JP6279209B2 - Wavelength conversion layer and wavelength conversion filter using the same - Google Patents

Description

The present invention relates to a wavelength conversion layer including a color conversion material having a maximum absorption range in a specific wavelength range and having an emission maximum above a specific wavelength, and a wavelength conversion filter using the same. More specifically, the present invention relates to a wavelength conversion filter that can be used in a lighting fixture using a white LED as a light source.

2. Description of the Related Art In recent years, lighting fixtures that use white LEDs as light sources in combination with phosphors and light emitting diode (LED) elements capable of emitting light with high power and high brightness in place of fluorescent lamps, etc. Is popular.
As elements necessary for a white LED light-emitting device used as a light source for illumination, an element of brightness and an element of color rendering properties are raised. The element of brightness represents the luminance, light quantity and luminous efficiency as a light source, and in recent years, there is a demand for higher luminance. Color rendering, on the other hand, is a term that expresses how a color looks when you look at it compared to sunlight. Generally, the color rendering index is a numerical value that represents the color reproducibility of a light source. Although Ra is used, in recent years, there is a demand for improvement of R9, which is an index of reproducibility regarding red with high saturation.
By the way, as a white LED light-emitting device, there is known a method of producing white light by mixing blue light emitted from a blue LED and light emitted from a yellow phosphor. Since the light emission of the component is insufficient, it becomes white light with a bluish color, and it is impossible to obtain a slightly reddish white light like a light bulb, and various improvements from the viewpoint of color rendering Has been proposed.
For example, a white LED light emitting device with improved color rendering properties has been devised and used by further mixing color-converted light with a plurality of phosphors such as a red phosphor and a green phosphor with a blue LED and a yellow phosphor. A red phosphor has been proposed.
However, if the electric power supplied to the white LED light emitting device is increased in order to respond to the demand for light luminance, the temperature of the white LED device itself rises, resulting in a decrease in light emission efficiency, and the balance between the phosphor and the luminance is lost. Color misregistration and various problems may occur.
On the other hand, Patent Document 1 proposes a lighting fixture that improves color rendering by absorbing light that has not been wavelength-converted by a yellow phosphor by a filter material in a method that produces white light composed of a blue LED and a yellow phosphor. However, since R9 is low and the appearance of red color is poor, it is insufficient as lighting for products such as food and clothing. Furthermore, since the total amount of light is reduced by absorbing light, the brightness is insufficient.

JP 2004-119984 A

The problem to be solved by the present inventor is to provide a wavelength conversion filter that can be used in a lighting apparatus using a white LED as a light source and can improve color rendering without reducing luminance and light quantity.

The inventors of the present invention have intensively studied a wavelength conversion filter that can be used in a lighting apparatus using a white LED as a light source. As a result, the present invention has been completed. That is, the present invention relates to (i) a wavelength conversion layer comprising at least one color conversion material having a maximum absorption region at a wavelength of 560 nm to 600 nm and having an emission maximum at a wavelength of 600 nm or more,
(Ii) The wavelength conversion layer according to (i), wherein the color conversion material is at least one selected from a pyromethene compound, a tetraazaporphyrin compound, and a perylene compound, and (iii) (i) to (ii) ), A wavelength conversion filter comprising the wavelength conversion layer according to any one of
(Iv) A wavelength conversion filter comprising two or more layers, one of which is the wavelength conversion layer according to any of (i) to (ii).
The present invention also provides:
(V) The wavelength conversion filter according to any one of (iii) to (iv), which is a filter for an LED lighting device.

The wavelength conversion layer of the present invention and the wavelength conversion filter using the same include a color conversion material having a maximum absorption region in a specific wavelength region and having a light emission maximum above a specific wavelength, thereby reducing luminance and light quantity. It became possible to improve the color rendering properties without doing so.

Hereinafter, the present invention will be described in detail.
The feature of the present invention resides in a wavelength conversion layer containing a color conversion material having a maximum absorption range in a specific wavelength range and having a light emission maximum above a specific wavelength range.
Furthermore, the present inventors have examined that, when a wavelength conversion filter using the wavelength conversion layer according to the present invention is attached to a white LED light-emitting device composed of a blue LED and a yellow phosphor, luminance and light quantity are not reduced. And found a filter capable of improving the color rendering.

<Color conversion material>
Examples of the color conversion material used in the wavelength conversion layer according to the present invention include a pyromethene compound, a tetraazaporphyrin compound, and a perylene compound. These color conversion materials may be used alone or in combination of two or more. May be.
Among them, since a wavelength conversion layer that can improve color rendering without reducing the amount of light can be obtained, a pyromethene compound, a tetramer that can absorb light with a wavelength of 560 nm to 600 nm and emit (emit) light with a wavelength of 600 nm or more. Most preferred are azaporphyrin compounds and perylene compounds.

  Although it does not specifically limit as said pyromethene compound, For example, the pyromethene boron complex represented by General formula (1) and the benzopyromethene boron complex represented by General formula (2) are preferable.

（式中、Ｒ１〜Ｒ７はそれぞれ独立に、水素原子、ハロゲン原子、シアノ基、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または未置換のアリール基を表す）
尚、本明細書において、アリール基とは、例えば、フェニル基、ナフチル基などの炭素環式芳香族基、例えば、フリル基、チエニル基、ピリジル基などの複素環式芳香族基を表し、好ましくは、炭素環式芳香族基を表す。
一般式（１）で表される化合物において、好ましくは、Ｒ１〜Ｒ７はそれぞれ独立に、水素原子、フッ素原子、臭素原子、塩素原子、シアノ基、炭素数１〜２４の直鎖、分岐または環状のアルキル基、炭素数１〜２４の直鎖、分岐または環状のアルコキシ基、炭素数４〜３０の置換または未置換のアリール基を表す。

(Wherein R1 to R7 each independently represents a hydrogen atom, a halogen atom, a cyano group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group. )
In the present specification, the aryl group represents, for example, a carbocyclic aromatic group such as a phenyl group or a naphthyl group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group or a pyridyl group, Represents a carbocyclic aromatic group.
In the compound represented by the general formula (1), preferably R1 to R7 are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, a cyano group, a linear, branched or cyclic group having 1 to 24 carbon atoms. An alkyl group having 1 to 24 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 24 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 30 carbon atoms.

  Specific examples of R1 to R7 in the general formula (1) include, for example, a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, a cyano group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group N-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methylpentyl group, 4-methyl-2-pentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3 , 3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 5- Tylhexyl group, 2,4-dimethylpentyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylhexyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 4 -Ethyloctyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, 1,3,5,7-tetramethyloctyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, n-tricosyl group, n-tetra Sill group, a cyclopentyl group, a cyclohexyl group, 4-methylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, straight chain, branched or cyclic alkyl groups such as cyclooctyl group,

  For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyloxy group 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n -Undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyl group Oxy group, n-eicosyloxy group, n-tricosyloxy group, n-tetrakoshi Linear, branched or cyclic alkoxy groups such as oxy group,

  For example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 4 -N-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl Group, 4-cyclohexylphenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4-n-nonylphenyl group, 4-n-decylphenyl group, 4-n-undecylphenyl group, 4 -N-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-n-hexadecylphenyl group, 4-n-octadecyl Phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group 3,4,5-trimethylphenyl group, 2,3,5,6-tetramethylphenyl group, 5-indanyl group, 1,2,3,4-tetrahydro-5-naphthyl group, 1,2,3, 4-tetrahydro-6-naphthyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 4-n-propoxyphenyl group, 4-iso Propoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 4-n-pentyloxyphenyl group, 4-n-hexyloxyphenyl 4-cyclohexyloxyphenyl group, 4-n-heptyloxyphenyl group, 4-n-octyloxyphenyl group, 4-n-nonyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-undecyl Oxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-n-hexadecyloxyphenyl group, 4-n-octadecyloxyphenyl group, 2,3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 2-methoxy-4-methylphenyl group 2-methoxy-5-methylphenyl group, 3-methoxy-4-methylphenyl group, 2-methyl-4-methoxy Phenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group 4-chlorophenyl group, 4-bromophenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4-dichlorophenyl group 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-methyl-4-chlorophenyl group, 2-chloro-4-methylphenyl group, 3-chloro-4-methylphenyl group, 2-chloro-4- A methoxyphenyl group, a 3-methoxy-4-fluorophenyl group,

3-methoxy-4-chlorophenyl group, 3-fluoro-4-methoxyphenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4 -(4'-methoxyphenyl) phenyl group, 3,5-diphenylphenyl group, 1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 4-ethoxy-1-naphthyl group, 6-n -Butyl-2-naphthyl group, 6-methoxy-2-naphthyl group, 7-ethoxy-2-naphthyl group, 2-furyl group, 2-thienyl group, 3-thienyl group, 2-pyridyl group, 3-pyridyl group 4-pyridyl group, 4-aminophenyl group, 3-aminophenyl group, 2-aminophenyl group, 4- (N-methylamino) phenyl group, 3- (N-methylamino) pheny Group, 4- (N-ethylamino) phenyl group, 2- (N-isopropylamino) phenyl group, 4- (Nn-butylamino) phenyl group, 2- (Nn-butylamino) phenyl group, 4- (Nn-octylamino) phenyl group, 4- (Nn-dodecylamino) phenyl group, 4-N-benzylaminophenyl group, 4-N-phenylaminophenyl group, 2-N-phenylamino Phenyl group, 4- (N, N-dimethylamino) phenyl group, 3- (N, N-dimethylamino) phenyl group, 2- (N, N-dimethylamino) phenyl group, 4- (N, N-diethylamino) ) Phenyl group, 2- (N, N-diethylamino) phenyl group, 4- (N, N-di-n-butylamino) phenyl group, 4- (N, N-di-n-hexylamino) phenyl group, 4- (N (Cyclohexyl-N-methylamino) phenyl group, 4- (N, N-diethylamino) -1-naphthyl group, 4-pyrrolidinophenyl group, 4-piperidinophenyl group, 4-morpholinophenyl group, 4-pyrrolidino -1-naphthyl group, 4- (N-benzyl-N-methylamino) phenyl group, 4- (N-benzyl-N-phenylamino) phenyl group, 4- (N-methyl-N-phenylamino) phenyl group 4- (N-ethyl-N-phenylamino) phenyl group, 4- (Nn-butyl-N-phenylamino) phenyl group, 4- (N, N-diphenylamino) phenyl group, 2- (N , N-diphenylamino) phenyl group, 4- [N, N-di (4′-methylphenyl) amino] phenyl group, 4- [N, N-di (3′-methylphenyl) amino] phenyl 4- [N, N-di (4′-ethylphenyl) amino] phenyl group, 4- [N, N-di (4′-tert-butylphenyl) amino] phenyl group, 4- [N, N -Di (4'-n-hexylphenyl) amino] phenyl group, 4- [N, N-di (4'-methoxyphenyl) amino] phenyl group, 4- [N, N-di (4'-ethoxyphenyl) ) Amino] phenyl group, 4- [N, N-di (4′-n-butoxyphenyl) amino] phenyl group, 4- [N, N-di (4′-n-hexyloxyphenyl) amino] phenyl group 4- [N, N-di (1′-naphthyl) amino] phenyl group, 4- [N, N-di (2′-naphthyl) amino] phenyl group, 4- [N-phenyl-N- (3 '-Methylphenyl) amino] phenyl group, 4- [N-phenyl-N- (4 -Methylphenyl) amino] phenyl group, 4- [N-phenyl-N- (4'-octylphenyl) amino] phenyl group, 4- [N-phenyl-N- (4'-methoxyphenyl) amino] phenyl group 4- [N-phenyl-N- (4′-ethoxyphenyl) amino] phenyl group, 4- [N-phenyl-N- (4′-n-hexyloxyphenyl) amino] phenyl group, 4- [N -Phenyl-N- (4'-fluorophenyl) amino] phenyl group, 4- [N-phenyl-N- (1'-naphthyl) amino] phenyl group, 4- [N-phenyl-N- (2'- Naphthyl) amino] phenyl group, 4- [N-phenyl-N- (4′-phenylphenyl) amino] phenyl group, 4- (N, N-diphenylamino) -1-naphthyl group, 6- (N, N -Giffeni Amino) -2-naphthyl group, 4-(N-Karubazoriiru) phenyl group, 4-(N-phenoxazyl) can be exemplified substituted or unsubstituted aryl group such as a phenyl group.

  In the compound represented by the general formula (1), more preferably, R1 to R7 are a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, carbon A linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms and a substituted or unsubstituted aryl group having 4 to 24 carbon atoms are represented.

（式中、Ｒ１１〜Ｒ１９はそれぞれ独立に、水素原子、ハロゲン原子、シアノ基、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または未置換のアリール基を表す）

(Wherein R11 to R19 each independently represents a hydrogen atom, a halogen atom, a cyano group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group. )

In the compound represented by the general formula (2), preferably, R11 to R19 are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, a cyano group, a linear, branched or cyclic group having 1 to 24 carbon atoms. An alkyl group having 1 to 24 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 24 carbon atoms, and a substituted or unsubstituted aryl group having 4 to 30 carbon atoms.
Specific examples of R11 to R19 in the general formula (2) are synonymous with the examples of the substituents represented by R1 to R7 in the general formula (1) described above, and their preferred embodiments are also synonymous.

  Although it does not specifically limit as said tetraazaporphyrin compound, For example, the metal-free tetraazaporphyrin complex represented by General formula (3) is preferable.

（式中、Ｘ１〜Ｘ８はそれぞれ独立に、水素原子、フッ素原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または未置換のアリール基、直鎖、分岐または環状のハロゲノアルコキシ基、直鎖、分岐または環状のアルコキシアルキル基を表す。ただしＸ１〜Ｘ８のすべてが水素原子であることはない）

(Wherein X1 to X8 are each independently a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, a linear or branched group, Or a cyclic halogenoalkoxy group, a linear, branched or cyclic alkoxyalkyl group (provided that not all of X1 to X8 are hydrogen atoms).

  In the compound represented by the general formula (3), X1 to X8 are preferably each independently a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, or 1 to 24 carbon atoms. Linear, branched or cyclic alkoxy group, substituted or unsubstituted aryl group having 4 to 30 carbon atoms, linear chain having 1 to 24 carbon atoms, branched or cyclic halogenoalkoxy group, linear chain having 2 to 24 carbon atoms Represents a branched or cyclic alkoxyalkyl group.

  Specific examples of X1 to X8 in the general formula (3) include, for example, a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, such as a fluoromethyl group, a 3-fluoropropyl group, a 6-fluorohexyl group, 8- Fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n-propyl group, 1,1,3-trihydro-perfluoro-n-propyl group, 2-hydro-perfluoro-2-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 1,1-dihydro-perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n -Hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydro-perfluoro-n-octyl group, 1,1-dihydro- -Fluoro-n-decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1,1-dihydro-perfluoro-n-tetradecyl group, 1,1-dihydro-perfluoro-n-hexadecyl group, Fluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, 2,2-bis (trifluoromethyl) propyl group, dichloromethyl group, 2-chloroethyl group, Linear, branched or cyclic halogenoalkyl groups such as 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chlorooctyl group, 2,2,2-trichloroethyl group, fluoromethyloxy group 3-fluoropropyloxy group, 6-fluorohexyloxy group, 8-fluorooctyloxy group, tri Fluoromethyloxy group, 1,1-dihydro-perfluoroethyloxy group, 1,1-dihydro-perfluoro-n-propyloxy group, 1,1,3-trihydro-perfluoro-n-propyloxy group, 2-hydro-perfluoro-2-propyloxy group, 1,1-dihydro-perfluoro-n-butyloxy group, 1,1-dihydro-perfluoro-n-pentyloxy group, 1,1-dihydro-perfluoro -N-hexyloxy group, 6-fluorohexyloxy group, 4-fluorocyclohexyloxy group, 1,1-dihydro-perfluoro-n-octyloxy group, 1,1-dihydro-perfluoro-n-decyloxy group, 1,1-dihydro-perfluoro-n-dodecyloxy group, 1,1-dihydro-perfluoro-n-tetradecyloxy group Xyl group, 1,1-dihydro-perfluoro-n-hexadecyloxy group, perfluoroethyloxy group, perfluoro-n-propyloxy group, perfluoro-n-pentyloxy group, perfluoro-n-hexyloxy Group, 2,2-bis (trifluoromethyl) propyloxy group, dichloromethyloxy group, 2-chloroethyloxy group, 3-chloropropyloxy group, 4-chlorocyclohexyloxy group, 7-chloroheptyloxy group, 8 A linear, branched or cyclic halogenoalkoxy group such as a chlorooctyloxy group or a 2,2,2-trichloroethyloxy group,

For example, methoxymethyl group, ethoxymethyl group, n-butoxymethyl group, n-pentyloxymethyl group, n-hexyloxymethyl group, (2-ethylbutyloxy) methyl group, n-heptyloxymethyl group, n-octyl Oxymethyl group, n-decyloxymethyl group, n-dodecyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxy Ethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group Group, 2- (2′-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3-n-butoxypropyl group, 3-n-pentyloxypropyl group, 3-n-hexyloxypropyl group, 3- (2′-ethylbutoxy) propyl group, 3-n-octyloxypropyl group, 3- ( 2'-ethylhexyloxy) propyl group, 3-n-decyloxypropyl group, 3-n-dodecyloxypropyl group, 3-n-tetradecyloxypropyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butyl group Xylbutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group 5-n-propoxypentyl group, 5-n-pentyloxypentyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyl Oxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-methoxyheptyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 8-ethoxyoctyl group, 9-methoxynonyl group, 9-ethoxynonyl group, 10-methoxydecyl group, 10-ethoxyde Group, 10-n-butoxydecyl group, 11-methoxyundecyl group, 11-ethoxyundecyl group, 12-methoxydodecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, 14-methoxytetradecyl group And linear, branched or cyclic alkoxyalkyl groups such as a tetrahydrofurfuryl group.
Specific examples of the linear, branched or cyclic alkyl group, the linear, branched or cyclic alkoxy group, and the substituted or unsubstituted aryl group are represented by R1 to R7 in the general formula (1) described above. It is synonymous with the illustration of the substituent made.

In the compound represented by the general formula (3), more preferably, X1 to X8 are a hydrogen atom, a fluorine atom, a chlorine atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, 16 straight-chain, branched or cyclic alkoxy groups, substituted or unsubstituted aryl groups having 4 to 24 carbon atoms, straight-chain, branched or cyclic halogenoalkoxy groups having 1 to 16 carbon atoms, straight chain having 2 to 16 carbon atoms Represents a chain, branched or cyclic alkoxyalkyl group.
The perylene compound is not particularly limited. For example, acenaphtho [1 ′, 2 ′: 5,6] indeno [1,2,3 having a skeleton represented by the general formula (4) -Cd] benzo [5,6] indeno [1 ', 2', 3'-lm] perylene derivative, bisphenanthreno [9 ', 10': 6 having a skeleton represented by general formula (5) , 7] Indeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene derivative and a bisbenzo [5,6] indeno [1 having a skeleton represented by the general formula (6) , 2, 3-cd: 1 ′, 2 ′, 3′-lm] perylene derivatives are preferred.

（式中、Ｚ１〜Ｚ２２はそれぞれ独立に、水素原子、ハロゲン原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または未置換のアリール基、置換または未置換のカルボキシル基を表す）
一般式（４）で表される化合物において、好ましくは、Ｚ１〜Ｚ２２はそれぞれ独立に、水素原子、フッ素原子、臭素原子、塩素原子、炭素数１〜２４の直鎖、分岐または環状のアルキル基、炭素数１〜２４の直鎖、分岐または環状のアルコキシ基、炭素数４〜３０の置換または未置換のアリール基、炭素数１〜２４の置換または未置換のカルボキシル基を表す。

Wherein Z1 to Z22 are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted Represents the carboxyl group of
In the compound represented by the general formula (4), preferably, Z1 to Z22 are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, or a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms. Represents a linear, branched or cyclic alkoxy group having 1 to 24 carbon atoms, a substituted or unsubstituted aryl group having 4 to 30 carbon atoms, and a substituted or unsubstituted carboxyl group having 1 to 24 carbon atoms.

Specific examples of Z1 to Z22 in the general formula (4) include, for example, a hydrogen atom, a fluorine atom, a bromine atom, and a chlorine atom, such as a carboxyl group, a methyl carboxyl group, an ethyl carboxyl group, a phenyl carboxyl group, and an isopropyl carboxyl group. Examples thereof include substituted or unsubstituted carboxyl groups such as 1-n-butenylcarboxyl group.
Specific examples of the linear, branched or cyclic alkyl group, the linear, branched or cyclic alkoxy group, and the substituted or unsubstituted aryl group are represented by R1 to R7 in the general formula (1). It is synonymous with the illustration of the substituent made.

  In the compound represented by the general formula (4), more preferably, Z1 to Z22 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, A linear, branched or cyclic alkoxy group having 1 to 16 carbon atoms, a substituted or unsubstituted aryl group having 4 to 24 carbon atoms, and a substituted or unsubstituted carboxyl group having 1 to 16 carbon atoms.

（式中、Ｚ３１〜Ｚ５６はそれぞれ独立に、水素原子、ハロゲン原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または未置換のアリール基、置換または未置換のカルボキシル基を表す）

(In the formula, each of Z31 to Z56 is independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Represents the carboxyl group of

  In the compound represented by the general formula (5), preferably, Z31 to Z56 are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, or a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms. Represents a linear, branched or cyclic alkoxy group having 1 to 24 carbon atoms, a substituted or unsubstituted aryl group having 4 to 30 carbon atoms, and a substituted or unsubstituted carboxyl group having 1 to 24 carbon atoms.

  Specific examples of Z31 to Z56 in the general formula (5) are synonymous with the examples of the substituents represented by Z1 to Z22 in the general formula (4) described above, and their preferred embodiments are also synonymous.

（式中、Ｚ６１〜Ｚ８０はそれぞれ独立に、水素原子、ハロゲン原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または未置換のアリール基、置換または未置換のカルボキシル基を表す）

(In the formula, each of Z61 to Z80 is independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, substituted or unsubstituted. Represents the carboxyl group of

In the compound represented by the general formula (6), Z61 to Z80 are preferably each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms. Represents a linear, branched or cyclic alkoxy group having 1 to 24 carbon atoms, a substituted or unsubstituted aryl group having 4 to 30 carbon atoms, and a substituted or unsubstituted carboxyl group having 1 to 24 carbon atoms.
Specific examples of Z61 to Z80 in the general formula (6) are synonymous with the examples of the substituents represented by Z1 to Z22 in the general formula (4) described above, and their preferred embodiments are also synonymous.

<Wavelength conversion layer>
The wavelength conversion layer of the present invention is characterized in that a color conversion material is contained in a transparent support.
The transparent support is not particularly limited, but a polymer material is used. For example, it may be a thermoplastic resin, a heat or photo-curing resin, or a mixture thereof.
In the case where the polymer material is a heat or photocurable resin, it represents that the monomer (monomer) or polymerization precursor of the resin is also included.
The polymer material is preferably transparent (visible light transmittance is 50% or more) or translucent.

Specific examples of the polymer material include curable resins having a reactive vinyl group such as acrylic resin, methacrylic resin, and poly (vinyl cinnamate), polycarbonate, polyimide, polyamide imide, polyester imide, polyether imide, polyether ketone, poly Ether ether ketone, polyether sulfone, polysulfone, polyparaxylene, polyester, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, polyurethane, polyvinyl alcohol, fluorinated resin, silicone resin, epoxy silicone resin, phenol resin , Alkyd resin, epoxy resin, maleic resin, melamine resin, urea resin, aromatic sulfonamide, benzoguanamine resin, silicone elastomer, cyclic olefin copolymer It can be mentioned. These resins may be used alone or in combination of two or more. The molecular weight of these polymer materials is usually about 1000 to 100,000 as the weight average molecular weight, but of course, polymer materials having molecular weights outside this range can also be used.
Any conventionally known technique can be used as a method for producing the wavelength conversion layer of the present invention.

Although not particularly limited, for example, (a) a method in which the color conversion material according to the present invention is kneaded and contained in a polymer material, and (b) the color conversion material according to the present invention and the polymer material are dissolved. There is a so-called casting method in which the organic solvent is removed after being dissolved and mixed in the organic solvent.
The wavelength conversion layer may be a film or a plate.
For (a), for example, color conversion material and polymer material powder or pellets are mixed using various mixers such as a tumbler or Henschel mixer, and this is mixed with a Banbury mixer, heating roll, Brabender, It heat-melt-kneads at 150-350 degreeC with well-known melt-kneaders, such as a shaft kneading extruder, a biaxial kneading extruder, a kneader. In addition, an additive used for normal resin molding such as a plasticizer may be added when kneading. Furthermore, the obtained kneaded material is formed with a thickness of 0.2 to 0.2 by a conventionally known film forming process such as a T-die molding method, a calendar molding method, a compression molding method, a transfer molding method, an extrusion molding method, or an injection molding method. You may shape | mold into a 10 mm plate shape.
Moreover, the raw material obtained by the T-die molding method, the calender molding method, etc. is produced, The method etc. which are extended | stretched to 1 axis | shaft and 2 axis | shafts and made into the film form of 10-200 micrometers thickness are mentioned.

  The polymer material used is preferably highly transparent when molded as a layer. Specifically, polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate, polyarylate, poly Polyethers such as ether ketone, polycarbonate, polyethylene, polypropylene and nylon 6, cellulose resins such as polyimide and triacetyl cellulose, fluorine resins such as polyurethane and polytetrafluoroethylene, vinyl compounds such as polyvinyl chloride, polyacrylic acid, poly Addition polymer of acrylic acid ester, polyacrylonitrile, vinyl compound, polymethacrylic acid, polymethacrylic acid ester, vinylidene compound such as polyvinylidene chloride, vinylidene fluoride / trifluoroethylene copolymer, ethylene / Mention may be made of vinyl compounds such as vinyl acetate copolymers or copolymers of fluorine-based compounds, polyethers such as polyethylene oxide, epoxy resins, polyvinyl alcohol, polyvinyl butyral and the like. The thing with high transparency here means that the light transmittance in a wavelength of 400-700 nm is 40% or more.

  In the method by casting listed in (b), a color conversion material is added and dissolved in an organic solvent containing a polymer material such as a resin or resin monomer, and if necessary, a plasticizer, a polymerization initiator, and an antioxidant are added. In addition, it can be produced by pouring onto a mold or drum having the required surface state, and solvent evaporation / drying or polymerization / solvent evaporation / drying.

Examples of resins used include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, Examples thereof include polyvinyl modified resins (PVA, EVA, etc.) or resin monomers of those copolymer resins.
Examples of the solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, and mixtures thereof.
The amount of the color conversion material used with respect to the polymer material is not particularly limited, but generally it is preferably 0.01 to 80% by weight, preferably 0.01 to 60% by weight based on the weight of the polymer material. % Content is more preferable.
In addition to the color conversion material according to the present invention, the wavelength conversion layer of the present invention includes, for example, a dye for correcting color tone, an antioxidant, and a phosphorus-based processing stabilizer, as long as the desired effects of the present invention are not impaired. It is possible to add light-resistant stabilizers such as processing / oxidation and heat stabilizers, UV absorbers, and silane coupling agents, etc., dyes for color correction, processing / oxidation and heat stabilizers, light resistance It is preferable to add an amount of the color stabilizer and the silane coupling agent that shows a color tone correcting effect and a stabilizing effect, and usually about 0.1 ppm to 10% by weight based on the weight of the polymer material. Is preferred.

<Wavelength conversion filter>
The wavelength conversion filter of the present invention has two or more layers, one of which is the above-described wavelength conversion layer, and other layers include “transparent substrate layer” and “functional transparent layer”. Is mentioned.
The “transparent substrate layer” is not particularly limited, but a transparent substrate made of an inorganic material such as transparent glass or a polymer material cited as a transparent support in the description of the wavelength conversion layer. means.
As the “functional transparent layer”, an antireflection function, an antiglare function, an antiglare function, a hard coat function (friction resistance function), depending on the installation method and required functions of the wavelength conversion filter of the present invention, It has at least one of an antistatic function, an antifouling function, a gas barrier function, an electromagnetic wave shielding function, an infrared cut function, an ultraviolet cut function, a polarization function, and a toning function.
The functional transparent layer may be a functional film itself having one or more of the above functions, or the functional film may be applied to the wavelength conversion layer or the transparent substrate layer by a known method such as a coating method or a printing method. It may be formed by various film forming methods, and further may be a support having each function or containing a functional film. The functional transparent layer may be formed by laminating a plurality of different functional transparent layers each having one or more of the above functions.

As the functional transparent layer having an antireflection function, for example, a thin film such as a fluorine-based transparent polymer resin having a refractive index of 1.5 or less in the visible light region, magnesium fluoride, a silicon-based resin, or silicon oxide is used. , For example, a single layer formed with an optical film thickness of ¼ wavelength, or an inorganic compound thin film made of metal oxide, fluoride, silicide, boride, carbide, nitride, sulfide, etc. having different refractive index, Or there exists what laminated | stacked the organic compound thin film which consists of a silicon-type resin, an acrylic resin, a fluorine resin etc. in order of 2 or more layers of the high refractive index layer and the low refractive index layer.
As a method for forming the inorganic compound thin film, for example, a known method such as a sputtering method, an ion plating method, a vacuum deposition method, or a wet coating method can be applied. As a method for forming the organic compound thin film, for example, a known method such as a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, or a comma coating method can be applied.
The visible light reflectance of the surface of the functional transparent layer having antireflection properties is generally adjusted to 2% or less, preferably 1.3% or less, and more preferably 0.8% or less.

As the functional transparent layer having an antiglare function, it is also possible to provide a layer transparent to the visible light region having a minute uneven surface state of about 0.1 to 10 μm. Alternatively, inorganic resin particles such as silica and organosilicon compounds or organic compound particles such as melamine and acrylic dispersed in a resin are coated and cured on a support. May be.
The functional transparent layer having an antireflection antiglare function can be prepared by forming an antireflection film on a film having an antiglare function or a support having an antiglare function.

  The functional transparent layer having a hard coat function may be a resin layer having a hard coat function, or a hard coat film formed on a support. Examples of the resin layer having a hard coat function include acrylic resins, silicone resins, melamine resins, urethane resins, alkyd resins, thermosetting resins such as fluorine resins, or photocurable resins. It is done. The thickness of the hard coat film is generally about 1 to 100 μm. An antireflection film may be formed on the hard coat film, and the functional transparent layer may have both an antireflection function and a hard coat function. Similarly, the functional transparent layer may have both functions of an antiglare function and a hard coat function. A functional transparent layer having both an antiglare function and a hard coat function can be prepared, for example, by forming an antireflection film on a hard coat film having irregularities by dispersing particles or the like. As for the surface hardness of the functional transparent layer having a hard coat function, the pencil hardness according to JISK5600 is at least H or more, preferably 2H or more.

Examples of the functional transparent layer having an antistatic function include, for example, ITO (Indium
Examples thereof include a transparent conductive film such as Tin Oxide), and a conductive film in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed. Moreover, the layer which comprises the functional transparent layer which has any one or more functions of an antireflection function, an anti-glare function, an anti-reflection glare function, and a hard-coat function may have electroconductivity.
Examples of the functional transparent layer having an antifouling function include a coat or a resin layer using a compound having non-wetting properties with respect to water and / or oils, such as a fluorine compound and a silicon compound.

  Examples of the functional transparent layer having a gas barrier function include, for example, silicon oxide, aluminum oxide, tin oxide, indium oxide, yttrium oxide, magnesium oxide, or a mixture thereof, or a metal obtained by adding other elements to these. Examples thereof include oxide thin films, or films made of various resins such as polyvinylidene chloride, acrylic resins, silicon resins, melamine resins, urethane resins, and fluorine resins. Examples of the film having a barrier function against moisture include, for example, polyethylene, polypropylene, nylon, polyvinylidene chloride, vinylidene chloride and vinyl chloride, copolymers of vinylidene chloride and acrylonitrile, and various resins such as fluorine resins. Mention may be made of membranes.

As the functional transparent layer having an electromagnetic wave shielding function, it may have the above-mentioned antistatic function, for example, a metal mesh, a conductive mesh such as a conductive grid pattern film, a metal thin film, It may be an oxide semiconductor thin film. A multilayer thin film in which a metal thin film and a high-refractive-index transparent thin film are laminated has favorable characteristics with respect to conductivity, near infrared cut function, and visible light transmittance. The layer having an electromagnetic wave shielding function is preferably provided as an individual layer or member independently of the functional transparent layer.
The functional transparent layer having an infrared cut function may be a layer having the above-mentioned antistatic function or electromagnetic wave shielding function, or a layer containing an organic near infrared absorbing dye. Examples of organic near-infrared absorbing dyes include diimonium, cyanine, phthalocyanine, metal complex, nickel dithiolene complex, squarylium, polymethine, azomethine, azo, polyazo, aminium, and anthraquinone dyes Etc. can be used.
As the functional transparent layer having an ultraviolet cut function, an inorganic thin film single layer that absorbs ultraviolet rays, an antireflection film comprising an inorganic thin film multilayer, or a transparent film containing an organic ultraviolet absorbing compound may be used. it can.
Any conventionally known technique can be used as a method for producing the wavelength conversion filter of the present invention.

Although not particularly limited, for example, (c) a method of bonding the wavelength conversion layer according to the present invention to a transparent base material layer or a functional transparent layer via a “transparent adhesive layer” described later, (d) Examples include a method of dispersing or dissolving the color conversion material according to the present invention in an organic solvent containing a polymer material such as a polymer resin or a resin monomer, and laminating a wavelength conversion layer on the transparent substrate layer or the functional transparent layer. It is done.
As the method mentioned in (d), the color conversion material is dissolved or mixed in an organic solvent and a binder resin to form a paint, or the color conversion material is finely pulverized into an uncolored acrylic emulsion paint (particle size 50 And a method of dispersing an acrylic emulsion-based water-based coating material.
Examples of binder resins used include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, and polyvinyl alcohols. Examples thereof include resins, polyvinyl-based modified resins (PVB, EVA, etc.) or copolymer resins thereof.
Examples of the organic solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, and mixtures thereof.
In the case of the acrylic emulsion water-based paint, it can be obtained by dispersing finely pulverized color conversion material (particle size 50 to 500 nm) in an uncolored acrylic emulsion paint as described above. In the paint, additives such as antioxidants that are usually used in paints may be added.
The paint produced by the above method is applied to the transparent substrate layer or the functional transparent layer by a bar coating method, a blade coating method, a spin coating method, a reverse coating method, a die coating method, or a coating method such as spraying. By forming, it can be laminated as a wavelength conversion layer. The thickness of the wavelength conversion layer is not particularly limited, but is about 1 to 50 μm.

The “transparent adhesive layer” is a layer made of a transparent adhesive material (adhesive, adhesive). Examples of the adhesive material include acrylic resins, silicon resins, urethane resins, polyvinyl butyral resins, Ethylene-vinyl acetate resin, polyvinyl ether, saturated polyester, melamine resin and the like are used.
In the case of the wavelength conversion filter of the present invention, the pressure-sensitive adhesive material is preferably an acrylic pressure-sensitive adhesive material containing an acrylic polymer in terms of excellent transparency, adhesiveness, heat resistance, and the like. In particular, when an alkyl alkyl ester having 4 to 8 carbon atoms in the alkyl group is used, the adhesive strength and flexibility of the resulting adhesive are improved. Moreover, when a carboxyl group-containing monomer and a hydroxyl group-containing monomer are copolymerized, crosslinking can be performed using an isocyanate-based crosslinking agent or the like.
As the curing agent for the acrylic adhesive material, an isocyanate curing agent, an epoxy curing agent, a metal chelate curing agent, or the like is used.
The adhesive material may be in the form of a sheet or liquid.
When a sheet-like pressure-sensitive adhesive material is used as the adhesive material, the sheet-like adhesive material is pasted or after the adhesive is applied, it is bonded by pressure bonding.
When a liquid material is used as the adhesive material, it is bonded by curing after application and bonding, by aging treatment at room temperature or under heating, or by irradiation with ultraviolet rays.
The thickness of the transparent adhesive layer is not particularly limited, but is generally 0.5 to 500 μm.
The surface on which the transparent adhesive layer is formed and the surface to be bonded are preferably subjected to an easy adhesion treatment such as an easy adhesion coat or a corona discharge treatment in advance. Furthermore, after bonding through the transparent adhesive layer, the air mixed between the members at the time of bonding is defoamed or dissolved in the adhesive material to further improve the adhesion between the members. It is preferable to perform the treatment under pressure and heating conditions.
The transparent adhesive layer is provided on at least one surface of the wavelength conversion layer, and is used, for example, for bonding the functional transparent layer and the wavelength conversion layer, or for bonding the functional transparent layer and the functional transparent layer.

<Filter for LED lighting device>
The wavelength conversion filter of the present invention is a filter applicable to a light emitting device such as an illumination device using an LED light source, a small light, an advertisement signboard or illumination, an automobile headlight, a traffic signal.
When the wavelength conversion filter of the present invention is used for an LED lighting device, there is no particular limitation on the configuration and usage, and any of the following structures may be used.
For example, a filter structure comprising a wavelength conversion layer according to the present invention, a filter structure comprising a wavelength conversion layer and a transparent adhesive layer according to the present invention, and a filter structure comprising a wavelength conversion layer, a transparent adhesive layer and a functional transparent layer according to the present invention Is mentioned. In addition, a filter structure in which a plurality of arbitrary layers having the above structure are combined may be used.
As described above, the functional transparent layer may be a plurality of layers having a plurality of functions. Furthermore, the functional transparent layer or the wavelength conversion layer may have an arbitrary overcoat layer or undercoat layer according to required characteristics, or may be subjected to an arbitrary treatment such as an antireflection treatment.

The wavelength conversion filter of the present invention functions as a dimming filter having a characteristic of correcting the emission spectrum of the white LED. The white LED is preferably a white LED composed of a blue light emitting LED and a yellow light emitting phosphor in terms of light emission efficiency.
This white LED has a white color obtained by a mixture of blue light emission near a wavelength of 470 nm and yellow light emission near a wavelength of 570 nm, but contains a lot of light near a wavelength of 570 nm to 605 nm, and therefore the wavelength conversion film of the present invention. In addition, the color rendering properties can be corrected to a preferable one without reducing the amount of light by using the filter.
This is because the color conversion material contained in the wavelength conversion filter of the present invention absorbs light in the wavelength range of 580 nm to 600 nm, for example, and converts it into light having a wavelength of 630 nm or more, thereby reducing the amount of light. Therefore, it is possible to correct the chromaticity without any problem and to obtain a preferable white light source with improved color rendering.
Here, the color of the white light source is JIS
It is expressed and evaluated by the average color rendering index measured by the method defined in Z8726. Hereinafter, the definition and measurement method of color rendering properties, average color rendering index, and special color rendering index will be described.

Color rendering is a phenomenon in which colors appear differently depending on the illumination light source, and the characteristic is called color rendering. In general, the color rendering property represents the property of a light source compared with natural light. Color rendering is generally expressed as “good” or “bad” with reference to light such as natural light, but JIS uses light close to that natural light as reference light.
The test light is examined by the method defined in Z 8726, and the color rendering properties of the illumination light are evaluated. The types of color rendering index are R1 to R15, and there are an average color rendering index and a special color rendering index. The average color rendering index is the numerical value of the color shift when the test color is illuminated with the sample light source and the reference light. The value when the color is viewed with the reference light is set to 100, and the numerical value increases as the color shift increases. Becomes smaller. The average color rendering index (Ra) is expressed as an average value of the color rendering evaluation numerical values from R1 to R8.

In the standard of the color rendering index by the CIE (International Lighting Commission), desirable average color rendering index is as follows.
Ra ≧ 90 ・ ・ Color comparison / inspection, clinical trial, museum.
90> Ra ≧ 80 ..House, restaurant, store, office, school, hospital, etc.
80> Ra ≧ 60: Factory for general work.
Special color rendering index is a test color for special color rendering evaluation (R9 to R15), red, yellow, green, blue, Western female complexion, leaf green, Japanese female complexion, etc. The evaluation is performed for the color, and the numerical value is also displayed for each test color.
Furthermore, since the wavelength conversion filter of the present invention has high heat resistance and light resistance, it can have a life of 40,000 hours required for illumination using an LED (time until the light flux self-supporting becomes 70%).
When the wavelength conversion filter of the present invention is applied to an LED lighting device, in detail, it is provided as a part of a wavelength conversion filter or LED module used by being provided outside or inside a housing in the LED lighting device. This is a wavelength conversion filter used. The housing is composed of, for example, an LED chip, an LED package, a printed circuit board for wiring, an LED module, an LED unit, and a lighting fixture housing.

Taking an LED lighting apparatus as an example, a package is a member that holds a chip, effectively extracts light from the chip and converts the light to white, and a module is a member that holds a package on a substrate, and is usually Part of the unit. The housing has a role of not only holding and designing the unit, but also protecting the unit from electrical and physical impacts and releasing heat to the outside.
For example, the wavelength conversion filter of the present invention can be installed on the outside air surface of the housing or on the inside surface of the housing. It should be noted that the provision and use of the wavelength conversion filter of the present invention as a part of the LED module means that the unit-side surface of the unit and the surface on the package side, the surface on the unit side of the package, and the surface on the chip side. It may be in the form installed in the crab.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
In all examples and comparative examples, the absorption spectra were measured using a toluene solution and a chloroform solution having a concentration of 0.01 g / L, and a U-3500 type self-recording spectrophotometer manufactured by Hitachi, Ltd. as a measuring instrument. The optical path length was 10 mm. The average color rendering evaluation was measured and evaluated with a CS-2000 type spectral radiance meter manufactured by Konica Minolta Sensing Co., Ltd.

[Example 1]
Spin coating method in which 500 parts by weight of toluene is mixed with 1 part by weight of the following pyromethene boron complex (1a) as a color conversion material and 100 parts by weight of polycarbonate (optical disk grade: weight average molecular weight 30,000) as a polymer compound. Is applied to a polyethylene terephthalate film (manufactured by Teijin DuPont Film, thickness 0.1 mm) at 2300 rpm to a dry film thickness of 25 μm, baked in an oven at 110 ° C., and dried to obtain a wavelength conversion filter. Produced.
The blending amount of the color conversion material is such that the absorption transmittance of the wavelength conversion filter at the absorption maximum wavelength of the color conversion material is 70%.

[Example 2]
The following benzopyromethene boron complex (2a) as a color conversion material was dissolved in a mixed solvent of ethyl acetate / toluene (50: 50% by weight) to a concentration of 0.15 wt% to prepare a diluent. Next, an acrylic pressure-sensitive adhesive (trade name PX4-IR-PT-076, manufactured by Nippon Shokubai Co., Ltd., solid content concentration: 37.5%) and this color conversion material-containing diluent were mixed at a weight ratio of 80:20. Then, it was coated on a polyethylene terephthalate film (manufactured by Teijin DuPont Film, thickness 75 μm) with a batch type die coater so as to have a dry film thickness of 25 μm, and dried to prepare a wavelength conversion filter.
The blending amount of the color conversion material is such that the absorption transmittance of the wavelength conversion filter at the absorption maximum wavelength of the color conversion material is 70%.

[Example 3]
0.015% by weight of the following metal-free tetraazaporphyrin complex (3a) as a color conversion material is mixed with polyethylene terephthalate pellets (trade name 1203, manufactured by Unitika Co., Ltd.), melted at 260 to 280 ° C., and thickened by an extruder. A 200 μm original fabric was prepared. This original fabric was stretched in the biaxial direction to produce a wavelength conversion filter having a thickness of 100 μm.
The blending amount of the color conversion material is such that the absorption transmittance of the wavelength conversion filter at the absorption maximum wavelength of the color conversion material is 70%.

[Example 4]
1000 parts by weight of a polymethyl methacrylate resin (manufactured by Asahi Kasei Co., Ltd .: 80N) and the following acenaphtho [1 ′, 2 ′: 5,6] indeno [1,2,3-cd] benzo [5,6] as a color conversion material Indeno [1 ′, 2 ′, 3′-lm] perylene derivative, (4a) 0.018 parts by weight was mixed by a tumbler for 20 minutes, and then, by a single screw extruder, a cylinder set temperature of 260 ° C. and a screw rotation speed of 56 rpm. The mixture was then melted and kneaded under the conditions of The pellets were mixed and extruded in a twin-screw extruder to produce a raw material having a thickness of about 200 μm. The temperature in the extrusion zone and the melting line was 275 ° C. at maximum, and the temperature of the cooling roll was 30 ° C. Then, this original fabric was stretched in the biaxial direction to produce a wavelength conversion layer having a thickness of 100 μm.
Meanwhile, 80 parts by weight of methyl ethyl ketone, 30 parts by weight of an acrylic pressure-sensitive adhesive (trade name PX4-IR-PT-076, manufactured by Nippon Shokubai Co., Ltd., solid content concentration 37.5%), product name L-55E, an isocyanate-based curing agent, Japan 0.057 part by weight of polyurethane industry) and 0.0057 part by weight of a curing accelerator (dibutyltin dilaurate manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred with a homogenizer at 10000 rpm for 10 minutes, and a solid content concentration of about 10%. A composition was obtained. This pressure-sensitive adhesive composition was applied to the previously prepared wavelength conversion layer using a bar coater so as to have a dry film thickness of 25 μm and dried. Thereafter, a release film having a silicone release layer formed thereon was bonded to the coated surface to prepare a wavelength conversion filter.
The blending amount of the color conversion material is such that the absorption transmittance of the wavelength conversion filter at the absorption maximum wavelength of the color conversion material is 70%.

[Example 5]
The following bisphenanthreno [9 ′, 10 ′: 6,7] indeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene derivative as a color conversion material in 80 parts by weight of methyl ethyl ketone (5a) 0.02 part by weight was dissolved. In this solution, 30 parts by weight of an acrylic pressure-sensitive adhesive (trade name PX4-IR-PT-076, solid concentration 37.5% made by Nippon Shokubai), an isocyanate-based curing agent (trade name L-55E, Nippon Polyurethane Industry) 0.057 parts by weight, and 0.0057 parts by weight of a curing accelerator (dibutyltin dilaurate manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred with a homogenizer at 10,000 rpm for 10 minutes, and a solid content concentration of about 10%. Got.
This pressure-sensitive adhesive composition was applied onto a polyethylene terephthalate film (manufactured by Teijin DuPont Films, thickness 75 μm) using a bar coater so as to have a dry film thickness of 25 μm, and dried at 90 ° C. for 2 minutes. A release film having a silicone release layer formed thereon was bonded to the coated surface to produce a wavelength conversion filter.
The blending amount of the color conversion material is such that the absorption transmittance of the wavelength conversion filter at the absorption maximum wavelength of the color conversion material is 70%.

[Example 6]
1000 parts by weight of a polymethyl methacrylate resin (Asahi Kasei Co., Ltd .: 80N) and the following bisbenzo [5,6] indeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] as a color conversion material After mixing 0.02 part by weight of the perylene derivative (6a) with a tumbler for 20 minutes, it was melted and kneaded with a single-screw extruder under conditions of a cylinder set temperature of 260 ° C. and a screw rotation speed of 56 rpm to form pellets. The pellets were mixed and extruded in a twin-screw extruder to produce a raw material having a thickness of about 200 μm. The temperature in the extrusion zone and the melting line was 275 ° C. at maximum, and the temperature of the cooling roll was 30 ° C. Then, this original fabric was stretched in the biaxial direction to produce a wavelength conversion layer having a thickness of 100 μm.
Meanwhile, 80 parts by weight of methyl ethyl ketone, 30 parts by weight of an acrylic pressure-sensitive adhesive (trade name PX4-IR-PT-076, manufactured by Nippon Shokubai Co., Ltd., solid content concentration 37.5%), product name L-55E, an isocyanate-based curing agent, Japan 0.057 part by weight of polyurethane industry) and 0.0057 part by weight of a curing accelerator (dibutyltin dilaurate manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred with a homogenizer at 10000 rpm for 10 minutes, and a solid content concentration of about 10%. A composition was obtained. This pressure-sensitive adhesive composition was applied to the surface of the wavelength conversion layer prepared previously using a bar coater so as to have a dry film thickness of 25 μm and dried. Thereafter, a release film having a silicone release layer formed thereon was bonded to the coated surface.
Next, the pressure-sensitive adhesive composition was applied and dried on the back surface of the wavelength conversion layer in the same manner, and a release film was bonded to the application surface to obtain a wavelength conversion filter A.
The release film on one surface of the obtained wavelength conversion filter A is peeled off and bonded to a polycarbonate hard coat film (MGP fill sheet Iupilon sheet MR58, thickness 0.5 mm) to produce a wavelength conversion filter. did.
The blending amount of the color conversion material is such that the absorption transmittance of the wavelength conversion filter at the absorption maximum wavelength of the color conversion material is 70%.

[Example 7]
The color rendering properties when the wavelength conversion filter was used were evaluated by the following operations.
The color rendering property evaluation was implemented about the wavelength conversion film of this invention produced in Examples 1-6. For this test, an LED bulb corresponding to daylight color (color temperature is 5654K, chromaticity coordinates are x = 0.329, y = 0.4211: trade name, LDA5N, manufactured by Toshiba Lighttech). The color rendering index is measured with a spectral radiance meter (CS-2000, manufactured by Konica Minolta Sensing) using natural light as a reference (100), and measured values such as the average color rendering index (Ra) are shown in Table 1.
[Example 8]
The color rendering properties when the wavelength conversion filter was used were evaluated by the following operations.
The color rendering property evaluation was implemented about the wavelength conversion film of this invention produced in Examples 1-6. In this test, an LED bulb corresponding to the bulb color (color temperature is 3194K, chromaticity coordinates are x = 0.4188, y = 0.3883: trade name, LDA5L, manufactured by Toshiba Lighttech). The color rendering index is measured with a spectral radiance meter (CS-2000 type, manufactured by Konica Minolta Sensing) using A light source as a reference (100), and measured values such as the average color rendering index (Ra) are shown in Table 1.

[Comparative Example 1]
In Example 7, it is the same as Example 7 except that the wavelength conversion filter of the present invention produced in Examples 1-6 is not attached to the front surface of an LED bulb equivalent to daylight color (trade name, LDA5N, manufactured by Toshiba Lighttech). And evaluated. The results are shown in Table 1.

[Comparative Example 2]
In Example 8, Example 8 except that the wavelength conversion filter of the present invention prepared in Examples 1 to 6 was not attached to the front surface of the LED bulb corresponding to the color of the bulb (trade name, LDA5L, manufactured by Toshiba Lighttech). Evaluation was performed in the same manner. The results are shown in Table 1.

From Table 1, by installing the wavelength conversion filters obtained in Examples 1 to 6, the color rendering index (Ra) is improved, the numerical value of R9 indicating the appearance of red is also high, and a preferable white light source is obtained. It was.

  A color conversion layer comprising a color conversion material having a maximum absorption range in a specific wavelength range and having a light emission maximum above a specific wavelength, and a wavelength conversion filter using the same, without reducing luminance and light quantity. Sexual improvement is brought about.

Claims (1)

As a color conversion material, a metal-free tetraazaporphyrin compound represented by the general formula (3) having a maximum absorption range at a wavelength of 560 nm to 600 nm and a light emission maximum at a wavelength of 600 nm or more:

(Wherein, in X ₁ to X ₈ are each independently, full Tsu atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, a linear, branched or cyclic halogenoalkoxy group, a linear, table to a branched or cyclic alkoxyalkyl group.)
Acenaphtho [1 ′, 2 ′: 5,6] indeno [1,2,3-cd] benzo [5,6] indeno [1 ′, 2 ′, 3 having a skeleton represented by the general formula (4) '-Lm] perylene derivative:

Wherein Z _{1 to} Z ₂₂ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, substituted or represents an unsubstituted carboxyl group), and having a skeleton represented by the general formula (5), bis phenanthryl Trueno [9 ', 10': 6,7] indeno [1, 2, 3-cd: 1 ' , 2 ′, 3′-lm] perylene derivatives:

Wherein Z _{31 to} Z ₅₆ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, substituted or an unsubstituted carboxyl group to the table)
Pressurized et selected at least one of the white LED illumination apparatus filter comprising a wavelength conversion layer containing the compound was.