TW201344998A - Wavelength conversion unit, method for manufacturing the same, light emitting device and illumination device each comprising the wavelength conversion unit therein, and resin composition - Google Patents

Abstract

To provide a wavelength conversion unit that can secure sufficient total luminous flux even in a white LED in particular, which has a low color temperature, and a method for manufacturing the same, a light emitting device and illumination device each comprising the wavelength conversion unit therein, and a resin composition. The problem is solved by a wavelength conversion unit that carries out a wavelength conversion of at least a part of an incident light to output an emitting light having a different wavelength from that of the incident light. The wavelength conversion unit has sheet structure comprising a phosphor which absorbs at least a part of the incident light to emit an emitting light having a different wavelength from that of the incident light, and a resin for holing the phosphor, wherein at least a part of the sheet structure has total light transmittance of 30% or more and 70% or less.

Description

Wavelength conversion member and method of manufacturing the same, the light-emitting device and the lighting fixture including the wavelength conversion member, and a resin composition

More particularly, the present invention relates to a wavelength conversion member containing a phosphor and a resin and applied to a light-emitting device or a lighting fixture, a method for producing the same, and a resin composition containing the phosphor and the resin.

A light-emitting device using a semiconductor light-emitting element (hereinafter also referred to simply as an LED (Light Emitting Diode) light-emitting device) is used as an energy-saving light-emitting device, and its presence is improved. The LED light-emitting device includes a semiconductor light-emitting element and includes a phosphor that is excited by light emitted from the semiconductor light-emitting element to emit light of different wavelengths.

The fluorescent system included in the LED light-emitting device is formed by, for example, a slurry in which a phosphor is dispersed in a resin, and is included in the LED light-emitting device as a wavelength conversion member (see, for example, Patent Documents 1 and 2).

As the LED light-emitting device, it is generally required to be brighter, that is, a higher total beam is required, and in order to emit more light beams from the LED light-emitting device, a light-transmitting material is used for the resin constituting the wavelength conversion member. For example, a polyoxyxylene resin is exemplified in Patent Document 2, and an epoxy resin, ceramics, glass, or the like is also used (for example, refer to Patent Documents 3 and 4).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-95770

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-159813

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-9470

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-21868

As mentioned above, a higher total beam is required in LED lighting devices. Further, in the white LED light-emitting device, there is a white color of a fluorescent color having a high radiation color temperature and a white color of a light bulb having a low radiation color temperature, and a white light emitting device of a white light emitting a low color temperature, particularly a full beam. Easy to reduce the problem.

The present invention has been made in view of the above problems, and provides a molded body which can constitute a wavelength conversion member which can secure a sufficient light beam particularly in a white LED light-emitting device of low color temperature.

In order to solve the above problems, the inventors of the present invention have repeatedly studied and found that the total light beam emitted from the light-emitting device is improved by setting the total light transmittance of the molded body constituting the wavelength conversion member to a specific range, thereby completing the present invention.

A first embodiment of the present invention is a wavelength conversion member that performs wavelength conversion on at least a portion of incident light to emit an emitted light of a different wavelength from the incident light, wherein the wavelength conversion member has a planar structure. The planar structure includes a phosphor that absorbs at least a portion of the incident light and emits light of a different wavelength from the incident light, and a resin that holds the phosphor, and at least a portion of the planar structure transmits the total light. The rate is 30% or more and 70% or less. Further, the total light transmittance is preferably 42% or more and 70% or less.

The thickness of the wavelength conversion member is preferably 0.3 mm or more and 5.0 mm or less.

Further, the content of the phosphor contained in the wavelength conversion member is preferably 15% by weight or less, and the average particle diameter of the phosphor is preferably 10 μm or more.

Further, it is preferable that the wavelength conversion member further contains a transmittance adjusting agent.

Further, the resin is preferably a crystalline resin or an amorphous resin, and the amorphous The resin is preferably a thermoplastic resin, and the resin may be an alloy.

Further, it is preferable that the wavelength conversion member is formed to be held by a single body without a holding member, and is preferably formed by injection molding.

A second embodiment of the present invention is a method for fabricating a wavelength converting member, which is a method for manufacturing the above-described wavelength converting member, comprising: a step of mixing a resin and a phosphor, and obtaining a step by the step The step of forming the mixture and performing the mixing step and/or the forming step under an inert gas atmosphere.

In the method of producing the wavelength conversion member, it is preferable to further add a transmittance adjusting agent in the mixing step, and the resin is preferably a crystalline resin or an amorphous resin.

A third embodiment of the present invention is a light-emitting device comprising the wavelength conversion member or a wavelength conversion member manufactured by the above-described manufacturing method, and a semiconductor light-emitting device.

Preferably, the light-emitting device has a color temperature of 5500 K or less.

Further, in the above-described light-emitting device, it is preferable that the wavelength conversion member is separated from the semiconductor light-emitting device, and that it is preferable to provide a transparent resin between the wavelength conversion member and the semiconductor light-emitting device, and further preferably the wavelength conversion member. There is a space between the above semiconductor light emitting elements.

Moreover, it is preferable that the light-emitting device has a wiring board on which a reflecting plate is provided, and an area of a portion having a reflectance of 80% or more is 50% or more of an area on the wiring board.

Further, the light-emitting device preferably includes the wiring board and the casing, and a reflector is provided on the wiring board and the inner wall surface of the casing, and an area having a reflectance of 80% or more is an inner wall surface of the casing. And 50% or more of the area on the wiring board.

A fourth embodiment of the present invention is an LED lighting fixture characterized by having the above-described light-emitting device.

According to a fifth aspect of the present invention, there is provided a resin composition comprising a phosphor and a resin, wherein the resin composition is formed into a planar structure having a planar structure. At least a portion of the total light transmittance is 30% or more 70% or less.

According to the first embodiment of the present invention, the total light beam emitted from the light-emitting device can be increased. In particular, in the case of a white LED light-emitting device that emits white light of a low color temperature, the total light beam is easily lowered, and the wavelength conversion member of the first embodiment of the present invention is applied to a white LED light-emitting device that emits white light of a low color temperature. At the same time, the reduction of the total beam can also be suppressed. Further, the amount of phosphor required can be reduced by adjusting the total light transmittance to a specific range as compared with a conventionally used full-beam light-emitting device. The total light transmittance of the wavelength conversion member can be selected, for example, by the type of the resin, the alloying of the resin, the heterogeneous mixing of the plurality of resins, the thickness of the wavelength converting member, the surface treatment of the wavelength converting member, the addition of the transmittance adjusting agent, and the like. And make adjustments. Therefore, in the case of a white LED light-emitting device that emits white light of a low color temperature, the reduction of the total light beam can be suppressed, and the amount of the phosphor used can be reduced.

Further, according to the second embodiment of the present invention, the wavelength conversion member can be manufactured.

Further, a third embodiment of the present invention is a light-emitting device using a semiconductor light-emitting device and the wavelength conversion member of the first or second embodiment, and the fourth embodiment is provided with illumination of the illumination device of the third embodiment. appliance.

Further, according to the fifth embodiment of the present invention, it is possible to provide a resin composition capable of producing a wavelength converting member which can adjust the total light transmittance.

1‧‧‧Blue semiconductor light-emitting elements

2‧‧‧Wiring substrate

2a‧‧‧ wafer mounting surface

3‧‧‧wavelength conversion components

4‧‧‧Shell

10‧‧‧Lighting device

Fig. 1 is a schematic view showing a configuration example of a semiconductor light-emitting device according to an embodiment of the present invention.

Fig. 2 is a schematic view showing a configuration example of a semiconductor light-emitting device according to an embodiment of the present invention.

Fig. 3 is a graph showing the relationship between the total light transmittance and the Lumen ratio in Examples 1 to 10 and Comparative Examples 1 and 2.

<1-1. Wavelength conversion member>

A first embodiment of the present invention relates to a wavelength conversion member that performs wavelength conversion on at least a portion of incident light to emit an emitted light of a different wavelength from the incident light, wherein the wavelength conversion member has a planar shape. a planar structure comprising a phosphor that absorbs at least a portion of the incident light and emits light having a different wavelength from the incident light, and a resin that holds the phosphor, and at least a portion of the planar structure The transmittance is 30% or more and 70% or less.

The term "full light transmittance" refers to the ratio of the total transmitted light beam to the parallel incident beam of the test piece. The total light transmittance can be measured in accordance with JIS K7361. Since the phosphor is contained, the wavelength conversion member having low transparency is colored. Therefore, it is necessary to measure the device using a halogen lamp as a light source with an inlet opening of 20 mmφ. The total light transmittance of the wavelength conversion member can be adjusted by, for example, the amount of the phosphor used, the type of the resin selected, the alloying of the resin, the heterogeneous mixing of the plurality of resins, the thickness of the wavelength converting member, and the wavelength. The surface treatment of the conversion member or the like is performed, and it can be carried out by including a transmittance adjusting agent.

In the LED light-emitting device, in order to increase the total light beam, it is necessary to transmit a large amount of light emitted from the semiconductor light-emitting element as the light-emitting source to the wavelength conversion member including the phosphor. Therefore, the wavelength conversion member is made of a material having high permeability such as polyfluorene oxide or epoxy.

However, the inventors of the present invention have found that when the total light transmittance of the wavelength converting member is too high, the total light beam of the light emitted from the light-emitting device is instead lowered. Then, after further research, it is thought that by using a wavelength conversion member having a total light transmittance in a range that is not too high, specifically, a total light transmittance of 30% or more and 70% or less, the light-emitting device can achieve a higher total. beam. Further, even in the case of a light-emitting device that emits white light of a low color temperature in which the full beam is easily lowered, a high total beam can be achieved.

Here, as described above, the wavelength conversion member of the present invention has a planar structure including a phosphor and a resin that holds the phosphor. The planar structure means a portion which becomes a light-emitting surface in the light-emitting device. For example, when the wavelength conversion member is provided in the light-emitting device, it does not mean a joint portion, a joint portion, or a meshing portion with other members visible from the end portion or the like. It is a portion that is mainly located near the center of the wavelength conversion member and that receives excitation light and emits light to the outside. Bit.

As will be described with reference to Fig. 1, the single-dot chain line portions in the wavelength conversion member 3 in Fig. 1 are all planar structure portions. On the other hand, the portion in the vicinity of the wiring substrate 2 in the wavelength conversion member 3 is not a planar structure.

In the present embodiment, at least a part of the planar structure of the wavelength conversion member satisfies the range of the total light transmittance, and it is preferable that the main portion satisfies the range of the total light transmittance, and more preferably the surface of the wavelength conversion member. All of the structures satisfy the above range of total light transmittance. Further, the total light transmittance is preferably 42% or more, more preferably 45% or more, still more preferably 47% or more. On the other hand, it is preferably 60% or less, more preferably 55% or less.

Here, the main part of the planar structure means that the light-emitting portion is the main light-emitting portion in the above-described planar structure in which light is emitted when incorporated in the semiconductor light-emitting device.

<1-2. Fluorescent body>

The wavelength conversion member of this embodiment includes a phosphor. The type of the phosphor to be contained is appropriately selected, but is preferably an inorganic phosphor. Examples of the red (orange), green, blue, and yellow phosphors include the following representative phosphors.

In this case, the phosphors may be used alone or in combination of two or more. By using two or more kinds of phosphors, the color temperature can be lowered or the color rendering property can be improved.

Further, the phosphor may be subjected to surface treatment by the third component. The surface treatment agent is not particularly limited, and for example, the same as the surface treatment agent of the transmittance adjusting agent described below can be used. Further, the phosphor of the present embodiment can be used as a surface treatment agent in advance, or a surface treatment agent can be directly added to a kneading machine during kneading to perform surface treatment in a kneading machine.

<1-2-1. Red phosphor>

The luminescence peak wavelength of the red phosphor is suitable for the following wavelength range: usually 565 nm or more, preferably 575 nm or more, more preferably 580 nm or more, and usually 780 nm or less, preferably 700 nm or less. More preferably below 680 nm.

The half-value width of the luminescence peak of the red phosphor is usually in the range of 1 nm to 120 nm. Moreover, the external quantum efficiency is usually 60% or more, preferably 70% or more, in weight. The value is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, and usually 40 μm or less, preferably 30 μm or less, and further preferably 20 μm or less.

As such a red phosphor, for example, CaAlSiN ₃ :Eu described in Japanese Laid-Open Patent Publication No. 2006-008721 (hereinafter, referred to as "CASN" in the present specification), Japanese Patent Laid-Open No. 2008- (Sr, Ca)AlSiN ₃ :Eu, and Ca _1-x Al _1-x Si _1+x N _3-x O _x :Eu described in Japanese Laid-Open Patent Publication No. 2007-231245 Ep-activated oxide, nitride or oxynitride phosphor, etc., or Japanese Patent Laid-Open Publication No. 2008-38081 (Sr, Ba, Ca) ₃ SiO ₅ :Eu (hereinafter sometimes referred to simply as "SBS phosphor"").

Further, as the red phosphor, an alkaline earth-based lanthanum nitride-based phosphor such as (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ :Eu or the like may be used; (La, Y) ₂ O ₂ S: Eu, etc. Eu-activated acid sulfide phosphor; (Y, La, Gd, Lu) ₂ O ₂ S: Eu and other Eu-activated rare earth oxychalcogenide-based phosphor; Y(V, P)O ₄ : Eu, Y ₂ O ₃ : Eu, etc., Eu-activated oxide phosphor; (Ba, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn, etc. Eu, Mn Revitalizing citrate phosphor; LiW ₂ O ₈ :Eu, LiW ₂ O ₈ :Eu,Sm,Eu ₂ W ₂ O ₉ ,Eu ₂ W ₂ O ₉ :Nb,Eu ₂ W ₂ O ₉ :Sm, etc. Eu Revitalizing the tungstate phosphor; (Ca, Sr) S: Eu and other Eu-activated sulfide phosphor; YAlO ₃ : Eu and other Eu-activated aluminate phosphor; Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, etc. Eu-activated phthalate phosphor; (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, (Tb, Gd) ₃ Al ₅ O ₁₂ : Ce, etc. Ce activating aluminate phosphor; (Mg, Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Mg, Ca, Sr, Ba) Si(N,O) ₂ :Eu, ( Mg, Ca, Sr, Ba) AlSi(N,O) ₃ :Eu, etc. Eu-activated oxide, nitride or oxynitride phosphor; (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu, Mn, etc. Eu , Mn activating halophosphate phosphor; Ba ₃ MgSi ₂ O ₈ :Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn,Mg)Si ₂ O ₈ :Eu, Mn, etc. Eu, Mn activating 矽Acid phosphor; 3.5MgO-0.5MgF ₂ -GeO ₂ : Mn and other Mn-activated citrate phosphor; Eu revitalizes Eu-activated oxynitride phosphor such as α-Sallon; (Gd, Y, Lu, La ₂ O ₃ : Eu, Bi, etc. Eu, Bi-activated oxide phosphor; (Gd, Y, Lu, La) ₂ O ₂ S: Eu, Bi, etc. Eu, Bi-activated acid sulfide phosphor; (Gd , Y, Lu, La) VO ₄ : Eu, Bi, etc. Eu, Bi-activated vanadate phosphor; SrY ₂ S ₄ : Eu, Ce, etc. Eu, Ce-activated sulfide phosphor; CaLa ₂ S ₄ : Ce Et enactivates sulfide phosphor; (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn, etc. Eu, Mn Phosphate phosphor; (Y, Lu) ₂ WO ₆ : Eu, Mo, etc. Eu, Mo-activated tungstate phosphor; (Ba, Sr, Ca) _x Si _y N _z : Eu, Ce (where x , y, z represents an integer of 1 or more, etc. Eu, Ce gives a living nitride phosphor; (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH): Eu, Mn, etc. Eu, Mn activating halophosphate phosphor; ((Y, Lu, Gd, Tb) _1-xy Sc _x Ce _y ) ₂ (Ca, Mg) _1-r (Mg, Zn) _2+r Si _zq Ge _q Ce such as O _{12+δ is} activated by a citrate phosphor or the like.

Further, in order to increase the color rendering property of the emitted light from the semiconductor light-emitting device or to improve the light-emitting efficiency of the light-emitting device, as the red phosphor, a red phosphor having a half-value width of 20 nm or less in the red light-emitting spectrum may be used alone ( Hereinafter, it may be referred to as "narrow-band red phosphor" or may be mixed with other red phosphors, particularly red phosphors having a half-value width of 50 nm or more. As such a red phosphor, A _{2+ x} M _y Mn _z F _n (A is Na and/or K; M is Si and Al; -1≦x≦1 and 0.9≦y+z≦1.1) And KSF, KSNAF and KSF and KSNAF solid solution represented by 0.001≦z≦0.4 and 5≦n≦7), from (kx)MgO-xAF ₂ -GeO ₂ :yMn ⁴⁺ (where k is The real number of 2.8~5, x is a real number of 0.1~0.7, y is a real number of 0.005~0.015, and A is a mixture of calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn) or the like) A manganese red active (600 nm to 670 nm) citrate phosphor represented by the chemical formula of 3.5MgO-0.5MgF ₂ -GeO ₂ :Mn, derived from (La _1-xy ,Eu _x ,Ln _y ) ₂ O ₂ S (x and y respectively represent the number of 0.02≦x≦0.50 and 0≦y≦0.50, and Ln represents the chemical formula of at least one trivalent rare earth element of Y, Gd, Lu, Sc, Sm and Er) Indicates the LOS phosphor and so on.

Further, SrAlSi ₄ N ₇ described in International Publication WO 2008-096300 or Sr ₂ Al ₂ Si ₉ O ₂ N ₁₄ :Eu described in U.S. Patent No. 7,524,437 may be used.

Among the above, as the red phosphor, a CASN phosphor, a SCASN phosphor, a CASON phosphor, and an SBS phosphor are preferable.

The red phosphors exemplified above may be used singly or in combination of two or more kinds in any combination and in any ratio.

<1-2-2. Green phosphor>

The wavelength of the luminescence peak of the green phosphor is usually greater than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, of which It is 540 nm or less, and further preferably in the range of 535 nm or less. If the wavelength of the luminescence peak is too short, the color tends to be bluish. On the other hand, if it is too long, it tends to be yellowish, and the characteristics as green light may be lowered.

The half-value width of the luminescence peak of the green phosphor is usually in the range of 1 nm to 80 nm. Further, the external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, and usually 40 μm or less. It is preferably 30 μm or less, and more preferably 20 μm or less.

For example, (Ba, Ca, Sr, Mg) ₂ SiO ₄ :Eu (hereinafter sometimes abbreviated as "BSS phosphor") as described in International Publication WO2007-091687 The Eu is represented by an alkaline earth silicate-based phosphor or the like.

Further, as the green phosphor, for example, Si _6-z Al _z N _8-z O _z :Eu described in Japanese Patent No. 3921545 (where 0<z≦4.2; An active oxynitride phosphor such as "β-SiAlON phosphor"), and M ₃ Si ₆ O ₁₂ N ₂ :Eu described in WO2007-088966 (where M represents an alkaline earth metal element) In the following, an Au-activated oxynitride phosphor such as "BSON phosphor" is used, and BaMgAl ₁₀ O ₁₇ :Eu, Mn, which is described in JP-A-2008-274254, activates aluminate fluorescence. Body (hereinafter sometimes referred to as "GBAM phosphor").

As other green phosphors, Eu (Og, Ca, Sr, Ba), Si ₂ O ₂ N ₂ :Eu, etc., may be used to activate an alkaline earth oxynitride lanthanide phosphor; Sr ₄ Al ₁₄ O ₂₅ :Eu, ( Ba, Sr, Ca) Al ₂ O ₄ : Eu and other Eu-activated aluminate phosphors; (Sr, Ba) Al ₂ Si ₂ O ₈ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, (Ba, Sr,Ca) ₂ (Mg,Zn)Si ₂ O ₇ :Eu,(Ba,Ca,Sr,Mg) ₉ (Sc,Y,Lu,Gd) ₂ (Si,Ge) ₆ O ₂₄ :Eu, etc. Eu Tellurite phosphor; Y ₂ SiO ₅ :Ce, Tb, etc. Ce, Tb, etc., citrate phosphor; Sr ₂ P ₂ O ₇ -Sr ₂ B ₂ O ₅ :Eu, etc. Eu-activated boric acid phosphate fluorescein Body; Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu and other Eu-activated halocate phosphor; Zn ₂ SiO ₄ : Mn and other Mn-activated phthalate phosphor; CeMgAl ₁₁ O ₁₉ : Tb, Y ₃ Al ₅ O ₁₂ : Tb and other Tb activating aluminate phosphor; Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Tb, La ₃ Ga ₅ SiO ₁₄ : Tb and the like Tb to activate the phthalate phosphor; (Sr, Ba,Ca)Ga ₂ S ₄ :Eu, Tb,Sm, etc. Eu, Tb, Sm activates thiogallate acid phosphor; Y ₃ (Al,Ga) ₅ O ₁₂ :Ce, (Y,Ga,Tb, La,Sm,Pr,Lu) ₃ (Al,Ga) ₅ O ₁₂ :Ce and other Ce activating aluminate phosphor; Ca ₃ Sc ₂ Si ₃ O ₁₂ :Ce, Ca ₃ (Sc,Mg,Na,Li ) ₂ S i ₃ O ₁₂ : Ce, etc., activating a phthalate phosphor; CaSc ₂ O ₄ :Ce, etc., activating an oxide phosphor; Eu activating an Eu-activated oxynitride phosphor such as β-Sialon, SrAl ₂ O ₄ : Eu and other Eu activating aluminate phosphor; (La, Gd, Y) ₂ O ₂ S: Tb and other Tb activating acid sulfide phosphor; LaPO ₄ : Ce, Tb, etc. Ce, Tb revitalizing phosphate Light body; ZnS: Cu, Al, ZnS: Cu, Au, Al, etc. sulfide phosphor; (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb, (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ke, Ce, Tb, etc. Ce, Tb revitalizes borate phosphor; Ca ₈ Mg(SiO ₄ ) ₄ Cl ₂ :Eu , Mn and other Eu, Mn to activate the halosilicate phosphor; (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu and other Eu-activated thioaluminate phosphor or thio gallate Salt phosphor; (Ca,Sr) ₈ (Mg,Zn)(SiO ₄ ) ₄ Cl ₂ :Eu, Mn, etc. Eu, Mn to activate the halosilicate phosphor; M ₃ Si ₆ O ₉ N ₄ :Eu Et is activated by an oxynitride phosphor or the like.

Further, Sr ₅ Al ₅ Si ₂₁ O ₂ N ₃₅ :Eu described in International Publication No. WO2009-072043 or Sr ₃ Si ₁₃ Al ₃ N ₂₁ O ₂ :Eu described in International Publication WO2007-105631 can also be used. .

Among the above, as the green phosphor, a BSS phosphor, a β-SiAlON phosphor, and a BSON phosphor are preferable.

The green phosphors exemplified above may be used singly or in combination of two or more kinds in any combination and in any ratio.

Further, in order to increase the color rendering property of the emitted light from the semiconductor light-emitting device or to improve the light-emitting efficiency of the light-emitting device, a green phosphor having a half-value width of 20 nm or less in the green light-emitting spectrum may be used alone (hereinafter sometimes referred to as " A narrow-band green phosphor") is used as a green phosphor.

<1-2-3. Blue phosphor>

The wavelength of the luminescence peak of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually less than 500 nm, preferably 490 nm or less, more preferably 480 nm or less. It is preferably 470 nm or less, and particularly preferably in the wavelength range of 460 nm or less.

The half-value width of the luminescence peak of the blue phosphor is usually in the range of 10 nm to 100 nm. Further, the external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, and more preferably 5.0 μm. The upper portion is usually 40 μm or less, preferably 30 μm or less, and more preferably 20 μm or less.

Examples of such a blue phosphor include an anthracene active halophosphate phosphor represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, and (Ca, Sr, Ba). ₂ B ₅ O ₉ Cl: an anthracene-derived alkaline earth chloroborate-based phosphor represented by Eu, from (Sr, Ca, Ba)Al ₂ O ₄ :Eu or (Sr,Ca,Ba) ₄ Al ₁₄ O ₂₅ : An alkali-like aluminate-based phosphor represented by Eu.

Further, as the blue phosphor, a phosphate phosphor such as Sr ₂ P ₂ O ₇ :Sn may be used to activate the phosphate phosphor; Sr ₄ Al ₁₄ O ₂₅ :Eu, BaMgAl ₁₀ O ₁₇ :Eu, BaAl ₈ O ₁₃ : Eu and other Eu-activated aluminate phosphor; SrGa ₂ S ₄ :Ce, CaGa ₂ S ₄ :Ce, etc. Ce activates the thioglycolate phosphor; (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ :Eu, Tb, Sm, etc. Eu, Tb, Sm activating aluminate phosphor; (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn, etc. Eu, Mn activating aluminate fluorite Light body; (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu, Mn, Eu, Tb, Sm such as Sb activates halophosphate phosphor; BaAl ₂ Si ₂ O ₈ :Eu, (Sr,Ba) ₃ MgSi ₂ O ₈ :Eu, etc. Eu-activated citrate phosphor; Sr ₂ P ₂ O ₇ : Eu and other Eu-activated phosphate phosphor; ZnS: Ag, ZnS: Ag, Al and other sulfide phosphors; Y ₂ SiO ₅ : Ce and other Ce-activated citrate phosphor; CaWO ₄ and other tungstic acid Salt phosphor; (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ -nB ₂ O ₃ : Eu, 2SrO-0.84P ₂ O ₅ -0.16B ₂ O ₃ : Eu, Eu, etc., activates the boric acid phosphate phosphor; Sr ₂ Si ₃ O ₈ -2SrCl ₂ :Eu, etc. Halogen halide phosphors, etc.

Among them, (Sr, Ca, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ²⁺ and BaMgAl ₁₀ O ₁₇ :Eu can be preferably used. Further, among the phosphors represented by (Sr, Ca, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ²⁺ , Sr _a Ba _b Eu _x (PO ₄ ) _c Cl _d can be preferably used. (c, d, and x satisfy the number of 2.7≦c≦3.3, 0.9≦d≦1.1, 0.3≦x≦1.2, and x is preferably 0.3≦x≦1.0; further, a and b satisfy a+b=5 For the condition of -x and 0.05 ≦b / (a + b) ≦ 0.6, b / (a + b) is preferably a phosphor represented by 0.1 ≦ b / (a + b) ≦ 0.6).

Further, in order to increase the color rendering property of the emitted light from the semiconductor light-emitting device or to improve the light-emitting efficiency of the light-emitting device, a blue phosphor having a half-value width of blue light emission of 20 nm or less may be used alone (hereinafter sometimes referred to as It is a "narrow-band blue phosphor") as a blue phosphor.

<1-2-4. Yellow phosphor>

The luminescence peak wavelength of the yellow phosphor is usually 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. .

The half-value width of the luminescence peak of the yellow phosphor is usually in the range of 80 nm to 130 nm. Further, the external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, and usually 40 μm or less. It is preferably 30 μm or less, and more preferably 20 μm or less.

Examples of such a yellow phosphor include various oxides such as an oxide system, a nitride system, an oxynitride system, a sulfide system, and an oxysulfide system. In particular, RE ₃ M ₅ O ₁₂ :Ce (here, RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents a group selected from Al, Ga, and Sc At least one element of the group consisting of or Ma ₃ Mb ₂ Mc ₃ O ₁₂ :Ce (here, Ma represents a divalent metal element, Mb represents a trivalent metal element, Mc represents a tetravalent metal element), etc. a garnet-based phosphor having a garnet structure; from AE ₂ MdO ₄ :Eu (here, AE represents at least one element selected from the group consisting of Ba, Sr, Ca, Mg, and Zn, Md represents a orthosilicate-based phosphor represented by Si and/or Ge); an oxynitride-based phosphor in which a part of oxygen of constituent elements of the phosphors is replaced by nitrogen; AEAlSiN ₃ :Ce (here, AE represents a phosphor selected from a group consisting of at least one element selected from the group consisting of Ba, Sr, Ca, Mg, and Zn), and a nitride-based phosphor having a CaAlSiN ₃ structure is activated by Ce.

Among these, a garnet-based phosphor is preferably used. Among them, Y ₃ Al ₅ O ₁₂ :Ce (in the present specification, it may be referred to as "YAG").

Further, as the yellow phosphor, a sulfide such as CaGa ₂ S ₄ :Eu, (Ca,Sr)Ga ₂ S ₄ :Eu, (Ca,Sr)(Ga,Al) ₂ S ₄ :Eu or the like may be used. Phosphor; a phosphor that is activated by Eu, such as an oxynitride-based phosphor having a SiAlON structure, such as Ca _x (Si, Al) ₁₂ (O, N) ₁₆ : Eu; (M _1-AB Eu _A Mn _B ) ₂ (BO ₃ ) _1-P (PO ₄ ) _P X (wherein M represents one or more elements selected from the group consisting of Ca, Sr and Ba, and X represents a composition selected from the group consisting of F, Cl and Br One or more elements in the group; A, B, and P respectively represent Eu-activated or Eu, Mn, etc., which satisfies 0.001≦A≦0.3, 0≦B≦0.3, 0≦P≦0.2, etc. A light body; a Ce-activated nitride-based phosphor having an alkaline earth metal element and having a La ₃ Si ₆ N ₁₁ structure. Further, a part of the above-mentioned Ce-activated nitride-based phosphor may be substituted with a Ca or O moiety.

In the present embodiment, the phosphor content when the total weight of the wavelength converting member is 100% by weight is preferably 0.5% by weight or more, and more preferably 1% by weight or more. On the other hand, it is preferably 15% by weight or less, more preferably 10% by weight or less. With this range, the thickness of the wavelength conversion member is likely to be in an appropriate range, and the decrease in strength of the wavelength conversion member can be suppressed.

Further, the average particle diameter of the phosphor contained in the wavelength converting member is preferably 10 μm or more, and more preferably 15 μm or more. By setting it as this range, the fall of wavelength conversion efficiency can be suppressed.

Here, the average particle diameter refers to the average particle diameter of the primary particles, and is a value measured by a laser particle size analyzer.

<1-3. Resin>

The resin used in the present embodiment may be a crystalline resin or an amorphous resin. Hereinafter, the crystalline resin and the amorphous resin which can be used in the present embodiment will be described.

<1-3-1. Crystalline Resin>

The resin having crystallinity used in the present embodiment is not particularly limited as long as it is a resin which is generally recognized as a crystalline resin. For example, it is typically observed that in the differential scanning calorimetry, 10 ° C is observed. The thermoplastic resin which is cooled from the molten state to room temperature or the peak of the heat of melting when the resin in a solid state is heated at 10 ° C /min is preferably 2 J/g or more.

In the thermoplastic resin having crystallinity, since the temperature difference between the glass transition temperature Tg and the melting point Tm is large, it can be molded at a relatively low temperature compared with an amorphous resin having the same heat resistance. Therefore, it is preferable because it is not easily colored at the time of molding.

The type of the thermoplastic resin having crystallinity is not particularly limited, and specific examples thereof include polyethylene, polypropylene, poly-3-methylbutene-1, poly-4-methylpentene-1, and polylactic acid. Polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polyether ether ketone, fluorine resin, and the like.

Among these, from the viewpoint of durability, a fluorine-containing resin is preferred as its specific Examples thereof include ETFE (ethylene-tetrafluoroethylene copolymer), PTFE (polytetrafluoroethylene), FEP (tetrafluoroethylene-hexafluoropropylene copolymer), PFA (perfluoroalkoxy fluororesin), and PVDF (poly). a mixture of vinylidene fluoride), PVF (polyvinyl fluoride), PCTFE (polychlorotrifluoroethylene), and tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride, among which durability and formability From the viewpoint of viewpoint, it is preferably ETFE, FEP, PFA, and most preferably ETFE. As ETFE, in addition to ethylene and tetrafluoroethylene, ETFE containing a small amount of a third component having a bulky side chain is further preferable in terms of light transmittance or chromaticity stability.

Only one type of such a crystalline thermoplastic resin may be used, or two or more types may be used in combination, and the total light transmittance may be adjusted by alloying, which deviates from the range of the total light transmittance in the present embodiment. Happening.

Further, the melting point of the crystalline thermoplastic resin is preferably 150 ° C or higher, more preferably 168 ° C or higher. When the melting point is 150 ° C or more, the heat resistance of the molded body is improved. On the other hand, the melting point is preferably 350 ° C or lower, more preferably 320 ° C or lower, and most preferably 300 ° C or lower. In the case of a resin having a melting point exceeding 350 ° C, even if it is a crystalline resin, the processing temperature is high, which is unsatisfactory due to coloring or decomposition of the resin.

<1-3-2. Amorphous resin>

The amorphous resin used in the present embodiment may, for example, be a thermosetting resin, a thermoplastic resin or a photocurable resin, and is preferably a thermoplastic resin. As the thermosetting resin, for example, an epoxy resin and a polyoxymethylene resin are preferably used.

Examples of the amorphous thermoplastic resin include: a polyolefin-based resin such as an alicyclic polyolefin resin such as a olefin; a copolymer of ethylene and methyl-, ethyl-, propyl-, butyl- acrylate or methacrylate, and an ethylene-acrylic acid copolymer Plasma polymer resin; styrene resin such as polystyrene resin, ABS resin, AS resin, AAS resin, AES resin, MBS resin; acrylic resin such as polymethyl methacrylate or polymethacrylate; polycarbonate Polyester resin such as resin; modified polyphenylene ether resin; polyurethane resin; polyarylate resin; polyether quinone imine resin; polyimine resin, etc., etc. A mixture of the above and the like.

Further, the resin may be an alloy, and the amount of the phosphor can be adjusted by using it in the form of an alloy, and as a result, it has an advantage that the total light transmittance can be adjusted.

Among these, a polycarbonate resin can be optimally used in terms of transparency, heat resistance, mechanical properties, and flame retardancy. The polycarbonate resin will be described in detail below.

The polycarbonate resin used in the present embodiment is a polymer having a basic structure of a carbonic acid bond represented by the following general chemical formula (1).

In the chemical formula (1), X ^{1 is} generally a hydrocarbon, and in order to impart various properties, X ^{1 which} introduces a hetero atom or a hetero bond may be used.

Further, the polycarbonate resin can be classified into an aromatic polycarbonate resin which is directly bonded to a carbonic acid bond and an aromatic polycarbonate resin which is an aromatic carbon, and an aliphatic polycarbonate resin which is an aliphatic carbon, and any of them can be used. Among them, from the viewpoints of heat resistance, mechanical properties, electrical properties, and the like, an aromatic polycarbonate resin is preferred.

The specific type of the polycarbonate resin is not limited, and examples thereof include a polycarbonate polymer obtained by reacting a dihydroxy compound with a carbonate precursor. In this case, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting carbon dioxide as a carbonate precursor with a cyclic ether can also be used. Further, the polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit, or a copolymer having two or more repeating units. In this case, the copolymer may be in various copolymerization forms such as a random copolymer or a block copolymer. Further, such a polycarbonate polymer is usually a thermoplastic resin.

Among the monomers which are raw materials of the aromatic polycarbonate resin, examples of the aromatic dihydroxy compound include 1,2-dihydroxybenzene and 1,3-dihydroxybenzene (i.e., resorcinol). Dihydroxybenzenes such as 1,4-dihydroxybenzene; dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2' dihydroxybiphenyl, 4,4'-dihydroxybiphenyl; , 2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6 -Dihydroxynaphthalene, 1,7- Dihydroxynaphthalenes such as dihydroxynaphthalene and 2,7-dihydroxynaphthalene; 2,2'dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4 , 4-dihydroxy-3,3' dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, etc. Aryl ethers; 2,2-bis(4-hydroxyphenyl)propane (ie bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl- 4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyl Phenyl)propane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2, 2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α'-double ( 4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(4-hydroxyphenyl)methane, Bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)(4-propenylphenyl)methane, bis(4-hydroxyphenyl) Diphenylmethane, bis(4-hydroxyphenyl)naphthylmethane, 1-bis(4-hydroxybenzene) Ethylene, 2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)- 1-naphthylethane, 1-bis(4-hydroxyphenyl)butane, 2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1, 1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1-bis(4-hydroxyphenyl)octane, 2-bis(4-hydroxyphenyl) Octane, 1-bis(4-hydroxyphenyl)hexane, 2-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-double Bis(hydroxyaryl)alkanes such as (4-hydroxyphenyl)decane, 10-bis(4-hydroxyphenyl)decane, 1-bis(4-hydroxyphenyl)dodecane; 1-double ( 4-hydroxyphenyl)cyclopentane, 1-bis(4-hydroxyphenyl)cyclohexane, 4-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5 - dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethyl Phenyl)-3,3,5-tributylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-double ( 4-hydroxyphenyl)-3- Butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane Bis(hydroxyaryl)cycloalkanes such as alkane, 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane; 9,9-bis(4-hydroxyphenyl)anthracene, 9,9 - bisphenols containing cardo structure such as bis(4-hydroxy-3-methylphenyl)anthracene; 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-di Dihydroxydiaryl sulfides such as methyl diphenyl sulfide; 4,4'-dihydroxydiphenylarylene, 4,4' dihydroxy-3,3'-dimethyldiphenylarylene, etc. Dihydroxydiarylhydrazone; 4,4'-dihydroxydiphenyl Dihydroxy diaryl hydrazines such as hydrazine and 4,4'-dihydroxy-3,3' dimethyldiphenyl hydrazine.

Among these, a bis(hydroxyaryl)alkane is preferable, and among them, a bis(4-hydroxyphenyl)alkane is preferable, and in particular, from the viewpoint of impact resistance and heat resistance, it is preferably 2 , 2-bis(4-hydroxyphenyl)propane (ie bisphenol A).

Further, the aromatic dihydroxy compound may be used alone or in combination of two or more kinds in any combination and in any ratio.

In addition, examples of the monomer which is a raw material of the aliphatic polycarbonate resin include ethane-1,2-diol, propane-1,2-diol, and propane-1,3-diol. , 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1, Alkane diols such as 5-diol, hexane-1,6-diol, decane-1,10-diol; cyclopentane-1,2-diol, cyclohexane-1,2-di Alcohol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4-(2-hydroxyethyl)cyclohexanol, 2,2,4,4-tetramethyl-cyclobutane a cycloalkane glycol such as an alkane-1,3-diol; a glycol such as 2,2'-oxydiethanol (i.e., ethylene glycol), diethylene glycol, triethylene glycol, propylene glycol or spirodiol ; 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis(2-hydroxyethoxy)benzene, 1, 4-bis(2-hydroxyethoxy)benzene, 2,3-bis(hydroxymethyl)naphthalene, 1,6-bis(hydroxyethoxy)naphthalene, 4,4'biphenyldimethanol, 4,4 '-biphenyldiethanol, 1,4-bis(2-hydroxyethoxy)biphenyl, bisphenol A bis(2-hydroxyethyl)ether, bisphenol S bis(2-hydroxyethyl)ether, etc. Alkylene glycols; 1,2-ethylene oxide (ie epoxy B) ), 1,2-propylene oxide (ie, propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl -1,2-epoxycyclohexane, 2,3-epoxy drop A cyclic ether such as an alkane or a 1,3-epoxypropane may be used alone or in combination of two or more kinds in any combination and in any ratio.

Among the monomers which are raw materials of the aromatic polycarbonate resin, examples of the carbonate precursor include a carbonyl halide, a carbonate, and the like. Further, one type of the carbonate precursor may be used, or two or more types may be used in any combination and in any ratio.

Specific examples of the carbonyl halide include a hafnium chloride, a bischloroformate of a dihydroxy compound, a haloformate such as a monochloroformate of a dihydroxy compound, and the like.

Specific examples of the carbonate include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. An ester; a dicarbonate of a dihydroxy compound, a monocarbonate of a dihydroxy compound, a carbonate of a dihydroxy compound such as a cyclic carbonate, or the like.

The method for producing the polycarbonate resin is not particularly limited, and any method can be employed. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, an interfacial polymerization method and a melt transesterification method which are particularly preferable among the methods will be specifically described.

(Interfacial polymerization method)

In the interfacial polymerization method, the pH is usually maintained at 9 or more in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and the dihydroxy compound is reacted with a carbonate precursor (preferably carbon ruthenium chloride). Interfacial polymerization is carried out in the presence of a polymerization catalyst, whereby a polycarbonate resin is obtained. Further, in the reaction system, a molecular weight modifier (end terminal blocking agent) may be present as needed, and an antioxidant may be present to prevent oxidation of the dihydroxy compound.

The dihydroxy compound and the carbonate precursor are as described above. Further, it is preferable to use carbonium chloride in the carbonate precursor, and the method in the case of using carbonium chloride is especially called carbonium chloride.

Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene, and xylene. Wait. In addition, one type of the organic solvent may be used, or two or more types may be used in any combination and in any ratio.

Examples of the basic compound contained in the alkaline aqueous solution include basic metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogencarbonate, and alkaline earth metal compounds. Among them, sodium hydroxide and hydrogen are preferred. Potassium oxide. In addition, one type of the basic compound may be used, or two or more types may be used in any combination and in any ratio.

The concentration of the basic compound in the alkaline aqueous solution is not limited, and is usually used in an amount of 5 to 10% by weight in order to control the pH in the alkaline aqueous solution of the reaction to 10 to 12. Further, for example, when carbonium chloride is sprayed, in order to control the pH of the aqueous phase to 10 to 12, preferably 10 to 11, it is preferred to use a molar ratio of the bisphenol compound to the basic compound. It is set to 1:1.9 or more, and is preferably 1:2.0 or more, and is usually set to 1:3.2 or less, and preferably 1:2.5 or less.

Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; N,N'-dimethylcyclohexylamine, N,N'- An alicyclic tertiary amine such as diethylcyclohexylamine; an aromatic tertiary amine such as N,N'-dimethylaniline or N,N'-diethylaniline; trimethylbenzylammonium chloride or chlorine A tetra-ammonium salt such as tetramethylammonium or triethylbenzylammonium chloride, or a salt of pyridine, guanine or guanidine. Further, one type of the polymerization catalyst may be used, or two or more types may be used in any combination and in any ratio.

Examples of the molecular weight modifier include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans and benzylidene imine; and among them, aromatic phenols are preferred. Specific examples of such an aromatic phenol include an alkane such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, or a long-chain alkyl-substituted phenol. a phenol containing a vinyl group, a phenol containing an epoxy group, a phenol containing an epoxy group, a phenol containing a carboxyl group such as 8-methyl-6-hydroxyphenylacetic acid, or the like. In addition, one type of the molecular weight modifier may be used, or two or more types may be used in any combination and in any ratio.

The molecular weight modifier is used in an amount of usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, based on 100 mol of the dihydroxy compound. By setting the amount of the molecular weight modifier to be in this range, the thermal stability and hydrolysis resistance of the polycarbonate resin composition can be improved.

At the time of the reaction, as long as the desired polycarbonate resin is obtained, the order of mixing the reaction substrate, the reaction medium, the catalyst, the additive, and the like is arbitrary, and an appropriate order can be arbitrarily set. For example, when carbonium chloride is used as the carbonate precursor, the molecular weight modifier may be used during the reaction from the reaction of the dihydroxy compound with the carbon ruthenium chloride (carbon ruthenium chloride) until the start of the polymerization reaction. Mix at any time. Further, the reaction temperature is usually from 0 to 40 ° C, and the reaction time is usually from several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

(melt transesterification method)

In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is carried out.

The dihydroxy compound is as described above. On the other hand, as a carbonic acid diester, an example Examples thereof include a dialkyl carbonate compound such as dimethyl carbonate, diethyl carbonate or di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate; and the like. Among them, diphenyl carbonate and substituted diphenyl carbonate are preferred, and diphenyl carbonate is preferred. Further, the carbonic acid diester may be used alone or in combination of two or more kinds in any combination and in any ratio.

The ratio of the dihydroxy compound to the carbonic acid diester is arbitrary as long as the desired polycarbonate resin is obtained, and it is preferable to use a carbonic acid diester or more in an amount equal to or more than the molar amount of the dihydroxy compound. For use above 1.01 Moule. Further, the upper limit is usually 1.30 m or less. By setting it as such a range, the terminal hydroxyl group can be adjusted to a preferable range.

In the case of a polycarbonate resin, the amount of terminal hydroxyl groups tends to have a large influence on thermal stability, hydrolytic stability, color tone, and the like. Therefore, the amount of terminal hydroxyl groups can also be adjusted as needed by any known method. In the transesterification reaction, a polycarbonate resin having a terminal hydroxyl group-adjusted amount can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the degree of pressure reduction during the transesterification reaction, and the like. Further, by this operation, the molecular weight of the obtained polycarbonate resin can usually also be adjusted.

When the mixing ratio of the carbonic acid diester and the dihydroxy compound is adjusted to adjust the amount of terminal hydroxyl groups, the mixing ratio thereof is as described above. Further, as a more aggressive adjustment method, a method of separately mixing the terminal blocking agent at the time of the reaction can be mentioned. Examples of the terminal blocking agent at this time include monohydric phenols, monocarboxylic acids, and carbonic acid diesters. Further, one type of the terminal blocking agent may be used, or two or more types may be used in any combination and in any ratio.

When a polycarbonate resin is produced by a melt transesterification method, a transesterification catalyst is usually used. Any one can be used for the transesterification catalyst. Among them, it is preferred to use, for example, an alkali metal compound and/or an alkaline earth metal compound. Further, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound or an amine compound may be used in combination. Further, one type of the transesterification catalyst may be used, or two or more types may be used in any combination and in any ratio.

In the melt transesterification method, the reaction temperature is usually from 100 to 320 °C. Further, the pressure at the time of the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt-condensation reaction can be carried out while removing a by-product such as an aromatic hydroxy compound under the above conditions.

The melt polycondensation reaction can be carried out by any of a batch method and a continuous method. When it is carried out in a batch form, the order of mixing the reaction substrate, the reaction medium, the catalyst, the additive, and the like is arbitrary as long as the desired aromatic polycarbonate resin is obtained, and an appropriate order can be arbitrarily set. However, in consideration of the stability of the polycarbonate resin and the polycarbonate resin composition, the melt-condensation reaction is preferably carried out in a continuous manner.

In the melt transesterification process, a catalyst deactivator may also be used as needed. As the catalyst deactivator, a compound which neutralizes the transesterification catalyst can be used arbitrarily. Examples of the examples include sulfur-containing acidic compounds and derivatives thereof. Further, one type of the catalyst deactivator may be used, or two or more types may be used in any combination and ratio.

The amount of the catalyst deactivator to be used is usually 0.5 equivalent or more, preferably 1 equivalent or more, and usually 10 equivalents or less, preferably 5 or less, based on the alkali metal or alkaline earth metal contained in the above-mentioned transesterification catalyst. Below the equivalent. Further, the amount is usually 1 ppm or more, and usually 100 ppm or less, and preferably 20 ppm or less, based on the aromatic polycarbonate resin.

The molecular weight of the polycarbonate resin is arbitrary, and can be appropriately selected and determined. The viscosity average molecular weight [Mv] in terms of solution viscosity is usually 10,000 or more, preferably 16,000 or more, more preferably 18,000 or more, and usually 40,000 or less. It is preferably 30,000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, and it is more preferable when it is used for applications requiring high mechanical strength. . On the other hand, when the viscosity average molecular weight is equal to or less than the upper limit of the above range, the fluidity of the polycarbonate resin composition of the present invention can be suppressed and improved, and the moldability can be improved and the molding process can be easily performed. Further, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be used in combination, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed.

Further, the viscosity average molecular weight [Mv] means that methylene chloride is used as a solvent, and the ultimate viscosity [η] (unit: dl/g) at a temperature of 20 ° C is obtained using a Ubbelohde viscometer. The viscosity value of Schnell is η = 1.23 × 10 ^-4 Mv ^0.83 and the value is calculated. In addition, the ultimate viscosity [η] is a value calculated by the following formula (1) by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g/dl).

The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary, and can be appropriately selected and determined, and is usually 1,000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less. Thereby, the retention heat stability and color tone of the polycarbonate resin composition of the present invention can be further improved. Further, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more. Thereby, the decrease in molecular weight can be suppressed, and the mechanical properties of the polycarbonate resin composition of the present invention can be further improved. Further, the unit of the terminal hydroxyl group concentration is expressed in ppm with respect to the weight of the terminal hydroxyl group of the weight of the polycarbonate resin. This measurement method is a colorimetric measurement by a titanium tetrachloride/acetic acid method (method described in Macromol. Chem. 88 215 (1965)).

The polycarbonate resin may be used singly or in combination of two or more kinds in any combination and in any ratio.

The polycarbonate resin may be used alone (so-called polycarbonate resin, and is not limited to one type containing only a polycarbonate resin, but includes a plurality of polycarbonates having, for example, a monomer composition or a molecular weight different from each other. The polycarbonate resin may be used in combination with an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. Further, for example, in order to further improve flame retardancy or impact resistance, a polycarbonate resin may be formed into a copolymer with an oligomer or a polymer having a decane structure; in order to further improve thermal oxidation stability or difficulty Flammability, made into a copolymer with a monomer, oligomer or polymer having a phosphorus atom; in order to improve thermal oxidative stability, it is made into a monomer, oligomer or polymer having a dihydroxyanthracene structure. a copolymer; in order to improve optical properties, a copolymer having an oligomer or polymer having an olefin structure such as polystyrene; and an oligomer or polymer with a polyester resin for improving chemical resistance The copolymer or the like is composed of a copolymer of a polycarbonate resin as a main component. When it is used in combination with another thermoplastic resin, the ratio of the polycarbonate resin in the resin component is preferably 50% by weight or more, more preferably 60% by weight, still more preferably 70% by weight or more.

In addition, in order to improve the appearance of the molded article or improve the fluidity, the poly The carbonate resin may also contain a polycarbonate oligomer. The polycarbonate oligomer has a viscosity average molecular weight [Mv] of usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Further, the polycarbonate oligomer contained is preferably 30% by weight or less of a polycarbonate resin (containing a polycarbonate oligomer).

Further, the polycarbonate resin may be not only a raw material but also a polycarbonate resin (i.e., a polycarbonate resin whose material is reused) which is regenerated from the finished product. Examples of the product to be used as described above include an optical recording medium such as a compact disc; a light guide plate; a vehicle transparent member such as an automobile window glass, a car headlight light distribution mirror, and a windshield; a container such as a water bottle; a lens; a soundproof wall and a glass window. Building components such as corrugated sheets. Further, a pulverized product obtained from a defective product, a runner, a flow path, or the like of the product, or a pellet obtained by melting the same may be used.

Among them, the recycled polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less, based on the polycarbonate resin contained in the polycarbonate resin composition of the present invention. The reason for this is that the recycled polycarbonate resin is highly likely to be deteriorated by thermal deterioration or deterioration over time, and therefore, when such a polycarbonate resin is used in a range larger than the above range, the hue or mechanical properties are lowered. The possibility.

In the case of the crystalline thermoplastic resin, the melting point of the resin used in the present embodiment is usually 80 ° C or higher, preferably 120 ° C or higher. On the other hand, it is usually 350 ° C or lower, preferably 300 ° C or lower. In the case of an amorphous thermoplastic resin, the glass transition point is usually 80 ° C or higher, preferably 120 ° C or higher. On the other hand, it is usually 350 ° C or lower, preferably 300 ° C or lower. By this range, injection molding is preferably carried out.

Further, in the case of a thermoplastic resin, the modulus of elasticity is preferably 300 MPa or more at room temperature, more preferably 700 MPa or more, still more preferably 800 MPa or more. By this range, even when it is used for a lighting fixture or the like, the situation in which the rigidity is insufficient due to the temperature rise caused by the lighting is suppressed.

<1-4. Transmission rate adjuster>

The transmittance adjusting agent is a substance having a refractive index different from the refractive index of the resin, and is a substance which can disperse light. The refractive index as the object here may be the refractive index of any wavelength in the visible light region, and is representative of any wave in the visible light region. The absolute value of the long-term refractive index difference is 0.005 or more. The measurement method is not particularly limited, and can be measured by an Abbe refractometer or a liquid immersion method by YOSHIYAMA et al. (AEROSOL Research Vol. 9, No. 1 Spring pp. 44-50 (1994)). By using a transmittance adjusting agent, the amount of the phosphor can be adjusted, and as a result, the total light transmittance can be adjusted. Examples of the transmittance adjusting agent include an inorganic light transmittance adjusting agent, an organic light transmittance adjusting agent, and a bubble.

As the inorganic light transmittance adjusting agent, for example, an inorganic light transmittance adjusting agent containing an element such as cerium, aluminum, titanium, zirconium, calcium, magnesium, zinc or cerium can be used, and it is preferable to use cerium or aluminum. An inorganic light transmittance adjusting agent of at least one element selected from the group consisting of titanium and zirconium. As the organic light transmittance adjusting agent material, an acrylic-based, styrene-based, polyamide-based or organic light-transmitting ratio adjusting agent containing cerium or fluorine as an element can be used. Among them, acrylic light transmittance adjustment is preferably used. An organic light transmittance adjusting agent containing cerium as an element.

Specific examples of the inorganic light transmittance adjusting agent include metal fluorides such as silica, white carbon, molten cerium oxide, talc, calcium fluoride or magnesium fluoride, magnesium oxide, zinc oxide, and oxidation. Titanium, aluminum oxide, zirconium oxide, boron oxide, boron nitride, aluminum nitride, tantalum nitride, calcium carbonate, barium carbonate, magnesium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, barium sulfate , calcium citrate, magnesium citrate, aluminum citrate, sodium alumininate, zinc citrate, zinc sulfide, glass particles, glass fiber, glass flakes, mica, apatite, zeolite, sepiolite, bentonite, Mongolia Desulphur, hydrotalcite, kaolinite, potassium titanate and other materials.

These inorganic transmittance adjusting agents may be treated with various surface treating agents such as a decane coupling agent, a titanate coupling agent, a methyl hydrogen polyoxyalkylene oxide, a polyoxyphthalic acid oil, or a fatty acid-containing hydrocarbon compound. Among them, an alkyltrimethoxydecane such as methyltrimethoxydecane, ethyltrimethoxydecane, octyltrimethoxydecane or dodecyltrimethoxydecane is preferred, and the dynamic viscosity is 25 Methylhydrogenpolyoxane in the range of 5 to 100,000 mm ² /s at ° C, kinetic viscosity of 5 to 100,000 mm ² /s of dimethylpolyphthalic acid or methylphenyl at 25 ° C The polyoxygenated oil is further preferably a methyl hydrogen polyoxyalkylene having an kinetic viscosity of 10 to 1000 mm ² /s at 25 ° C. In the present embodiment, a transmittance adjusting agent which is treated with the surface treating agent in advance may be used, or a transmittance adjusting agent which is used by directly adding a surface treating agent to a kneading machine and performing surface treatment in a kneading machine during kneading may be used. .

Examples of the organic light transmittance adjusting agent include a styrene-based (co)polymer, an acrylic (co)polymer, a decane-based (co)polymer, a sesquiterpene derivative, and a polyamine. (total) materials such as polymers. Some or all of the molecules of the organic transmittance adjusting agents may or may not be crosslinked. Here, the term "(co)polymer" means both "aggregate" and "co-aggregate".

The transmittance adjusting agent preferably contains at least one selected from the group consisting of ceria, glass, calcium carbonate, titanium oxide, sesquiterpene oxide, polyfluorene oxide, calcium fluoride, magnesium fluoride, and mica. 1 species.

Further, as the transmittance adjusting agent, the Mohs hardness is preferably less than 8, and further preferably less than 7. By using such a hardness transmittance adjusting agent, discoloration of the wavelength converting member is suppressed, and the container is not damaged, and impurities are not mixed.

Further, as the transmittance adjusting agent, the ratio L/D of the major axis L to the minor axis D is preferably 200 or less. By using such a range of transmittance adjusting agent, discoloration of the wavelength converting member is suppressed, and the container is not damaged, and impurities are not mixed. The L/D is preferably 50 or less.

Further, when the transmittance of the wavelength conversion member is adjusted by the transmittance adjusting agent, for example, a transmittance adjusting agent having a small average particle diameter can be added, and a transmittance difference between the refractive index difference and the wavelength converting member can be adjusted. The agent or the addition amount of the transmittance adjusting agent is increased to reduce the transmittance of the wavelength conversion member, thereby adjusting.

The average particle diameter of the transmittance adjusting agent is preferably 100 μm or less, more preferably 0.1 μm or more and 30 μm or less, further preferably 0.1 μm or more and 15 μm or less, and still more preferably 1 μm or more and 5 μm or less.

In the case of the present embodiment, when the transmittance adjusting agent is used, the total weight of the wavelength converting member is 100% by weight, and usually 0.1% by weight or more, and preferably 0.3% by weight or more. Further, it is usually contained in an amount of 70% by weight or less, preferably 40% by weight or less.

The transmittance adjusting agent has a total weight of the resin composition before molding of 100% by weight, and usually 0.1% by weight or more, preferably 0.3% by weight or more. Further, it is usually contained in an amount of 70% by weight or less, preferably 40% by weight or less.

<1-5. Other additives>

As another additive, an effective amount of an additive generally used for a resin can be used in the wavelength conversion member or the resin composition of the present embodiment. Specific examples thereof include other thermoplastic resins, mold release agents, crystal nucleating agents, antioxidants, anti-caking agents, ultraviolet absorbers, light stabilizers, plasticizers, heat stabilizers, colorants, flame retardants, and anti-wear agents. Electrostatic agent, anti-fogging agent, surface wetting improving agent, calcining auxiliary agent, slip agent, flame retardant, crosslinking agent, dispersing aid or various surfactants, slip agent, hydrolysis preventing agent, neutralizing agent, reinforcing material , heat conductive materials, etc. These may be used alone or in combination of two or more.

<1-5-1. Antioxidant>

Specific examples of the antioxidant include 2,6-di-t-butyl-4-hydroxytoluene and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,3',3",5,5',5"-hexa-t-butyl -a,a',a"-(homotriene-2,4,6-triyl)tri-p-cresol, octadecyl-3-(3,5-di-t-butyl-4- Hydroxyphenyl)propionate, 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-tri -2,4,6(1H,3H,5H)-trione, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, diethylbis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphine Calcium acid, bis(2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethylphenyl)ethane, N,N'-hexane-1,6 -Dibasic bis[3-(3,5-di-t-butyl-4-hydroxyphenylpropanamide) and other hindered phenolic antioxidants; tridecyl phosphite, diphenyl decyl phosphite , tetrakis(2,4-di-t-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite diester, bisphosphite bis[2,4-double (1 Phosphate-based antioxidants such as 1-methylethyl)-6-methylphenyl]ethyl ester and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite; 3-hydroxy- a lactone-based antioxidant such as a reaction product of 5,7-di-t-butyl-furan-2-one with xylene; dilauryl thiodipropionate, distearyl thiodipropionate A sulfur-based antioxidant, etc. These antioxidants may be used alone or in combination of two or more kinds in any combination and in any ratio.

The amount of the antioxidant to be used is not particularly limited as long as the effect of the present invention is not significantly impaired, and the resin composition is usually 100 ppm by weight or more and 50,000 ppm by weight or less. If it is less than the lower limit of the range, the effect of the antioxidant is small, and if it exceeds the upper limit, the antioxidant bleeds out and causes coloration.

<1-5-2. Release agent>

In the case of using an amorphous resin, it is preferred to add a release agent. Examples of the release agent include higher fatty acid esters of higher fatty acids, monohydric or polyhydric alcohols, natural animal waxes such as beeswax, natural plant waxes such as carnauba wax, natural petroleum waxes such as paraffin wax, and natural charcoal systems such as montan wax. A wax, an olefin wax, a polyoxygenated oil, an organic polyoxyalkylene or the like is particularly preferably a higher fatty acid ester of a higher fatty acid, a monohydric or a polyhydric alcohol.

As the higher fatty acid ester, a substituted or unsubstituted carbon number of 1 to 20 carbon atoms or a partial ester of a substituted or unsubstituted carbonic acid having 10 to 30 carbon atoms or Full ester. As a partial ester or a full ester of the monohydric or polyhydric alcohol and a saturated fatty acid, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, and stearin may be mentioned. Acid stearyl ester, behenic acid monoglyceride, behenyl behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetradecanoate, propylene glycol single hard Fatty acid ester, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl bisphenolate, sorbitan monostearate , 2-ethylhexyl stearate, and the like. Among them, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

As the higher fatty acid, a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferred. Examples of such a saturated fatty acid include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.

These release agents may be used alone or in combination of two or more. The content of the release agent is preferably 0.0001% by weight or more, more preferably 0.01% by weight or more, even more preferably 0.1% by weight or more, and particularly preferably 1% by weight or less, and more preferably the resin composition. It is preferably 0.7% by weight or less, and particularly preferably 0.5% by weight or less.

<1-5-3. Crystal nucleating agent>

In the case of using a crystalline resin, it is preferred to add a crystallization nucleating agent. Specific examples of the crystal nucleating agent include, as an inorganic nucleating agent, talc, kaolinite, montmorillonite, synthetic mica, clay, zeolite, cerium oxide, graphite, carbon black, zinc oxide, magnesium oxide, and oxidation. Metal salts of titanium, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, cerium oxide and phenyl phosphonate. Moreover, the inorganic nucleating agents can also be modified by organic matter to Improve the dispersion in the composition.

On the other hand, examples of the organic nucleating agent include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, bismuth benzoate, lithium terephthalate, sodium terephthalate, and benzene. Potassium diformate, calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octadecanoate, calcium octadecanoate, sodium stearate, stearic acid Potassium, lithium stearate, calcium stearate, magnesium stearate, barium stearate, sodium montanate, calcium montanate, sodium toluene, sodium salicylate, potassium salicylate, zinc salicylate, diphenyl An organic carboxylic acid metal salt such as aluminum formate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate or sodium cyclohexanecarboxylate; organic sulfonate such as sodium p-toluenesulfonate or sodium sulfoisophthalate; Carboxamide which is stearylamine, exoethyl dilaurosamine, palm amide, hydroxystearylamine, mustard amide, 1,3,5-benzenetricarboxylic acid tris(t-butyl decylamine); Low density polyethylene, high density polyethylene, polypropylene, polyisopropene, polybutene, poly-4-methylpentene, polyethylene cycloalkane, polyethylene trialkyl a polymer such as an alkane or a high melting point polylactic acid; a sodium salt of a polymer having a carboxyl group such as a sodium salt of an ethylene-acrylic acid or methacrylic acid copolymer; a sodium salt of a styrene-maleic anhydride copolymer; Ionic polymer); benzylidene sorbitol and its derivatives, sodium metal salt of phosphorus compound such as sodium-2,2'-methylenebis(4,6-di-t-butylphenyl) phosphate; , 2-methylbis(4,6-di-t-butylphenyl) sodium; polyethylene wax, and the like.

The average particle diameter of the nucleating agent is arbitrary within a range that does not significantly impair the effects of the present invention. More preferably, it is usually 50 μm or less, preferably 10 μm or less. The preferred amount of the nucleating agent is usually 0.01% by weight or more and 5% by weight or less based on the resin composition.

<1-5-4. Light stabilizer>

As the light stabilizer, bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl)ester, 1,1-dimethylethyl phthalate may be mentioned. Reaction product of hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethyl) 4-hydroxyphenyl]methyl]butyl malonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 1,2, Methyl 2,6,6-pentamethyl-4-piperidinyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 1-[2 -[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]ethyl]-4-[3-(3,5-di-t-butyl-4- Hydroxyphenyl)propoxycarbonyl]-2,2,6,6-tetramethylpiperidine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3 , 5-three -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido]hexamethylene {(2,2,6,6-tetramethyl-) A hindered amine stabilizer such as 4-piperidinyl)imido}.

The light stabilizer may be used singly or in combination of two or more kinds in any combination and in any ratio.

Further, the amount of the light stabilizer used is usually 0.1% by weight or more and 5% by weight or less based on the resin composition.

<1-5-5. UV absorber>

Examples of the ultraviolet absorber include a benzotriazole compound, a benzophenone compound, and the like, in addition to an inorganic ultraviolet absorber such as cerium oxide or zinc oxide. An organic ultraviolet absorber such as a compound. Among these, it is preferably selected from the group consisting of a benzotriazole compound, 2-(4,6-diphenyl-1,3,5-three -2-yl)-5-[(hexyl)oxy]-phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-three 2-yl]-5-(octyloxy)phenol, 2,2'-(1,4-phenylene)bis[4H-3,1-benzo At least one of the group consisting of -4-keto] and [(4-methoxyphenyl)-methylene]-malonic acid-dimethyl ester.

Specific examples of the benzotriazole compound include methyl-3-[3-t-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate- a condensate of polyethylene glycol. Further, specific examples of the other benzotriazole compound include 2-bis(5-methyl-2-hydroxyphenyl)benzotriazole and 2-(3,5-di-t-butyl- 2-hydroxyphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3-third Butyl 5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(3, 5-di-t-pentyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzene And triazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol][A Alkyl-3-[3-t-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol] condensate or the like.

The ultraviolet absorber may be used singly or in combination of two or more kinds in any combination and in any ratio.

Further, the amount of the ultraviolet absorber used is 100% by weight, and usually 100 ppm or more and 5% by weight or less, based on the total weight of the resin composition.

<1-5-6. Flame Retardant>

Examples of the flame retardant include an organic halogen system, a phosphorus system, an organic acid metal salt system, and a polyfluorene. An organic flame retardant and an inorganic flame retardant which are oxygen-based and nitrogen-based compounds, and examples of the flame retardant auxiliary include a fluororesin-based compound and a bismuth compound-based flame retardant auxiliary. It is also possible to use a combination of a flame retardant and a flame retardant, or a combination of a plurality of types. Among them, a phosphorus-based flame retardant, an organic acid metal salt-based flame retardant, and a fluororesin-based flame retardant auxiliary agent are preferable.

Examples of the organic halogen compound include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, and polyacrylic acid. Bromobenzyl ester and the like.

Examples of the phosphorus-based flame retardant include an aromatic phosphate, a polyphosphoric acid, ammonium polyphosphate, red phosphorus, or a phosphorus-nitrogen compound having a bond between a phosphorus atom and a nitrogen atom in the main chain. Specific examples of the phosphate-based flame retardant include triphenyl phosphate, resorcinol bis(di(xylene) phosphate), hydroquinone bis(di(xylene) phosphate), and 4 , 4'-biphenol bis(di(xylene) phosphate), bisphenol A bis(di(xylene) phosphate), resorcinol bis(diphenyl phosphate), hydroquinone bis (phosphoric acid) Diphenyl ester), 4,4'-biphenol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), and the like. The organic acid metal salt-based flame retardant is preferably an organic sulfonic acid metal salt, particularly preferably a fluorine-containing organic sulfonic acid metal salt, and specific examples thereof include potassium perfluorobutanesulfonate. Examples of the nitrogen-based compound include melamine, cyanuric acid, and melamine cyanurate. Examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide, a ruthenium compound, and a boron compound. The fluorine-based flame retardant auxiliary agent is preferably a fluoroolefin resin, and a tetrafluoroethylene resin having a fiber structure can be exemplified. The fluorine-based flame retardant auxiliary may be in the form of a powder or a dispersion, or may be in the form of a powder in which the fluororesin is coated with another resin, and may be in any form. Examples of the antimony compound-based flame retardant auxiliary include antimony trioxide, antimony pentoxide, and sodium antimonate.

The blending ratio of the flame retardant and the flame retardant auxiliary may be adjusted to an amount necessary to achieve a desired flame retardancy level, and is usually preferably in the case of a phosphorus-based flame retardant in the resin composition. In the range of 1 to 20% by weight, in the case of the organic acid metal salt, it is in the range of 0.01 to 1% by weight, and in the case of the fluororesin-based flame retardant auxiliary agent, it is in the range of 0.01 to 1% by weight. One type or two or more types of flame retardant and flame retardant auxiliary can be used in the above range. If it is less than this range, the effect of improving the flame retardancy is less likely to occur, and if it is more than this range, thermal stability and mechanical properties tend to be lowered, which is not preferable. Further, the flame retardance level can be determined, for example, by a combustion test represented by UL94 or the like.

<2. Method of Manufacturing Wavelength Conversion Member>

The method of manufacturing the wavelength conversion member of the second embodiment is characterized by comprising the steps of mixing a resin and a phosphor and forming a mixture obtained by the step, and performing the above mixing step under an inert gas atmosphere and / or the above forming step. These steps are not particularly limited as long as they are manufactured according to the conventional practice.

Regarding the step of mixing the resin and the phosphor, for example, in order to manufacture a wavelength converting member provided with a resin and a phosphor, preferably a transmittance adjusting agent, and other additives formulated as needed, uniaxial or biaxial extrusion may be used. Take the machine as a mixing machine. The resin and the other additives including the phosphor and the transmittance adjusting agent may be supplied from one place at a time, or other additives such as a phosphor may be sequentially supplied after the resin is supplied. Further, two or more components selected from the respective components may be mixed and kneaded in advance. In particular, the phosphor is preferably supplied after being mixed with other powder components. Further, the extruder may be a vent having a volatility volatile component.

Further, the phosphor and the transmittance adjusting agent may be subjected to surface treatment by the third component. The step of molding the mixture obtained by the mixing step may be followed by press molding or injection molding, hollow molding, extrusion molding, compression molding, equalization pressure molding, transfer molding, rotational molding, or the like after the kneading. Formed by the method. Among these, in consideration of the applicability to the light-emitting device or the illumination device, it is preferable to perform injection molding from the viewpoint of the degree of freedom of shape of the formable wavelength conversion member.

The injection molding includes RIM (Reaction Injection Molding) molding and liquid injection (LIM) molding for a thermosetting resin such as polyfluorene oxide. In the injection molding of a general thermoplastic resin, the resin composition is melted by heating, and the molten resin composition is molded into a mold. Further, two or more kinds of different types of particles may be blended and blended in an arbitrary ratio, and supplied, and melt-mixed and molded in an injection molding machine. The temperature at the time of melting is preferably a temperature higher than the glass transition point in the case of an amorphous resin, and preferably a temperature higher than the melting point in the case of a crystalline resin, for example, 150 ° C or higher, preferably 170 ° C or higher. . When the molding temperature is too high, the molded body is colored. Therefore, it is preferably molded at a temperature of 170 ° C or more and 320 ° C or less.

Furthermore, if the injection molding device with the hot runner is used for injection molding, the pouring can be reduced. The loss of the channel is preferred.

The molded body may have any shape as long as it has a planar structure that is a light-emitting surface in the white LED light-emitting device. At this time, the wavelength conversion member may be in a state in which the shape is maintained by the monomer without the holding member. However, the wavelength conversion member requires a certain thickness. In this case, the thickness of the wavelength converting member is preferably 0.3 mm or more and 5 mm or less, more preferably 0.5 mm or more and 3 mm or less.

Further, the wavelength conversion member of the present invention has a planar structure including a phosphor and a resin for holding the phosphor, and at least a part of the planar structure has a total light transmittance of 30% or more, preferably 42 More preferably, it is a single layer structure, more preferably 45% or more, further preferably 47% or more, and on the other hand, 70% or less, preferably 60% or less, more preferably 55% or less. It can also be a multi-layered structure of two or more layers.

Further, the main portion of the planar structure may have a total light transmittance of 30% or more, preferably 42% or more, more preferably 45% or more, still more preferably 47%, and on the other hand, 70% or less. It is preferably 60% or less, more preferably 55% or less. Further, the surface may be a mirror surface, or may have a fine structure such as wrinkles, or may be hard coated, printed, or the like on the outer surface.

The environment in which the resin and the phosphor are mixed and the step of forming the mixture obtained by the step is not particularly limited, and it is preferably carried out under an inert gas atmosphere, more preferably under a nitrogen atmosphere. When a polyarylate resin, a cycloolefin copolymer resin or the like is used, the luminous efficiency is particularly increased by the nitrogen atmosphere. In addition, when the glass transition temperature Tg is 150 ° C or more and the molding temperature is 300 ° C or more, the luminous efficiency is improved.

<3. Light-emitting device>

A third embodiment of the present invention is a light-emitting device including a semiconductor light-emitting element and a wavelength conversion member of the first or second embodiment.

The light-emitting device of the present embodiment is a wavelength conversion member of the first or second embodiment of the present invention which contains at least a blue semiconductor light-emitting device and a wavelength conversion member that converts the wavelength of blue light. The blue semiconductor light-emitting element may be in close contact with the wavelength conversion member of the first or second embodiment of the present invention, or may be separated, and may have a transparent resin or a space. Preferably, as shown in the schematic diagram of FIG. 1, there is a space between the light-emitting element and the wavelength conversion member.

Hereinafter, the configuration will be described with reference to FIGS. 1 and 2 .

Fig. 1 is a schematic view showing a light-emitting device according to a third embodiment of the present invention.

In the light-emitting device 10, at least the blue semiconductor light-emitting element 1 and the wavelength conversion member 3 are included as constituent members. The blue semiconductor light-emitting element 1 emits excitation light for exciting the phosphor contained in the wavelength conversion member 3.

The blue semiconductor light-emitting element 1 generally emits excitation light having a peak wavelength of 425 nm to 475 nm, preferably an excitation light having a peak wavelength of 430 nm to 470 nm. The number of the blue semiconductor light-emitting elements 1 can be appropriately set in accordance with the intensity of the excitation light necessary for the device.

On the other hand, a purple semiconductor light emitting element can be used instead of the blue semiconductor light emitting element 1. The violet semiconductor light-emitting element generally emits excitation light having a peak wavelength of 390 nm to 425 nm, preferably an excitation light having a peak wavelength of 395 to 415 nm.

The blue semiconductor light emitting element 1 is mounted on the wafer mounting surface 2a of the wiring substrate 2. A wiring pattern (not shown) for supplying electrodes to the blue semiconductor light-emitting elements 1 is formed on the wiring substrate 2 to constitute a circuit. Although the wavelength conversion member 3 is placed on the wiring board 2 in FIG. 1, the present invention is not limited thereto, and the wiring board 2 and the wavelength conversion member 3 may be disposed via other members.

For example, in FIG. 2, the wiring board 2 and the wavelength conversion member 3 are arranged via the casing 4. The casing 4 may also be tapered to impart directivity to the light. Also, the casing 4 may be a reflective material.

From the viewpoint of improving the light-emitting efficiency of the light-emitting device 10, the wiring board 2 is preferably excellent in electrical insulation, has good heat dissipation, and has high reflectance, and may not have blue on the wafer mounting surface of the wiring substrate 2. A reflector having a high reflectance is provided on at least a part of the surface of the color semiconductor light-emitting element 1 or the inner surface of the other member connecting the wiring board 2 and the wavelength conversion member 3.

The reflectance of the reflector used in the wiring board or the reflectance of the reflector covering a part of the wiring board is preferably 80% or more, and more preferably the area of the portion having a reflectance of 80% or more is the wiring board. 50% or more of the area, more preferably 70% or more, particularly preferably 80% or more, and further preferably a portion having a reflectance of 90% or more, more preferably The area of the portion having a reflectance of 90% or more is 50% or more of the area of the wiring substrate, more preferably 70% or more, and particularly preferably 80% or more. Further, the reflectance means the reflectance of light in the visible light region.

Similarly, in the case of using the casing, the reflectance of the reflecting plate used in the casing or the reflectance of the reflecting plate covering a part of the casing is preferably 80% or more, more preferably 80%. The area of the above portion is 50% or more of the area of the casing and the wiring board, more preferably 70% or more, and particularly preferably 80% or more. Further, it is preferable to have a portion having a reflectance of 90% or more, and more preferably a portion having a reflectance of 90% or more, which is 50% or more of the area of the casing and the wiring board, and more preferably 70% or more. Particularly good is more than 80%. Further, the reflectance means the reflectance of light in the visible light region.

As a material for achieving such a reflectance, a reflective material containing a filler in a resin can be mentioned. Specifically, it is preferable to contain a reflection of a metal oxide filler such as alumina, titania, cerium oxide, zinc oxide or magnesium oxide in a polyoxyxylene resin, a polycarbonate resin or a polyphthalamide resin. A material or a reflective material containing a metal oxide in a ceramic.

Examples of the reflective material containing a metal oxide such as titanium oxide in the polycarbonate resin include, for example, Iupilon EHR3100 and EHR3200.

Examples of the reflective material containing a metal oxide such as alumina or titanium oxide in the polyoxyxene resin include a reflective material described in WO2011/078239 and WO2011/136302.

Further, a reflective material containing a metal oxide such as alumina or titania in polyphthalic acid phthalamide is preferably exemplified.

The wavelength conversion member 3 wavelength-converts a portion of the incident light emitted from the blue semiconductor light-emitting element 1, and emits light of a different wavelength from the incident light. The wavelength conversion member 3 contains a resin and a phosphor. The type of the phosphor (not shown) is not particularly limited. When the light-emitting device is a white light-emitting device, the type of the phosphor can be appropriately adjusted in accordance with the type of the excitation light of the semiconductor light-emitting device to emit white light.

In the case where the semiconductor light-emitting element is a blue semiconductor light-emitting element, a light-emitting device that emits white light can be produced by using a yellow phosphor or using a green phosphor and a red phosphor.

In the case where the semiconductor light emitting element is a purple semiconductor light emitting element, by using blue A color phosphor, a green phosphor, and a red phosphor can be used to make a white light emitting device.

Further, it is preferable that the wavelength converting member 3 contains a phosphor and contains a small amount of a transmittance adjusting agent. Examples of the transmittance adjusting agent include an inorganic light transmittance adjusting agent, an organic light transmittance adjusting agent, and a bubble. The transmittance adjusting agent preferably comprises one selected from the group consisting of ceria, glass, calcium carbonate, titanium oxide, sesquiterpene oxide, polyfluorene oxide, calcium fluoride, magnesium fluoride, and mica. More than one species.

Further, the wavelength conversion member 3 preferably has a distance from the blue semiconductor light-emitting element 1. The wavelength conversion member 3 and the blue semiconductor light-emitting element 1 may be spaces or may be provided with a transparent resin. In this manner, the distance between the wavelength conversion member 3 and the blue semiconductor light-emitting element 1 is such that the heat generated by the blue semiconductor light-emitting element 1 can suppress the fluorescence included in the wavelength conversion member 3 and the wavelength conversion member. Deterioration of the body. The distance between the blue semiconductor light-emitting device 1 and the wavelength conversion member 3 is preferably 10 μm or more, more preferably 100 μm or more, particularly preferably 1.0 mm or more, and more preferably 1.0 m or less. It is preferably 500 mm or less, and particularly preferably 100 mm or less.

The light-emitting device according to the third embodiment of the present invention is preferably a light-emitting device that emits white light. Preferably, the light-emitting device that emits white light has a deviation duv of -0.0200 to 0.0200 from the light emitted from the light-emitting device and the black body radiation trajectory from the light color, and the color temperature is 1800 K or more and 7,000 K or less.

The illuminating device of the third embodiment can also achieve a high beam when emitting light of a low color temperature. Therefore, it is particularly preferable to emit a light having a color temperature of 5500 K or less, 5000 K or less, and 4500 K or less.

The light-emitting device that emits white light in this way is preferably provided in the illumination device.

<4. Lighting fixtures>

A fourth embodiment of the present invention is a lighting fixture comprising the light-emitting device of the third embodiment. As described above, since the light-emitting device of the third embodiment emits a high total light beam, and even a light-emitting device that emits white light of a low color temperature in which the full beam is easily reduced, a high total beam can be obtained, and thus it is possible to obtain A lighting fixture with a high total beam. Preferably, the lighting fixture is provided with a diffusion member that covers the wavelength conversion member in the light-emitting device such that the color of the wavelength conversion member is inconspicuous when the light is extinguished. As the diffusion member, as long as the haze is 40% or more, the total light The linear transmittance is not particularly limited as long as it is 60% or more, and may be disposed as a lighting fixture as long as it is disposed outside the wavelength conversion member, or may be incorporated in the light-emitting device. At least a part of the other members in the space including the diffusion member and the wavelength conversion member are preferably reflectors having a high reflectance.

<5. Resin composition constituting the wavelength converting member>

The resin composition according to the fifth embodiment of the present invention contains a phosphor and a resin, and the resin composition is molded into at least a part of the planar structure when the wavelength conversion member having a planar structure is formed. The total light transmittance is 30% or more and 70% or less. Further, it is preferable that the total light transmittance of the main portion of the planar structure is 30% or more and 70% or less.

Further, the total light transmittance is preferably 42% or more, more preferably 45% or more, still more preferably 47% or more. On the other hand, it is preferably 60% or less, more preferably 55% or less.

In other words, a resin composition capable of adjusting the total light transmittance of the wavelength conversion member can be produced, and the description of the raw material is the same as that described in <1-1. Wavelength conversion member>.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, although the invention is not limited to the embodiments described below.

<Materials>

The resin, the phosphor, the transmittance adjuster, the oxidation stabilizer, and the release agent shown below are prepared. Moreover, the physical properties of the transmittance adjusting agents 1 to 14 are shown in Table 1.

(amorphous thermoplastic resin)

Resin 1: manufactured by Mitsubishi Engineering Plastics Co., Ltd. Polycarbonate resin S-3000F glass transfer temperature = 149 ° C

Resin 2: manufactured by Mitsubishi Rayon Co., Ltd. PMMA resin ACRYPET VH001 glass transfer temperature = 100 ° C

Resin 3: manufactured by JSR Co., Ltd. Rotary olefin resin ARTON F5023 glass transfer temperature = 165 ° C

Resin 4: U polymer U100 glass transfer temperature manufactured by UNITIKA Co., Ltd. = 198 ° C

(The crystalline thermoplastic resin)

Resin 5: manufactured by Asahi Glass Co., Ltd. Fluon ETFE C-88AXP Flexural modulus: 880 MPa Melting point: 150 ° C or more and 320 ° C or less

Resin 6: manufactured by KUREHA Co., Ltd. PVDF KF polymer W#850 flexural modulus: 1600 MPa Melting point: 150 ° C or more and 320 ° C or less

Resin 7: Mitsui Chemicals Co., Ltd. manufactures PMP (polymethylpentene) TPX RT18 flexural modulus: 1600 MPa Melting point: 150 ° C or more and 320 ° C or less

Resin 8: PE (polyethylene) high density polyethylene manufactured by Nippon Polyethylene Co., Ltd. NOVATEC HD HB420R flexural modulus: 1300 MPa Melting point: 150 ° C or less

Resin 9: manufactured by DAIKIN Industrial Co., Ltd. NEOFLON ETFE2 EP610 flexural modulus: 840 MPa Melting point: 150 ° C or more and 320 ° C or less

Resin 10: manufactured by Asahi Glass Co., Ltd. Fulon LM-ETFE LM730AP flexural modulus: 650 MPa Melting point: 150 ° C or more and 320 ° C or less

Resin 11: manufactured by DAIKIN Industrial Co., Ltd. NEOFLON FEP NP101 flexural modulus: 490 MPa Melting point: 150 ° C or more and 320 ° C or less

(fluorescent body)

Phosphor 1: Daimling Chemical Co., Ltd. manufactures YAG commercial product BY102D average particle size = 17 μm.

Phosphor 2: manufactured by Mitsubishi Chemical Corporation, CASN trade name BR101A average particle size = 8.5 μm

Phosphor 3: YAG average particle size manufactured by Mitsubishi Chemical Corporation = 7 μm

(transmittance adjuster)

Transmittance adjuster 1: Maxim's Tospearl 120 average particle size = 2.0 μm

Transmittance Adjuster 2: Manufactured by Ishihara Sangyo Co., Ltd. The average particle size of titanium oxide CR60 = 0.21 μm

Transmittance Adjuster 3: Manufactured by Electric Chemical Industry Co., Ltd. Fused cerium oxide FB20D

Transmittance Adjuster 4: Manufactured by Denki Kogyo Co., Ltd. Fused cerium oxide FB5D

Transmittance modifier 5: manufactured by Nippon Electric Glass Co., Ltd. Chopped strands T480H

Transmittance Adjuster 6: Made by Nippon Sheet Glass Co., Ltd. Glass Flake REF160

Transmittance Adjuster 7: Made by Nippon Sheet Glass Co., Ltd. Glass Flake REF015

Transmittance Adjuster 8: Made by Nippon Sheet Glass Co., Ltd. Glass Foil RCF160

Transmittance modifier 9: manufactured by CO-OP CHEMICAL Co., Ltd. Synthetic mica micro-mica MK300

Transmittance Adjuster 10: Manufactured by Marui Co., Ltd. Calcium Carbonate N35

Transmittance adjuster 11: manufactured by Marui Co., Ltd. Calcium carbonate Calfine200

Transmittance Adjuster 12: EP zirconia manufactured by First Rare Earth Chemical Industry Co., Ltd.

Transmittance adjuster 13: Ganzpearl SI-020 manufactured by Ganz Chemical Co., Ltd.

Transmittance Adjuster 14: Manufactured by UBE MATERIAL Co., Ltd. Calcium Citrate Whisker Zonohigi

Transmittance adjuster 15: The transmittance adjuster 3 was treated with 0.5% polyoxyphthalic acid SH1107 (manufactured by Dow Corning Toray Co., Ltd.)

Transmittance Conditioner 16: Treatment of Transmittance Conditioner 3 with 2% Ethyltrimethoxydecane

(Antioxidants)

Antioxidant 1: ADEKA Co., Ltd. phenolic antioxidant AO60

Antioxidant 2: ADEKA Co., Ltd. Phosphorus-based antioxidant Adekastab 2112

(release agent)

Release Agent 1: Unistar H476 manufactured by Nippon Oil Co., Ltd.

<Examples 1 to 10, Comparative Examples 1 to 2>

The resin 1 to 4 was dried at 80 to 120 ° C for 4 hours, and then kneaded by the composition and processing conditions of Table 2. Here, the kneading conditions are as follows. Further, when an inert gas is used, a kneading operation is performed in a nitrogen atmosphere.

(kneading conditions)

Kneading condition 1: A 20 mm Φ single-axis extruder manufactured by Toyo Seiki Co., Ltd. was used, and kneading was carried out at a screw rotation speed of 30 to 50 rpm at the temperatures shown in Table 2.

Kneading condition 2: A closed type kneading machine (laboplastomill) manufactured by Toyo Seiki Co., Ltd. was used for kneading at a rotation speed of 80 rpm for 3 minutes.

After kneading, molding was carried out at the temperatures described in Table 2. Further, the injection molding system used an injection molding machine Minimat M8/7A manufactured by Sumitomo Heavy Industries, Ltd.

The obtained wavelength conversion member has a thickness of 1 mm and is a disk shape of 35 mmΦ or more and 45 mmΦ or less. With respect to the obtained wavelength conversion member, total light transmittance measurement and measurement of light emission characteristics were carried out by the method described below. The results are shown in Table 2, and a graph showing the relationship between the total light transmittance (%) and the Lumen ratio (%) is shown in Fig. 3 .

<Measurement of total light transmittance>

A turbidity meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. was used, and a halogen lamp was used as a light source, and the inlet opening was set to 20 mmΦ, and the measurement was performed in accordance with JIS K7361.

<Measurement of luminescence characteristics>

The molded article is held on an LED light-emitting element that emits light at 450 nm, and the characteristics of the light beam, the color temperature (K), the chromaticity (x, y), and the average color evaluation number (Ra) are measured as wavelength-transformed light transmitted through the molded article. . The beam is based on the Lumen ratio (%) of the light beam of the material of Example 1.

Further, the distance between the LED light-emitting element and the wavelength conversion member is about 2.6 cm, and a space is provided therebetween.

As can be understood from the above examples and comparative examples, the total light flux of the molded body including the phosphor and the resin and having a total light transmittance of 30% or more and 70% or less is high. At the same time, it can be understood that the total beam is also high when emitting light of a lower color temperature of about 4000 K to 5500 K.

Therefore, when the light-emitting device using the molded body of the present invention emits light of a low color temperature, a high total light beam can be achieved.

<Examples 11 to 13, Comparative Example 3>

In the sealed kneading machine manufactured by Toyo Seiki Seisakusho Co., Ltd., the mixture was kneaded at 80 rpm for 3 minutes to obtain a resin composition. The obtained resin composition was molded by press molding to obtain a wavelength conversion member. In addition, the molding temperature and the kneading temperature were different depending on the resin, and were 300 ° C in Examples 11 and 12, 200 ° C in Example 13, and 280 ° C in Comparative Example 3.

With respect to the obtained wavelength conversion member, the total light transmittance measurement and the measurement of the light emission characteristics were carried out in the same manner as described above, and the color difference measurement was carried out by the method shown below. Further, it was confirmed whether or not the color conversion member was discolored. Further, the result of the measurement of the luminescence characteristics (beam) was expressed by the Lumen ratio (%) using the light beam of Example 11 as a reference.

<Color difference measurement>

Using the colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd., the white phase is used to measure the reflection of L, a, b, and the hue (L0, a0) in the absence of the transmittance adjusting agent of each composition. , b0) The distance from the Lab space coordinates of the hue (L1, a1, b1) in the case of the transmittance modifier: =E={(L0-L1) ² +(a0-a1) ² +(b0-b1) ² } ^0.5 means.

<Examples 14 to 22, Comparative Examples 4 to 5>

In the sealed kneading machine manufactured by Toyo Seiki Seisakusho Co., Ltd., the mixture was kneaded at 80 rpm for 3 minutes to obtain a resin composition. The obtained resin composition was molded by press molding to obtain a wavelength conversion member. Further, the molding temperature and the kneading temperature were set to 300 °C.

With respect to the obtained wavelength conversion member, total light transmittance measurement, color difference measurement, and light emission characteristics were measured in the same manner as described above. Further, the result of the measurement of the luminescence characteristics (beam) was expressed by the Lumen ratio (%) using the light beam of Example 14 as a reference.

<Examples 23 to 28, Comparative Examples 6 to 7>

Using the composition shown in Table 5, using 20 mm The end shaft extruder was kneaded to obtain pellets as a resin composition. The obtained pellets were made using the injection molding machine Minimat M8/7A manufactured by Sumitomo Heavy Industries, Ltd. to make 3.5 mm. , 1 mm thick disc with 3 mm The 1 mm thick arcuate shaped body was injection molded. Further, the molding temperature and the kneading temperature were set to 240 °C.

The obtained disc was used for total light transmittance measurement, color difference measurement, and an arcuate forming system for measurement of luminescence characteristics. The measurement method is the same as the above method. Further, the result of the measurement of the luminescence characteristics (beam) was expressed by the Lumen ratio (%) using the light beam of Example 23 as a reference.

As can be understood from the above examples and comparative examples, the total light flux of the molded body including the crystalline thermoplastic resin and having a total light transmittance of 30 to 70% is high. At the same time, it can be understood that the total beam is also high when a light of a lower color temperature of about 3000 K to 4000 K is emitted.

Therefore, when the light-emitting device using the molded body of the present invention emits light of a low color temperature, a high total light beam can be achieved.

<Examples 29 to 33>

In the sealed kneading machine manufactured by Toyo Seiki Seisakusho Co., Ltd., the mixture was kneaded at 80 rpm for 3 minutes to obtain a resin composition. The obtained resin composition was molded by press molding to obtain a wavelength conversion member. Further, the molding temperature and the kneading temperature were set to 300 °C.

With respect to the obtained wavelength conversion member, total light transmittance measurement, color difference measurement, and light emission characteristics were measured in the same manner as described above. Further, the result of the measurement of the luminescence characteristics (beam) was expressed by the Lumen ratio (%) using the light beam of Example 29 as a reference.

According to the above embodiment, when the transmittance adjusting agent for surface treatment is used, the total light transmittance and the total light beam can be improved without causing a large change in the color temperature.

<Light-emitting device using a reflective material having a high reflectance> <Reference Example 1~2>

Using the same wavelength conversion member (total light transmittance: 50%), in the same luminescence measurement method as described above, it was confirmed that the wiring substrate (reflectance is less than 80%) and the casing (reflectance is less than 80%) of the light-emitting device. The light-emitting efficiency is improved in the case where a reflective material having a reflectance of 93 to 95% is provided (in the case where the wiring substrate is not present on the surface of the semiconductor light-emitting device). The measurement results are shown in Table 7. The reflectance was measured using U-3310 manufactured by Hitachi High-Technologies Corporation and using barium sulfate as a standard sample.

It can be seen that high efficiency can be achieved in the present wavelength conversion member by using a certain amount or more of a reflective material having a high reflectance.

1‧‧‧Blue semiconductor light-emitting elements

2‧‧‧Wiring substrate

2a‧‧‧ wafer mounting surface

3‧‧‧wavelength conversion components

10‧‧‧Lighting device

Claims (23)

A wavelength conversion member that converts at least a portion of incident light to emit light having a wavelength different from that of the incident light, wherein the wavelength conversion member has a planar structure including absorption of the incident A phosphor that emits light of a different wavelength from the incident light and a resin that holds the phosphor at least a part of the light, and at least a part of the planar structure has a total light transmittance of 30% or more and 70% or less. The wavelength conversion member according to claim 1, wherein at least a part of the planar structure has a total light transmittance of 42% or more and 70% or less. The wavelength conversion member according to claim 1 or 2, wherein the wavelength conversion member has a thickness of 0.3 mm or more and 5.0 mm or less. The wavelength conversion member according to any one of claims 1 to 3, wherein the content of the phosphor contained in the wavelength conversion member is 15% by weight or less. The wavelength conversion member according to any one of claims 1 to 4, wherein the phosphor of the wavelength conversion member has an average particle diameter of 10 μm or more. The wavelength conversion member according to any one of claims 1 to 5, further comprising a transmittance adjusting agent. The wavelength conversion member according to any one of claims 1 to 6, wherein the resin is a crystalline resin or an amorphous resin. The wavelength conversion member according to claim 7, wherein the amorphous resin is a thermoplastic resin. The wavelength conversion member according to any one of claims 1 to 8, wherein the resin is an alloy. The wavelength conversion member according to any one of claims 1 to 9, wherein the wavelength conversion member can maintain its form in a single body without having a holding member. The wavelength conversion member according to any one of claims 1 to 10, which is formed by injection molding. A method of manufacturing a wavelength conversion member, which is a method for manufacturing a wavelength conversion member according to any one of claims 1 to 11, characterized in that: The steps of mixing the resin and the phosphor, and the step of forming the mixture obtained by the step, and performing the mixing step and/or the forming step under an inert gas atmosphere. The method for producing a wavelength conversion member according to claim 12, wherein a transmittance adjusting agent is further added to the mixing step. The method for producing a wavelength conversion member according to claim 12, wherein the resin is a crystalline resin or an amorphous resin. A light-emitting device comprising a wavelength conversion member according to any one of claims 1 to 11 or a wavelength conversion member manufactured by the method of any one of claims 12 to 14, and a semiconductor light-emitting device element. The illuminating device of claim 15, wherein the color temperature of the emitted light is 5500 K or less. The light-emitting device of claim 15 or 16, wherein the wavelength conversion member is separated from the semiconductor light-emitting device. The light-emitting device of claim 17, wherein the wavelength conversion member and the semiconductor light-emitting device are provided with a transparent resin. The light-emitting device of claim 17, wherein the wavelength conversion member and the semiconductor light-emitting device have a space therebetween. The light-emitting device according to any one of claims 15 to 19, wherein the light-emitting device has a wiring substrate on which a reflecting plate is provided, and an area of a portion having a reflectance of 80% or more is the wiring substrate. More than 50% of the area above. The light-emitting device according to any one of claims 15 to 20, wherein the light-emitting device includes the wiring board and the casing, and a reflector is provided on the wiring board and the inner wall surface of the casing, and the reflectance is 80. The area of the portion above % is 50% or more of the area on the inner wall surface of the casing and on the wiring board. An LED lighting fixture having the illumination device of any one of claims 15 to 21. A resin composition containing a phosphor and a resin, wherein a total light transmittance of at least a part of the planar structure when the resin composition is molded into a molded body having a planar structure is 30 More than % and less than 70%.