioxide weight ratio. Then, a predetermined amount was weighed so as to obtain the value shown in Table 1, diluted with the same amount of isopropyl alcohol, added to titanium dioxide, and mixed. After the completion of mixing, it was dried in a dryer to obtain surface-treated titanium dioxide.

Preparation of Resin Composition The reflective material (C), the polyamide (A), the inorganic fiber (D) and the additive (E) treated by the above method were weighed in the proportions shown in Table 1 and dry-mixed. After dry mixing, a resin composition was prepared by melt-kneading at 320 ° C. using a twin-screw extrusion kneader.

Fluidity Evaluation of Resin The fluidity of the resin was evaluated by MFR (Melt Florate).
The measurement method was performed according to JIS K 7210, and the measurement conditions were 320 ° C. and a load of 0.65 gf. The values shown as the evaluation results are shown as relative values when the MFR (g / 10 min) of the resin composition of Comparative Example 1 containing 35 parts by weight of titanium oxide that has not been surface-treated is 100.

  When the fluidity of the resin compositions of Examples 1 to 4 and Comparative Example 2 containing 40 parts by weight of titanium oxide was compared with 49 parts by weight of polyamide, the following can be seen.

  The resin compositions of Examples 1 to 3 include titanium oxide surface-treated with the titanate coupling agent (B1) as shown in Table 1, and titanium oxide not surface-treated is the same as that of the resin. In comparison with the resin composition of Comparative Example 2 which is contained in a ratio, the fluidity is good in all cases. From this result, it is understood that when titanium oxide is surface-treated with the titanate coupling agent (B1) and contained in the resin, the fluidity of the resin is improved.

  Further, the resin compositions of Examples 2 and 3 were prepared by adding 0.3 parts by weight and 0.5 parts by weight of titanium oxide surface-treated with the titanate coupling agent (B1) to 100 parts by weight of titanium oxide, respectively. The resin composition of Example 1 using titanium oxide surface-treated with 0.1 part by weight of the titanate coupling agent (B1) was used for 100 parts by weight of titanium oxide. It is good. From these results, it can be seen that it is preferable to use titanium oxide surface-treated with more than 0.1 part by weight of the titanate coupling agent (B1) per 100 parts by weight of titanium oxide.

  Further, the resin composition of Example 4 contains titanium oxide surface-treated with the titanate coupling agent (B2) as shown in Table 1, and titanium oxide not surface-treated is the same as the resin. In comparison with the resin composition of Comparative Example 2 which is contained in a ratio, the fluidity is good in all cases. From the results, it is understood that when titanium oxide is surface-treated with the titanate coupling agent (B2) and contained in the resin, the fluidity of the resin is improved.

  In addition, the resin composition of Example 5 was surface-treated with 1.5 parts by weight of the titanate coupling agent (B1) per 100 parts by weight of titanium oxide, despite having a large content of titanium oxide. Since titanium oxide is used, the fluidity is better than the other examples.

  As Examples 6 to 9, light emitting devices were produced using packages produced by injection molding the resin compositions of Examples 2 to 5, and the total luminous flux emitted was evaluated. Table 2 shows the results. Here, the light emitting devices of Examples 6 to 9 have the light emitting element 10 having the nitride semiconductor layer having an emission peak wavelength at about 450 nm and the recess 60 having the bottom surface 20a and the side wall 20b. The package 20 molded using the resin composition is created. The package 20 uses NSSW304D (manufactured by Nichia Corporation). The package 20 and the lead electrode 30 are integrally formed, and the lead electrode 30 is made of copper as a base material and silver is plated on the surface. Phenyl silicone resin (model number OE6630: manufactured by Toray Dow Corning Co., Ltd.) is used as the sealing member 40.

The total luminous flux of each light emitting device was evaluated by an integral type total luminous flux measuring instrument, and the total luminous flux ratio is shown when the total luminous flux of Comparative Example 3 is 100.
The light emitting device of Comparative Example 3 was manufactured in the same manner as in Examples 6 to 9 except that the resin composition of Comparative Example 1 was used.

  As shown in Table 2, it was confirmed that the light emitting devices of Examples 6 to 9 had a larger total luminous flux than the light emitting devices of the comparative examples.

10 light emitting element 20 package 20a bottom surface 20b side wall 30 lead electrode 40 sealing member 60 recess 100 light emitting device

Claims (13)

Polyamide (A), seeing containing phosphite-type titanate coupling agent represented by the following general formula 1 treated reflector in (B) (C),
It said reflective material (C) is including a resin composition titanium oxide.
(R'-O) _6-a- Ti- [P- (OR ") _m (OH) _3-m ] _a ... General formula 1
R ′ is an alkyl group a is an integer of 1 to 6 R ″ is an alkyl group represented by CnH _{n + 1} where _n is an integer of 1 to 30 and m is an integer of 0 to 3.   The resin composition according to claim 1, wherein the reflective material (C) contains a metal compound. The resin composition according to claim 1, wherein the reflective material (C) further contains a metal oxide other than titanium oxide. Said reflective material (C) is magnesium oxide, aluminum oxide, zinc oxide, acid zirconium, niobium oxide, barium titanate, magnesium hydroxide and yttrium oxide, boron nitride, one selected from the group consisting of magnesium hydroxide The resin composition according to claim 1, which comprises:   The resin composition according to any one of claims 1 to 4, wherein a is 2.   n is an integer of 4-20, The resin composition as described in any one of Claims 1-5.   m is 2. The resin composition according to any one of claims 1 to 6.   The resin composition according to any one of claims 1 to 7, which contains a fibrous mineral (D).   The fibrous mineral (D) is glass fiber, potassium titanate fiber, wollastonite, zinc oxide fiber, sodium titanate fiber, aluminum borate fiber, magnesium borate fiber, magnesium oxide fiber, aluminum silicate fiber, silicon nitride fiber. The resin composition according to claim 8, comprising one selected from the group consisting of: and a carbon fiber.   A package including a resin molding part made of the resin composition according to claim 1 and a lead electrode embedded in the resin molding part, and a light emitting element connected to the lead electrode. Light emitting device.   11. The light emitting device according to claim 10, wherein the package has a recess for accommodating the light emitting element, and a minimum thickness of a side wall of the resin molding portion surrounding the recess is 200 μm or less. A treatment step of treating the reflecting material (C) with the phosphorous acid titanate coupling agent (B) represented by the following general formula 1,
(R'-O) _6-a- Ti- [P- (OR ") _m (OH) _3-m ] _a ... General formula 1
R ′ is an alkyl group a is an integer of 1 to 6 R ″ is an alkyl group represented by CnH _{n + 1} where _n is an integer of 1 to 30 is an integer of 0 to 3 Polyamide (A), and A mixing step of mixing the phosphorous acid-type titanate-based coupling agent (B) and the reflecting material (C),
Only including,
Method for producing a reflecting material (C) is including a resin composition titanium oxide.   The resin composition according to claim 12, wherein 100 parts by weight of the reflecting material (C) is treated with 0.1 to 10 parts by weight of the phosphorous acid type titanate coupling agent (B) in the treatment step. Method.

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