Extruded PET film with light-stable dyes for color conversion

Abstract

The present invention relates to a color converter, which comprises: (a) a polyethylene terephthalate matrix material; and (b) at least one organic fluorescent dye selected from the compounds of formula (Ia), (Ib), (Ic) or a mixture thereof, wherein EWG1 and EWG2 are CN, CH(O), C(O)R 13 ,OC(O)R 13 ,COOR 14 ,CH(COOR 14 )2, SO2R 14 , C(O)NR 15 R 16 , SO2NR 15 R 16 or C1‑C 20 Fluoroalkyl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 13 , R 14 , R 15 and R 16 As defined in the claims and the description. The invention also relates to a backlight unit, a liquid crystal display module and a light emitting device comprising the color converter. The invention also relates to a novel compound having formula (Ib), wherein EWG1=EWG2=CN. #imgabs0#

Description

[0001] The present invention relates to a color converter comprising a polyethylene terephthalate (PET) matrix material and at least one boron-dipyrromethene (BODIPY) compound having at least two electron withdrawing groups on its core carbon skeleton, and to a backlight unit, a liquid crystal display device and a lighting device each comprising the color converter. The present invention also relates to a novel boron-dipyrromethene compound having cyano groups at the 2- and 6-positions. Background of the Invention

[0003] Color converters, also known as color conversion films, are used in many optical devices, such as liquid crystal display (LCD) panels or conventional lighting devices. LCD panels generally include a liquid crystal display unit, which uses liquid crystals as optical modulators, and a backlight unit for illuminating the LCD panel. The backlight unit generally contains an array of blue or white light emitting diodes (LEDs) as light sources in combination with a color converter. White light is usually produced by using a combination of blue LEDs and color converters. The color converter generally includes a layer containing a polymer material and one or more phosphors as wavelength conversion materials, or consists of them. The wavelength conversion material converts the light emitted from the LED light source into light with a second longer wavelength, for example, the emitted blue light is converted into emitted green or red light, and the mixing of the transmitted blue light with the converted light results in white light. The phosphor in the polymer material can be applied directly to the LED chip, and the construction in which the phosphor is directly applied without intervening space for the LED chip is also called a "phosphor on chip" type construction. In a phosphor on chip type LED, the polymer material and the phosphor are subjected to higher thermal and irradiation stresses. Therefore, inorganic phosphors are used. Inorganic oxides doped with rare earth ions are most commonly used as inorganic phosphors. The most widely used white LEDs are based on the emission of blue light from an InGaN chip coated with a cerium-doped yttrium aluminum garnet (Ce:YAG) phosphor that emits in the yellow spectral range (about 560 nm). The emission of the Ce:YAG phosphor is very broad. In addition, such white LEDs do not show a separate emission band for the green color.

[0004] In order to produce white light from blue light by color conversion, there is another concept that there is a certain distance between the color converter, which usually includes an organic phosphor (organic fluorescent dye) and a polymer matrix material, and the LED chip. This structure is called a "remote phosphor". The spatial distance between the initial light source, the LED and the color converter reduces the stress caused by heat and irradiation to the extent that the stability requirements that can be achieved by organic fluorescent dyes are usually achieved. However, when using the organic fluorescent dyes of the prior art in remote phosphor applications based on LED lighting systems, the main disadvantage is generally still their poor light stability. Organic fluorescent dyes are usually embedded in thermoplastic polymer matrix materials, such as polycarbonate (PC), polystyrene (PS) or polymethyl methacrylate (PMMA). Compared with inorganic phosphors, organic fluorescent dyes have many advantages: first, they have a high mass specific absorption ratio, which means that for effective irradiation conversion, organic fluorescent dyes require significantly less material than inorganic phosphors. Second, their emission spectra can be easily adjusted in terms of wavelength and bandwidth. In addition, they usually have a narrower spectral width than inorganic phosphors. Third, they do not require any rare earth element-containing materials, which must be mined and supplied in an expensive and cumbersome manner and are only available to a limited extent. Fourth, they are soluble in the polymer matrix in which they are embedded and therefore do not aggregate. In addition, they can generally be easily processed via solution casting or extrusion.

[0005] In conventional liquid crystal displays (LCDs), backlights based on a combination of blue or white LEDs and color converters are commonly used. The light source simultaneously emits red, green and blue (RGB) light. A wide range of colors can be obtained by mixing red, green and blue primary colors of different intensities. When light emitted from a prior art white LED passes through a color filter, red and green are generally unsaturated. This also applies to the case where a blue LED is combined with a prior art color converter. However, a disadvantage of prior art displays is generally a narrow color gamut. The color gamut of a display is typically evaluated by comparing the triangular area connecting the chromaticity points of the RGB primary colors in the CIE 1931 or CIE 1976u'v' chromaticity diagram with those of the RGB standard, such as rec 709 (for high-definition TV), DPI-P3 (for digital projection and 4K Ultra HD TV) or rec 2020 (for ultra-high-definition TV). In order to produce a large color gamut or saturated colors, the backlight should provide a narrow emission band in the initial wavelength. The most widespread color gamut technology solution is the adjustment of the backlight structure, such as quantum dot enhanced film (QDEF), which acts as a color conversion film. In principle, organic fluorescent dyes with narrow emission bands in the original wavelength can play the same role as quantum dots, but they are more competitive in price and environmentally friendly.

[0006] At present, boron-dipyrromethene (BODIPY) compounds have attracted attention as organic fluorescent dyes in optical applications, because they have high extinction coefficients, high fluorescence quantum yields and narrow emission band widths. However, it is known that BODIPY substituted with nitro groups have low fluorescence quantum yields or even do not show fluorescence, so they are not suitable for use in color converters for LCD backlights and lighting equipment. It is also known that the absorption and emission spectra of BODIPY can be adjusted by changing the substitution pattern on the core carbon skeleton. For example, the extension of conjugation with aromatic systems or olefins causes the absorption and fluorescence spectra to shift to the red part of the visible spectrum.

[0007] WO 2017 / 155297, US 2016 / 0223162, US2017 / 267921, US 2018 / 0134953, US 2018 / 0274753 and US 2019 / 093008 describe color converters comprising a BODIPY dye in a resin matrix, which may in particular be a cyano-substituted BODIPY dye; also describe a backlight unit comprising such a color converter and its use in a display device.

[0008] US 2016 / 230960 describes a color conversion layer comprising a BODIPY compound in a resin matrix. The resin matrix material is preferably a thermosetting polymer or a heat curing polymer. The color conversion layer may have a substrate, for example provided on one surface of PET.

[0009] US 2017 / 0247610 proposes a color conversion film, which includes a resin matrix and a fluorescent substance. A high color gamut can be obtained by using a BODIPY compound emitting green light and a BODIPY compound emitting red light, wherein the BODIPY compound emitting green light has a maximum emission wavelength in the range of 510-560nm and a FWHM of 50nm or less, and the BODIPY compound emitting red light has a maximum emission wavelength in the range of 600-660nm and a FWHM of 90nm or less. Suitable BODIPY compounds are especially those with cyano groups on the core carbon skeleton. The resin matrix is ​​preferably a thermosetting polymer or a heat-curing polymer, especially based on poly (meth) acryloyl, based on polycarbonate, based on polystyrene, based on polyaromatic hydrocarbons, based on polyurethane, based on styrene-acrylonitrile, based on polyvinylidene fluoride, based on a resin matrix material of modified polyvinylidene fluoride. Polyethylene terephthalate film can be used as a carrier for color conversion film. The color conversion film can be prepared by coating a resin solution in which the BODIPY compound is dissolved on a substrate and drying; or by extruding the BODIPY compound with a resin such as a polycarbonate-based, poly(meth)acryl-based or styrene-acrylonitrile-based resin.

[0010] US 2018 / 0208838, US 2018 / 0134952 and US 2018 / 0134953 describe color conversion compositions comprising red and green emitting BODIPY compounds and binder resins. The BODIPY compounds may be those substituted with cyano groups in particular. The binder resin is preferably a thermoplastic resin, such as an epoxy resin, a silicone resin, an acrylic resin or a mixture thereof. The color conversion film prepared from the color conversion composition has good emission properties, but low light stability in an acrylate or siloxane matrix.

[0011] US 2019 / 0062348 relates to red fluorescent BODIPY compounds, which may carry cyano groups at the 2- and 6-positions of the carbon core skeleton, and the use of the compounds in color conversion films. The color conversion film comprises these compounds dispersed in a resin matrix. The resin matrix material is preferably a thermoplastic polymer or a heat-curable polymer, in particular based on poly(meth)acryloyl, based on polycarbonate (PC), based on polystyrene (PS), based on polyaromatic hydrocarbons (PAR), based on polyurethane (TPU), based on styrene-acrylonitrile (SAN), based on polyvinylidene fluoride (PVDF), based on modified polyvinylidene fluoride (modified-PVDF).

[0012] WO2018 / 068299 describes a light-emitting device comprising a blue backlight unit and a color conversion array containing a green color conversion layer and a red color conversion layer, comprising surface-modified particles that emit green light or red light, respectively, wherein the surface-modified particles comprise sol-gel nanoparticles and a plurality of luminophores, such as BODIPY dye, attached to the surface of the sol-gel nanoparticles.

[0013] None of these documents specifically describes the use of BODIPY compounds in polyethylene terephthalate matrix materials.

[0014] Unpublished EP 18179281.3 describes a color converter comprising at least one green-fluorescing cyano-substituted BODIPY dye and a backlight unit for a liquid crystal display comprising the color converter.

[0015] Color converters are often exposed to blue LED light for a long time. Therefore, it is important to maintain the long-term stability of the organic fluorescent dye. US 9,897,285 describes a color converter with an extended lifetime, which comprises an organic fluorescent compound and a polymer carrier material having a low oxygen diffusion coefficient at 25° C. Polyethylene terephthalate (PET) is said to be particularly suitable as a polymer carrier material.

[0016] The disadvantages of the color converters of the prior art are usually insufficient light stability and / or unsatisfactory color performance, in particular they cannot provide high-quality colors via a combination of high-purity red, green and blue. In addition, the fluorescent dyes of the prior art usually fade or bleed out of the color converter.

[0017] Therefore, the object of the present invention is to provide a stable organic green fluorescent dye whose emission spectrum has a narrow full width at half maximum (FWHM), preferably whose central emission wavelength should be close to the primary green wavelength of standard DCI-P3 or rec2020 (the spectral position of pure primary green is about 530nm). The object of the present invention is also to provide a stable organic red fluorescent dye whose emission spectrum has a narrow FWHM, preferably whose central emission wavelength should be close to the primary red wavelength of standard DCI-P3 or rec2020 (the spectral position of pure primary red is about 630-640nm). The object of the present invention is also to provide a color converter with long-term durability, preferably with high color purity emission according to DCI-P3 or rec2020 (the emission wavelength is close to the spectral position of pure primary red and green), which is used in liquid crystal displays or LED lighting. From an economic point of view, the object of the present invention is to prepare a color converter by extrusion. The object of the present invention is also to provide a liquid crystal display having a wide color gamut and high light stability. SUMMARY OF THE INVENTION

[0019] Surprisingly, it has been found that the thermal stability of BODIPY compounds can be significantly improved by introducing at least two electron withdrawing groups on their core carbon skeleton, which allows their extrusion in polyethylene terephthalate (PET). It has also been found that the introduction of these BODIPY compounds in a polyethylene terephthalate matrix material allows the provision of color converters with excellent photostability and thus improved lifetime when irradiated with blue light. Advantageously, the BODIPY compounds of the invention and used according to the invention have a sharp emission spectrum with a narrow bandwidth and a central emission wavelength very close to or even corresponding to the DPI-P3 or rec 2020 wavelength of the primary colors. The BODIPY compounds of the invention also have a high fluorescence quantum yield.

[0020] Therefore, the present invention relates to a color converter comprising:

[0021] (a) a polyethylene terephthalate base material; and

[0022] (b) at least one organic fluorescent dye selected from the compounds of formula (Ia), (Ib), (Ic) or mixtures thereof:

[0023]

[0024] in

[0025] EWG1 and EWG2 are independently selected from CN, CH(O), C(O)R 13 ,OC(O)R 13 ,COOR 14 ,CH(COOR 14 )2, SO2R 14 , C(O)NR 15 R 16 , SO2NR 15 R 16 or C1-C 20 Fluoroalkyl;

[0026] When present in formula (Ia), (Ib) and (Ic), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently selected from hydrogen, fluorine, COOR 14 ,CH(COOR 14 )2, C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkenyl, C6-C 14 aryl, heterocyclic or heteroaryl,

[0027] Among them, C1-C 20 Alkyl, C2-C 20 Alkenyl and C2-C 20 Alkynyl is unsubstituted or substituted by one or more substituents R 8 replace,

[0028] Among them, C3-C 20 Cycloalkyl and C4-C 20 The cycloalkenyl group is unsubstituted or substituted by one or more substituents R 9 replace,

[0029] Among them, C6-C 14 The aryl group is unsubstituted or substituted by one or more substituents R 10 replace,

[0030] Wherein the heterocyclic group and the heteroaryl group are unsubstituted or substituted by one or more substituents R 10 replace;

[0031] R 7a , R 7b and R 7cIt is hydrogen, fluorine, cyano, C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkenyl, C6-C 14 aryl or heteroaryl;

[0032] Among them, C1-C 20 Alkyl, C2-C 20 Alkenyl and C2-C 20 Alkynyl is unsubstituted or substituted by one or more substituents R 8 replace,

[0033] Among them, C3-C 20 Cycloalkyl and C4-C 20 The cycloalkenyl group is unsubstituted or substituted by one or more substituents R 9 replace,

[0034] Among them, C6-C 14 The aryl group is unsubstituted or substituted by one or more substituents R 11 replace;

[0035] Each R 8 independently selected from fluorine, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkenyl, C6-C 14 Aryl, C6-C 14 an aryloxy group or a heteroaryl group,

[0036] Among them, C3-C 20 Cycloalkyl and C4-C 20 The cycloalkenyl group is unsubstituted or substituted by one or more substituents R 9 Replace, and

[0037] Among them, C6-C 14 Aryl and C6-C 14 The aryloxy group is unsubstituted or substituted by one or more substituents R 10 replace;

[0038] Each R 9 are independently selected from cyano, fluoro, C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkoxy or tri-(C1-C 10 Alkyl)silyl;

[0039] Each R 10 are independently selected from cyano, fluoro, C1-C10 Alkyl, C1-C 10 Fluoroalkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkoxy, tri-(C1-C 10 alkyl) silyl, heteroaryl, phenyl or phenoxy, wherein the aromatic rings in the last two groups may be substituted by one or more substituents R 12 replace;

[0040] Each R 11 Independently selected from EWG1, fluorine, chlorine, bromine, C1-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkoxy, tri-(C1-C 10 Alkyl) silyl, N(C1-C 20 Alkyl)2, N(C6-C 14 aryl)2, heteroaryl, biphenyl, terphenyl, spirofluorenyl, C6-C 14 Aryl, C6-C 14 Aryl-C1-C 10 Alkylene, C6-C 14 Aryl-C1-C 10 Alkylene-O-, wherein the last six groups are unsubstituted in the aryl moiety or are substituted by one or more substituents R 12 replace;

[0041] Each R 12 Independently selected from EWG1, C1-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkoxy, tri-(C1-C 10 Alkyl) silyl or C3-C 20 Cycloalkyl;

[0042] R 13 Selected from C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, C3-C 20 Cycloalkyl, C3-C 20 Cycloalkyl-C1-C 10 Alkylene, C6-C 14 Aryl or C6-C 14 Aryl-C1-C 10 Alkylene,

[0043] Among them, C6-C 14 Aryl and C6-C 14 Aryl-C1-C 10The aryl moiety in the alkylene group is unsubstituted or substituted with one or more substituents R 10 replace;

[0044] R 14 Selected from hydrogen, C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, C3-C 20 Cycloalkyl, C3-C 20 Cycloalkyl-C1-C 10 Alkylene, C6-C 14 Aryl or C6-C 14 Aryl-C1-C 10 Alkylene,

[0045] Among them, C6-C 14 Aryl and C6-C 14 Aryl-C1-C 10 The aryl moiety in the alkylene group is unsubstituted or substituted with one or more substituents R 10 replace;

[0046] R 15 and R 16 Each occurrence is independently hydrogen, C1-C 10 Alkyl or C1-C 10 Fluoroalkyl.

[0047] The inventors have found that when the core carbon skeleton is replaced by electron-withdrawing groups EWG1 and EWG2, the thermal stability of the BODIPY dye is significantly improved. This allows the preparation of a color converter comprising a BODIPY compound and a polyethylene terephthalate matrix material by an extrusion process. This also allows the preparation of a color converter without the addition of an additional solvent. In addition, the inventors have found that the introduction of the BODIPY dye into the polyethylene terephthalate matrix material can increase the life of the BODIPY dye, thereby increasing the life of the color converter. Therefore, the color converter of the present invention has high light stability, high fluorescence quantum yield, and a narrow emission bandwidth of the fluorescent BODIPY dye. Due to these properties, the color converter is particularly suitable for use in backlighting or in LED lighting.

[0048] Another aspect of the invention relates to a backlight unit comprising: a light source for emitting light; and a color converter as defined above, wherein the color converter is remotely arranged with respect to the LED.

[0049] Another aspect of the present invention relates to a liquid crystal display assembly comprising:

[0050] (i) a liquid crystal panel comprising a thin film transistor (TFT) array, a liquid crystal layer and a color filter array, wherein the color filter array comprises red, green and blue color filters;

[0051] (ii) at least one light source; and

[0052] (iii) at least one color converter as defined above.

[0053] Yet another aspect of the present invention relates to a light emitting device comprising: (i) at least one LED selected from a blue LED having a central emission wavelength of 400-480 nm and a cool white LED having a correlated color temperature of 3,000-20,000 K; and (ii) at least one color converter as defined above, wherein the at least one color converter is remotely arranged relative to the at least one LED.

[0054] Another aspect of the present invention relates to novel compounds of formula (Ib), wherein R 1 and R 6 Each is phenyl; R 3 and R 4 Each is 4-methoxyphenyl or 4-(2,6-diisopropylphenoxy)phenyl; EGW1 and EWG2 are each cyano; and R 7b is phenyl, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 groups R selected from 11 Substitution: EWG1, Fluorine, Chlorine, C1-C 10 Alkyl, C1-C 10 Alkoxy, phenyl, biphenyl, terphenyl or phenyl-C1-C 10 Alkylene.

[0055] Another aspect of the present invention relates to novel compounds of formula (Ib), wherein R 1 , R 3 , R 4 and R 6 Each is a methyl group; EWG1 and EWG2 are each a cyano group; and R 7b yes phenyl, 2-chlorophenyl, 2-fluorophenyl, 2,6-dichlorophenyl, 2,6-difluorophenyl, 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0056] Another aspect of the present invention relates to novel compounds of formula (Ib), wherein R 1 and R 6 Each is a methyl group; R 3 and R 4 Each is 4-cyanophenylvinyl; EWG1 and EWG2 are each cyano; and R 7b yes phenyl, 2-chlorophenyl, 2-fluorophenyl, 2,6-dichlorophenyl, 2,6-difluorophenyl, 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl. DETAILED DESCRIPTION OF THE INVENTION

[0058] In the present invention, the term "luminescent material" is also referred to as "phosphor" or "conversion material". These terms refer to a material that absorbs light having a specific wavelength or wavelength range and converts it into light that is re-emitted at a different wavelength or wavelength range (longer wavelength).

[0059] In the present invention, the term "color converter", also referred to as converter for short, is understood to mean all physical devices that absorb light with a specific wavelength and convert it into light of a second wavelength. The color converter comprises one or more layers, at least one of which comprises at least one organic fluorescent dye according to the invention in a polyethylene terephthalate matrix material. Each layer comprising the organic fluorescent dye according to the invention has a planar structure extending essentially in two dimensions. The color converter may comprise further layers, for example substrate layers and / or barrier layers.

[0060] In the present invention, the term "polyethylene terephthalate matrix material" means that at least one organic fluorescent dye of the present invention is dispersed or dissolved in polyethylene terephthalate at a molecular level.

[0061] Organic fluorescent dyes can be classified into green light-emitting dyes, red light-emitting dyes, and the like according to the color of light (wavelength of light).

[0062] In the present invention, the term "blue light" is light with a wavelength in the range of 400 to more than 500 nm, preferably a wavelength in the range of 420-480 nm.

[0063] In the present invention, the term "green light" is light with a wavelength in the range of 500-560nm.

[0064] In the present invention, the term "yellow light" is light having a wavelength in the range of greater than 560 to less than 595 nm.

[0065] In the present invention, the term "red light" refers to light with a wavelength in the range of 595-780 nm, preferably a wavelength in the range of 610-660 nm.

[0066] In the present invention, the term "central wavelength" with respect to a given spectral distribution F(λ) is defined as the average value of: λ c =∫λ·F(λ)dλ / ∫F(λ)dλ.

[0067] In the present invention, the term "full width at half maximum (FWHM)" means the width of a line shape at half of its maximum amplitude.

[0068] In the present invention, the term "fluorescence quantum yield (QY)" means the ratio of the number of emitted photons to the number of absorbed photons.

[0069] The term "LED" as used herein means an inorganic light emitting diode. In the present invention, "blue LED" is understood to mean an LED that emits light in the blue range of 400-480nm, preferably 420-480nm, more preferably 440-470nm, and most preferably 440-460nm, with a central emission wavelength of the electromagnetic spectrum. Suitable semiconductor materials are silicon carbide, zinc selenide, and nitrides such as aluminum nitride (AlN), gallium nitride (GaN), indium nitride (InN), and indium gallium nitride (InGaN). LEDs typically have a narrow wavelength distribution that is tightly concentrated around their peak wavelength. Standard InGaN-based blue LEDs are manufactured on sapphire substrates, and the peak emission wavelength is typically concentrated at 445-455nm.

[0070] In the present invention, "micro LED" and "mini LED" refer to LEDs that mainly emit blue light. They are formed of semiconductor materials such as gallium nitride (GaN) or zinc selenide (ZnSe). The chip size of mini LEDs is generally 100-200 μm. Micro LEDs (μ-LEDs) generally have a maximum width of 1-100 μm.

[0071] In the present invention, "white LED" (LED that produces or emits white light) means an LED that emits light that the human eye perceives as white. An example is a multi-LED (also called RGB LED system) consisting of red, green and blue LEDs, whose emission is mixed to form white light. Other representative examples include blue LEDs, whose light passes through a color converter containing a phosphor. Preferred are blue LEDs coated with inorganic phosphors, especially yellow phosphors, such as doped yttrium aluminum garnet.

[0072] In the present invention, the term "white light" relates to light having a correlated color temperature (CCT) of 2000-20000 K, especially 2500-20000 K. Commercially available white LEDs typically have a correlated color temperature of 3000 K or higher, for example in the range of 3000-20000 K or 4000-20000 K.

[0073] In the present invention, electromagnetic radiation comprising the visible spectrum range of 420-780 nm is also referred to as visible light.

[0074] In the present invention, the term "color gamut" defines the range of colors that a display can produce. A conventional method for representing the color gamut of a display is the xy chromaticity diagram of the XYZ color system, which is established by the International Commission on Illumination (CIE). The color gamut is defined by the triangular area on the xy chromaticity diagram. Additionally or alternatively, the u'v' diagram established by the International Commission on Illumination is used to evaluate the color gamut.

[0075] In the present invention, the term "RGB color space" is defined by the chromaticity of the three primary colors, namely red, green and blue, where red, green and blue light are added together to produce a color.

[0076] As used in this specification and the claims, the singular forms "a," "an," and "the" include plural referents unless expressly stated otherwise.

[0077] Similarly, the terms "first", "second" do not exclude a plurality.

[0078] The term "at least" means one or more than one, for example 1, 2, 3 or 4, preferably 1, 2 or 3. Also preferably, the term "at least" defines a plural meaning.

[0079] The term "optionally substituted" means that the referenced group is unsubstituted or substituted.

[0080] In the present invention, the term "substantially" encompasses the words "completely", "entirely" and "all". This term includes a proportion of 90% or more, such as 95% or more, especially 99% or 100%.

[0081] The definitions of the variables in the above formulae use collective terms, which are generally representative examples of the corresponding substituents. n -C m ” gives in each case the number of carbon atoms which may be present in the corresponding substituent or substituent moiety.

[0082] The term "BODIPY" refers to compounds having a boron-dipyrromethene core (also known as a 4-boron-3a,4a-diaza-s-indacene core). The numbering of the BODIPY core used herein is as follows. The 8-position is also known as the meso position.

[0083]

[0084] The organic moieties mentioned in the above definitions of the variables, such as the term halogen, are collective terms for the list of the individual group members listed. n -C mIn each case the possible number of carbon atoms in the radical is indicated.

[0085] The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular chlorine, bromine or iodine.

[0086] The term "alkyl" as used herein (and alkyl moieties in other alkyl-containing groups, such as alkoxy, alkylamino, alkylcarbonyl, alkoxycarbonyl) denotes in each case a straight-chain or branched alkyl group having usually 1 to 20 carbon atoms, usually 1 to 10 carbon atoms, generally 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of C1-C4-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl (= sec-butyl), isobutyl and tert-butyl. Examples of the C1-C6 alkyl group are those exemplified above with respect to the C1-C4 alkyl group, as well as n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl. 10 Examples of alkyl groups include, but are not limited to, those described above for C1-C6 alkyl groups, as well as n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, n-octyl, 1-methyloctyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1,2-dimethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl, decyl, 2-propylheptyl and 3-propylheptyl.

[0087] The term "alkylene" (or alkanediyl) as used herein denotes in each case an alkyl group as defined above, wherein one hydrogen atom at any position of the carbon skeleton is replaced by one further attachment position, thereby forming a divalent moiety. 10 Alkylene or C1-C 10-Alkanediyl is a straight or branched divalent alkyl radical having 1 to 10 carbon atoms. Representative examples include, but are not limited to: -CH2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-, -C(CH3)2-, -CH2CH2CH2CH2-, -CH(CH3)CH2CH2-, -CH2CH2CH(CH3)-, -C(CH3)2-, -CH2CH2CH2CH2-, -CH(CH3)CH2CH2-, -CH2CH2CH(CH3)-, -C(CH3)2CH2-, and -CH2C(CH3)2-.

[0088] The term "fluoroalkyl" refers to a saturated straight-chain or branched hydrocarbon group having 2 to 20 carbon atoms, in which at least one, for example 1, 2, 3, 4 or all hydrogen atoms are replaced by fluorine atoms ("C2-C 20 The preferred fluoroalkyl moieties are selected from C1-C4 fluoroalkyl groups, more preferably C1-C2 fluoroalkyl groups. Representative examples of C1-C2 fluoroalkyl groups include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoroethyl.

[0089] The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group which is attached via an oxygen atom to the remainder of the molecule, i.e. "alkoxy" may be represented as -O-alkyl, wherein alkyl is as defined above. 10 Representative examples of alkoxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-methylethoxy (isopropoxy), butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy), 1,1-dimethylethoxy (tert-butoxy), pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy, as well as positional isomers of the last six of these groups.

[0090] The term "fluoroalkoxy" as used herein denotes in each case a straight-chain or branched alkoxy radical as defined above having 1 to 10 carbon atoms ("C1-C 10 The fluoroalkoxy group is a fluoroalkoxy group having 1 to 8 carbon atoms (a "fluoroalkoxy group"). The fluoroalkoxy group has 1 to 6 carbon atoms (a "fluoroalkoxy group"). The fluoroalkoxy group has 1 to 4 carbon atoms (a "fluoroalkoxy group"). The fluoroalkoxy group has 1 to 4 carbon atoms (a "fluoroalkoxy group"). The hydrogen atoms of the fluoroalkoxy group are partially or completely replaced by fluorine atoms.

[0091] As used herein, the term "alkenyl" refers to a straight or branched hydrocarbon chain containing 2 to 20 carbon atoms and containing at least one carbon-carbon double bond, such as 1, 2, 3 or 4 carbon-carbon double bonds. Representative examples of alkenyl groups having 2 to 10 carbon atoms and 1 carbon-carbon double bond include, but are not limited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 2-heptenyl, 2-methyl-1-heptenyl and 3-decenyl. Representative examples of alkenyl groups having 4 to 10 carbon atoms and 2 carbon-carbon double bonds are buta-1,3-dienyl, 1-methyl-buta-1,3-dienyl, penta-1,3-dienyl, 4-methyl-penta-1,3-dienyl and the like. Representative examples of alkenyl groups having 6 to 10 carbon atoms and 3 carbon-carbon double bonds are hexa-1,3,5-trienyl, 1-methyl-hexa-1,3,5-trienyl, hept-1,3,5-trienyl, 6-methyl-hept-1,3,5-trienyl and the like.

[0092] The term "fluoroalkenyl" denotes an unsaturated straight or branched hydrocarbon group as defined above having 2 to 20 carbon atoms and at least one carbon-carbon double bond, wherein at least one, for example 1, 2, 3, 4 or all hydrogen atoms are replaced by fluorine atoms.

[0093] The term "alkynyl" as used herein means a straight chain or branched hydrocarbon group containing 2 to 20 carbon atoms and containing at least one carbon-carbon triple bond. Representative examples of alkynyl groups having 2 to 6 carbon atoms include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl.

[0094] The term "fluoroalkynyl" denotes an unsaturated straight or branched hydrocarbon group as defined above having 2 to 20 carbon atoms and at least one carbon-carbon triple bond, wherein at least one, for example 1, 2, 3, 4 or all hydrogen atoms are replaced by fluorine atoms.

[0095] The term "cycloalkyl" as used herein denotes in each case a monocyclic, bicyclic, tricyclic or tetracyclic saturated hydrocarbon radical having usually 3 to 20 carbon atoms ("C3-C 20Representative examples of monocyclic groups having 3-6 carbon atoms include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Representative examples of monocyclic groups having 3-8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Representative examples of bicyclic groups having 7-12 carbon atoms include, but are not limited to, bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]

[0063] octyl, bicyclo[3.3.0]octyl, bicyclo[3.2.1]octyl, bicyclo[3.3.1]nonyl, bicyclo[4.2.1]nonyl, bicyclo[4.3.1]decyl, bicyclo[3.3.2]decyl, bicyclo[4.4.0]decyl, bicyclo[4.2.2]decyl, bicyclo[4.3.2]undecyl, bicyclo[3.3.3]undecyl, bicyclo[4.3.3]dodecyl, and perhydronaphthyl. Representative examples of tricyclic and tetracyclic groups having 10-20 carbon atoms include, but are not limited to, perhydroanthracenyl, perhydrofluorenyl, perhydrochrysene, and adamantyl.

[0096] The term "cycloalkyl-alkyl" as used herein means a cycloalkyl group as defined above attached via an alkylene group to the rest of the molecule (or an alkyl group as defined above wherein one hydrogen atom is replaced by a cycloalkyl group as defined above). 20 Cycloalkyl-C1-C 10 "Alkylene" means a C3-C 20 Cycloalkyl, which is cycloalkyl as defined above, 10 The alkyl group is attached to the rest of the molecule. Representative examples include, but are not limited to, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclopentylpentyl, cyclopentylhexyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cycloheptylmethyl, cycloheptylethyl, cycloheptylpropyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, cyclohexylpentyl, cyclohexylhexyl, and the like.

[0097] The term "cycloalkenyl" as used herein denotes in each case a monocyclic, bicyclic, tricyclic or tetracyclic partially unsaturated, non-aromatic hydrocarbon radical having generally 4 to 20 carbon atoms ("C4-C 20Representative examples of monocyclic groups having 4 to 8 carbon atoms include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclopenta-1,3-dien-1-yl, cyclopenta-1,3-dien-2-yl, cyclopenta-1,3-dien-5-yl, cyclohex-1-en-1-yl, cyclohex-1-en-3-yl, cyclohex-1-en-4-yl, cyclohex-1,3-dien-1-yl, cyclohex-1,3-dien-2-yl, cyclohex-1,3-dien-5-yl, cyclohex-1,4-dien-1-yl, and cyclohex-1,4-dien-3-yl.

[0098] The term "aryl" as used herein means a monocyclic aromatic hydrocarbon group (i.e., phenyl) or a fused bicyclic, tricyclic, or polycyclic aromatic hydrocarbon group having 6 to 14 carbon atoms. Representative examples of bicyclic or tricyclic aromatic carbocyclic rings include, but are not limited to, naphthyl, phenanthrenyl, anthracenyl, 9H-fluorenyl, and the like. The term "C6-C 10 "Aryl" means phenyl and naphthyl.

[0099] The term "aryloxy" is an aryl group as defined above attached via an oxygen atom to the remainder of the molecule. 10 "Aryloxy" is phenoxy or naphthoxy.

[0100] The term "arylalkyl" means that an aryl group as defined above is connected to the remainder of the molecule via an alkyl group as defined above. The aryl group can in turn be unsubstituted or substituted. Representative examples of arylalkyl include, but are not limited to: phenyl-C1-C4 alkyl, such as benzyl, 1-phenylethyl, 2-phenylethyl (phenethyl), 1-phenylpropyl, 2-phenylpropyl, 3-phenyl-1-propyl, 2-phenyl-2-propyl and naphthyl-C1-C4 alkyl, such as 1-naphthylmethyl, 1-naphthylethyl, 2-naphthylmethyl, 2-naphthylethyl.

[0101] The term "arylalkenyl" as used herein means an alkenyl group as described above, wherein one hydrogen atom is replaced by an aryl group as defined above. The aryl group may in turn be unsubstituted or substituted. Examples of preferred arylalkenyl groups include, but are not limited to, phenyl-C2-C6 alkenyl, such as phenylvinyl (phenylvinyl) or 2-phenyl-prop-1-enyl.

[0102] The heterocycle or heterocyclic radical or heteroaromatic ring or heteroaryl or heteroaryl group contains one or more heteroatoms as ring members, i.e. atoms different from carbon. In the present invention, these heteroatoms are N, O and S, wherein N and S can also be present as oxidized heteroatom groups, i.e. NO, SO or SO2. Therefore, in the present invention, the ring which is a heterocycle or heterocyclic radical or heteroaromatic ring or heteroaryl or heteroaryl group contains one or more heteroatoms and / or heteroatom groups as ring members which are selected from N, O, S, NO, SO and SO2, preferably from N, O and S.

[0103] The heterocycle or heterocyclic radical or heteroaromatic ring or heteroaryl or heteroaryl can be connected to the rest of the molecule via a carbon ring member or via a nitrogen ring member. Of course, these rings contain at least one carbon ring atom. If the ring contains more than one O ring atom, they are not adjacent.

[0104] The term "heterocyclyl" (also known as heterocycloalkyl) refers to a non-aromatic partially unsaturated or fully saturated monocyclic, bicyclic or tricyclic heterocyclic ring, which generally has 3-20 ring members. Representative examples of monocyclic heterocycloalkyl include, but are not limited to: pyrrolidinyl, piperidinyl, imidazolidinyl, pyrazolidinyl, Oxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, isothiazolidinyl oxazolidinyl, piperazinyl, tetrahydrothienyl, dihydrothien-2-yl, tetrahydrofuranyl, dihydrofuran-2-yl, tetrahydropyranyl, 2- Oxazolinyl, 3- Oxazolinyl, 4- Azoline and di Alkyl. Bicyclic heterocycles are usually 8-, 9- or 10-membered rings, which contain 1-3 nitrogen atoms and / or 1 oxygen or sulfur atom or 1 or 2 oxygen or sulfur atoms as ring members in addition to carbon members. Representative examples of bicyclic heterocycles include, but are not limited to: benzopyranyl, benzothiopyranyl, chromanyl, 2,3-dihydrobenzofuranyl.

[0105] The term "heteroaryl" (also referred to as heteroaryl) as used herein includes heteroaromatic monocyclic or polycyclic groups. The heteroatoms are preferably selected from oxygen, nitrogen and sulfur. The heteroaryl group preferably has 5-18 ring atoms, for example 5, 6, 8, 9, 10, 11, 12, 13 or 14 ring atoms. Monocyclic heteroaryl is a 5- or 6-membered ring. The 5-membered ring contains 2 double bonds. The 5-membered ring may contain 1 heteroatom selected from O or S; or 1, 2, 3 or 4 nitrogen atoms and optionally 1 oxygen or sulfur atom. The 6-membered ring contains 3 double bonds and 1, 2, 3 or 4 nitrogen atoms. Representative examples of monocyclic heteroaryl include, but are not limited to: furanyl, imidazolyl, isothiocyanate ... Azolyl, isothiazolyl, Oxazolyl, 1,3- The bicyclic heteroaryl groups include oxazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrazolyl, pyrrolyl, tetrazolyl, thiadiazolyl, 1,3-thiazolyl, thienyl, triazolyl, and triazinyl. The bicyclic heteroaryl groups include monocyclic heteroaryl groups fused to phenyl. Representative examples of bicyclic heteroaryl groups include quinolyl, isoquinolyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothienyl, benzo Azolyl, benzyl oxazolyl, benzothiazolyl, benzo oxadiazolyl, benzothiadiazolyl, benzo The polycyclic heteroaryl group has 3 or 4 fused rings.

[0106] The term "electron withdrawing group" ("EWG") refers to a functional group that can itself attract more electrons than a hydrogen atom would and would occupy the same position in a molecule.

[0107] The term "cyano" means CN.

[0108] When the symbols # or * appear in a substructure showing a compound of the invention, this indicates a bond to the rest of the molecule. BRIEF DESCRIPTION OF THE DRAWINGS

[0110] Figure 1 The emission intensity of two color converters according to the invention with a thickness of 130 μm and 150 μm is plotted as a function of wavelength, as measured by irradiation with a Fortimo blue LED in an integrating sphere. DETAILED DESCRIPTION OF THE INVENTION

[0112] A specific embodiment of the present invention relates to a color converter comprising:

[0113] (a) a polyethylene terephthalate base material; and

[0114] (b) at least one organic fluorescent dye selected from the compounds of formula (Ia), (Ib), (Ic) or mixtures thereof:

[0115]

[0116] Among them, EWG1 and EWG2, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 8 , R 9 , R 12 , R13 , R 14 , R 15 and R 16 is as defined above; and

[0117] Each R 10 are independently selected from cyano, fluoro, C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkoxy, tri-(C1-C 10 alkyl)silyl, phenyl, phenoxy or heteroaryl;

[0118] Each R 11 Independently selected from EWG1, fluorine, C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkoxy, tri-(C1-C 10 Alkyl) silyl, N(C1-C 20 Alkyl)2, N(C6-C 14 aryl)2, heteroaryl, biphenyl, terphenyl, spirofluorenyl, C6-C 14 Aryl, C6-C 14 Aryl-C1-C 10 Alkylene, C6-C 14 Aryl-C1-C 10 Alkylene-O-, wherein the last six groups are unsubstituted in the aromatic moiety thereof or are substituted by one or more substituents R 12 replace.

[0119] Another specific embodiment relates to a color converter comprising:

[0120] (a) a polyethylene terephthalate base material; and

[0121] (b) at least one organic fluorescent dye selected from the compounds of formula (Ia), (Ib), (Ic) or mixtures thereof

[0122]

[0123] in

[0124] EWG1 and EWG2, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R7b , R 7c , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 and R 16 is as defined above; and

[0125] Each R 10 are independently selected from cyano, fluoro, C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkoxy, tri-(C1-C 10 alkyl)silyl, phenyl, phenoxy or heteroaryl;

[0126] Each R 11 Independently selected from EWG1, fluorine, chlorine, bromine, C1-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkoxy, tri-(C1-C 10 Alkyl) silyl, N(C1-C 20 Alkyl)2, N(C6-C 14 aryl)2, heteroaryl, biphenyl, terphenyl, spirofluorenyl, C6-C 14 Aryl, C6-C 14 Aryl-C1-C 10 Alkylene, C6-C 14 Aryl-C1-C 10 Alkylene-O-, wherein the last six groups are unsubstituted in the aromatic moiety thereof or are substituted by one or more substituents R 12 replace.

[0127] According to the present invention, the color converter comprises a polyethylene terephthalate matrix material. The term "polyethylene terephthalate matrix material" includes a homopolymer of polyethylene terephthalate or a copolymer thereof. The polyethylene terephthalate or a copolymer thereof may be recycled or virgin polyethylene terephthalate or a copolymer thereof. Polyethylene terephthalate homopolymers are usually obtained by polycondensation of ethylene glycol with dimethyl terephthalate or terephthalic acid at high temperatures, while removing methanol (or water). Copolymers can be obtained by partially replacing ethylene glycol with another diol, triol or polyol based on higher functionality, and / or by partially replacing terephthalic acid with another dicarboxylic acid. Representative examples of diols different from ethylene glycol are 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and polyether diols, such as diethylene glycol, and combinations thereof. A representative example of a polyol based on higher functionality is pentaerythritol. Representative examples of suitable dicarboxylic acids different from terephthalic acid are isophthalic acid, 1-naphthoic acid, 2-naphthoic acid, glutaric acid, and combinations thereof. The same effect can be obtained by replacing the dimethyl ester formed from terephthalic acid with another diester formed from a dicarboxylic acid different from terephthalic acid. For example, a polyethylene terephthalate copolymer (glycol-modified polyethylene terephthalate) called PETG comprises structural units derived from a mixture of terephthalic acid and mainly ethylene glycol and a smaller amount of 1,4-cyclohexanedimethanol. The copolymer inhibits the cyclization of polyethylene terephthalate.

[0128] The term "polyethylene terephthalate matrix material" also includes high molecular weight polyethylene terephthalate having chain extender units introduced into the polymer backbone or polymer chain. Chain extenders are particularly useful for linking the terminal carboxyl groups of two individual ester molecules. Representative examples of chain extenders include tetracarboxylic dianhydrides, such as pyromellitic dianhydride, polyacyl lactams, diamines and polyamines, and compounds with high epoxy functionality, such as the commercially available EPOXY-2000 from BASF SE, Germany. Brand chain extender.

[0129] Preferably, the polyethylene terephthalate matrix material comprises at least 90% by weight of polyethylene terephthalate homopolymers, based on the total polymer content of the polyethylene terephthalate matrix material. In other words, up to 10% by weight of the polyethylene terephthalate, based on the total polymer content, is a copolymer of polyethylene terephthalate. More preferably, the polyethylene terephthalate matrix material comprises at least 95% by weight of polyethylene terephthalate homopolymers, based on the total polymer content of the polyethylene terephthalate matrix material. In particular, the polyethylene terephthalate matrix material consists entirely of polyethylene terephthalate homopolymers. According to another embodiment, the polyethylene terephthalate polymer matrix material does not contain any chain extender in the polymer backbone.

[0130] In one embodiment of the present invention, the polyethylene terephthalate has a semi-crystalline structure and is opaque. In another embodiment of the present invention, the polyethylene terephthalate has an amorphous structure and is transparent.

[0131] The following description of preferred embodiments of the individual variables (substituents) in the compounds of the formulae (Ia), (Ib) and (Ic) applies both per se and preferably in combination with one another.

[0132] The groups EWG1 and EWG2 in the compounds of formula (Ia), (Ib) and (Ic) are electron withdrawing groups which reduce the electron density of the BODIPY core carbon skeleton and thereby increase the stability of the BODIPY compounds. In particular, they do not impair the color purity of the BODIPY compounds used according to the invention. Preferably, EWG1 and EWG2 are independently selected at each occurrence from cyano (CN), C1-C 10 Fluoroalkyl, CH(O), C(O)R 13 ,COOR 14 ,CH(COOR 14 )2, SO2R 14 , C(O)NR 15 R 16 or SO2NR 15 R 16 , where R 13 , R 14 , R 15 and R 16 is as defined herein. In EWG1 and EWG2, R 13 Preferably, it is C1-C6 alkyl, C1-C6 fluoroalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C4 alkylene, phenyl or phenyl-C1-C4 alkylene. 14 and CH(COOR14 )2, R 14 Preferably, it is C1-C6 alkyl, phenyl-C1-C4 alkylene, C3-C8 cycloalkyl, or C3-C8 cycloalkyl-C1-C4 alkylene; and in SO2R 14 In, R 14 Preferably, it is C1-C6 alkyl or phenyl, and the phenyl is unsubstituted or substituted by C1-C6 alkyl. In EWG1 and EWG2, R 15 and R 16 is independently selected at each occurrence from C1-C6 alkyl.

[0133] More preferred compounds of the present invention are compounds of formula (Ia), (Ib) and (Ic), wherein EWG1 and EWG2 are independently selected at each occurrence from CN, CF3, CH(O), C(O)(C1-C4 alkyl), COO(C1-C4 alkyl) or CH(COO(C1-C4 alkyl))2. In particular, EWG1 and EWG2 are independently selected at each occurrence from CN, CF3, CHO, C(O)CH3, C(O)C2H5, C(O)C3H7, CH(COOCH3)2, CH(COOC2H5)2, CH(COOC3H7)2, COOCH3, COOC2H5 or COOC3H7.

[0134] In addition, the synthesis of compounds of formula (Ia), (Ib) and (Ic) in which EWG1 and EWG2 are identical is generally simpler than the synthesis of compounds of formula (Ia), (Ib) and (Ic) in which EWG1 and EWG2 are different. Therefore, further preferred are compounds of formula (Ia), (Ib) and (Ic) in which EWG1 and EWG2 have the same meaning. In particular, EWG1 and EWG2 are each cyano.

[0135] Preferred compounds of the present invention are compounds of formula (Ia), (Ib) and (Ic) wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 When present, each is independently selected from hydrogen, C1-C 10 Alkyl, C2-C 10 Alkenyl, C3-C 20 Cycloalkyl, C(O)O(C1-C6 alkyl), CH(COO(C1-C6 alkyl))2, phenyl or naphthyl, wherein C1-C 10 Alkyl and C2-C 10 Alkenyl is unsubstituted or substituted by 1 or 2 substituents R 8substituted, and wherein phenyl and naphthyl are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents R 10 Substitution, where R 8 and R 10 is as defined herein. In particular, preferably R 1 and R 6 is different from hydrogen. It is also preferred that R 1 , R 2 , R 3 , R 4 , R 5 and R 6 When present, they are different from hydrogen.

[0136] More preferably, when present in formula (Ia), (Ib) and (Ic), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each independently selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C3-C 20 Cycloalkyl, CH(COO(C1-C4 alkyl))2 or phenyl, where C1-C 10 Alkyl and C2-C 10 Alkenyl is unsubstituted or substituted by 1 or 2 substituents R 8 substituted, wherein the phenyl group is unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents R 10 Replace. Each R 8 Preferably, phenyl and naphthyl are selected from the group consisting of phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents R 10 In one embodiment, R 10 are independently selected from cyano, fluoro, C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, C1-C 10 Alkoxy, C1-C 10 Fluoroalkoxy, tri-(C1-C 10 Preferably, R 10 is selected from CN, F, C1-C6 alkyl, C1-C6 fluoroalkyl, C1-C6 alkoxy, C1-C6 fluoroalkoxy, phenyl or phenoxy. 10 is selected from phenoxy, which is substituted by 1, 2, 3, 4 or 5 substituents R 12 More preferably, each R 8 is selected from phenyl, which is unsubstituted or substituted by 1 or 2 substituents R 10 Replace. Each R10 More preferably, it is selected from CN, C1-C6 alkyl, C1-C6 fluoroalkyl, C1-C6 alkoxy, C1-C6 fluoroalkoxy, tri-(C1-C 10 alkyl) silyl, phenyl, phenoxy, 5- or 6-membered monocyclic heteroaryl having, in addition to carbon atoms, 1 or 2 heteroatoms selected from oxygen, sulfur or nitrogen atoms as ring members; and 1, 2 or 3 substituents R 12 Substituted phenoxy. Each R 10 In particular, it is selected from CN, CF3, OCF3, C1-C4 alkyl, C1-C4 alkoxy, phenyl or phenoxy, wherein the phenoxy group may be substituted by 1, 2 or 3 groups R 12 In this regard, R 12 Preferred is C1-C4 alkyl, such as isopropyl or tert-butyl.

[0137] Even more preferably, when present, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each independently selected from C1-C 10 Alkyl, especially C1-C4-alkyl, C2-C6-alkenyl, CH(COO(C1-C4-alkyl))2, phenyl, phenyl-C1-C4-alkyl and phenyl-C2-C6-alkenyl, especially phenyl-CH═CH-, wherein phenyl and the phenyl moiety in phenyl-C1-C4-alkyl and phenyl-C2-C6-alkenyl, especially phenyl-CH═CH-, are unsubstituted or substituted by 1, 2, 3, 4 or 5 radicals R 10 Substitution, where R 10 is as defined above, in particular having one of the preferred meanings given above. Even more preferably, when present in formulae (Ia), (Ib) and (Ic), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each independently selected from C1-C 10 alkyl, phenyl or phenyl-C2-C6-alkenyl, wherein the phenyl in the last two radicals and the phenyl moiety in phenyl-C2-C6-alkenyl may be substituted by 1, 2 or 3 substituents R 10 Substitution, where R 10 is as defined above, in particular having one of the preferred meanings given above.

[0138] According to a preferred embodiment, when present in formula (Ia), (Ib) and (Ic), all R 1 , R 2, R 3 , R 4 , R 5 and R 6 Each independently selected from C1-C 10 Alkyl is particularly selected from C1-C4 alkyl, more particularly selected from methyl, ethyl, n-propyl, isopropyl and tert-butyl. In particular, when present in formula (Ia), (Ib) and (Ic), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Each is independently selected from methyl or ethyl. The compounds of formula (Ia), (Ib) and (Ic) are fluorescent dyes emitting green light.

[0139] According to another preferred embodiment, when present in formula (Ia), (Ib) and (Ic), all R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from phenyl, which is unsubstituted or carries 1, 2, 3, 4 or 5 substituents R 10 , where R 10 is as defined above, in particular having one of the preferred meanings given above. In particular, when present in formulae (Ia), (Ib) and (Ic), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently selected from phenyl, 4-methylphenyl, 4-ethylphenyl, 4-n-propylphenyl, 4-isopropylphenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-propylphenyl, 4-butylphenyl, 4-trifluoromethylphenyl, 4-fluorophenyl, 4-cyanophenyl, 4-trimethylsilylphenyl, 4-phenylphenyl, 2,4-dimethylphenyl, 3,4-dimethylphenyl, 2,4-dimethoxyphenyl, 3,4-dimethoxyphenyl, 4-(3-pyridyl)phenyl, 4-(2-thienyl)phenyl, 4-(2-furyl)phenyl, 4- The compounds of formula (Ia), (Ib) and (Ic) are red-emitting fluorescent dyes.

[0140] According to another preferred embodiment, in formula (Ib), R 1 and R 6 Is selected from C1-C 10Alkyl, preferably C1-C4 alkyl. 3 and R 4 is selected from phenyl-C2-C6 alkenyl, preferably phenyl-CH=CH-, wherein the phenyl moiety in the last group is unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents R 12 These compounds are red-emitting dyes. Preferably, R 3 and R 4 Each is independently selected from 4-(2,6-diisopropylphenoxy)phenyl, 4-(4-tert-butylphenoxy)phenyl, 4-(2,4-di(tert-butyl)phenoxy)phenyl or 4-(2,6-di(tert-butyl)phenoxy)phenyl. Preferably, R 3 and R 4 have the same meaning, and R 1 and R 6 Have the same meaning.

[0141] Preferably, R in formula (Ia) 7a , in formula (Ib) R 7b and R in formula (Ic) 7c is hydrogen, CF3, cyano, C1-C4 alkyl, pyridyl, dibenzofuranyl, C6-C 14 Aryl, of which C6-C 14 The aryl group is unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents R 11 Substitution, where R 11 More preferably, in formula (Ia), R 7a , in formula (Ib) R 7b and R in formula (Ic) 7c is hydrogen, cyano, CF3, C1-C4 alkyl, pyridyl, dibenzofuranyl or phenyl, wherein phenyl is unsubstituted or substituted by 1, 2 or 3 substituents R 11 More preferably, in formula (Ia), R 7a , in formula (Ib) R 7b and R in formula (Ic) 7c is phenyl, which is substituted by 4 or 5 groups R 11 Replace. Each R 11 Preferably selected from EWG1, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, tri-(C1-C 10 Alkyl) silyl, N(C1-C 10 Alkyl)2, N(C6-C 10 aryl)2, heteroaryl, phenyl, biphenyl, terphenyl, spirofluorenyl, naphthyl, C6-C 10 Aryl-C1-C 10Alkylene, C6-C 10 Aryl-C1-C 10 Alkylene-O-, wherein the last 7 groups are unsubstituted in the aryl moiety or are substituted in the aryl moiety by one or more substituents R 12 Substitution, where R 12 is as defined above. 11 In the embodiment, EWG1 is preferably C1-C4 fluoroalkyl, COR 13 , C(O)NR 15 R 16 or SO2NR 15 R 16 In addition, each R 11 It can also be selected from fluorine, chlorine, cyano, C5-C 10 Alkyl or C5-C 10 In this regard, each R 12 Preferably, each R is selected from CN, CF3, C(O)(C1-C4 alkyl), C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy or tri-(C1-C4 alkyl)silyl. 11 Each is independently selected from fluorine, chlorine, cyano, C1-C4 alkyl, C1-C4 fluoroalkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, benzyloxy, COO(C1-C4 alkyl), pyridine, phenyl-C1-C 10 Alkylene, phenyl, biphenyl, terphenyl, 9,9-dimethylfluorenyl, wherein the aromatic structure of the last 5 groups is unsubstituted or substituted by 1, 2 or 3 groups R selected from CN, C1-C4 alkyl, C(O)C1-C4 alkyl or COO(C1-C4 alkyl) 12 replace.

[0142] In particular, R in formula (Ia) 7a , in formula (Ib) R 7b and R in formula (Ic) 7c is hydrogen, C1-C4 alkyl, especially C1-C2 alkyl, or phenyl, said phenyl being unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of 11 Substituted: fluorine, chlorine, cyano, C1-C4 alkyl, C1-C4 fluoroalkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, benzyloxy, C(O)C1-C4 alkyl, COO(C1-C4 alkyl), pyridine, phenyl, biphenyl, terphenyl, or 9,9-dimethylfluorenyl, wherein the aromatic moieties of the last four groups are unsubstituted or substituted by 1, 2 or 3 groups R selected from CN, C1-C4 alkyl, C(O)C1-C4 alkyl or COO(C1-C4 alkyl) 12 In particular, R11 R is selected from fluorine, chlorine or C1-C4 alkyl. 7b It may also be hydrogen.

[0143] In addition, regardless of the situation in which it occurs, the symbol R 9 In particular, cyano, fluorine, C1-C4-alkyl, C1-C4-fluoroalkyl, C1-C4-alkoxy or C1-C4-fluoroalkoxy.

[0144] In a particular embodiment, the compound of formula (Ia) is a green-emitting compound wherein:

[0145] R 1 , R 2 , R 5 and R 6 independently selected from C1-C4 alkyl or phenyl-C1-C4 alkyl, wherein the phenyl moiety in the phenyl-C1-C4 alkyl is unsubstituted or substituted by 1, 2 or 3 groups R 10 Substitution, where R 10 is as defined above, in particular having one of the above preferred meanings; preferably R 1 , R 2 , R 5 and R 6 Independently selected from C1-C4 alkyl;

[0146] EGW1 and EWG2 are identical and are selected from cyano, CF3, CH(O), C(O)(C1-C4 alkyl), C(O)O-C1-C4 alkyl or CH(COOC1-C4 alkyl)2; preferably cyano; and

[0147] R 7a is hydrogen, cyano, CF3, C1-C4 alkyl, or phenyl, wherein the phenyl group is unsubstituted or substituted by 1, 2 or 3 substituents R 11 Substitution, where R 11 is as defined above, in particular having one of the preferred meanings given above. Also preferably, R 7a It is 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0148] In another embodiment, the compound of formula (Ia) is a red-emitting compound wherein:

[0149] R 1 , R 2 , R 5 and R 6 independently selected from phenyl, which is unsubstituted or substituted by 1, 2 or 3 substituents R 10 Substitution, where R 10 is as defined above, in particular having one of the above preferred meanings;

[0150] EGW1 and EWG2 are identical and are selected from cyano, CF3, CH(O), C(O)(C1-C4 alkyl), C(O)O-C1-C4 alkyl and CH(COOC1-C4 alkyl)2; preferably cyano; and

[0151] R 7a is hydrogen, cyano, CF3, C1-C4 alkyl, or phenyl, wherein the phenyl group is unsubstituted or substituted by 1, 2 or 3 substituents R 11 Substitution, where R 11 is as defined above, in particular having one of the preferred meanings given above. Also preferably, R 7a It is 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0152] In another embodiment, the compound of formula (Ib) is a green-emitting compound wherein:

[0153] R 1 , R 3 , R 4 and R 6 independently selected from C1-C4 alkyl or phenyl-C1-C4 alkyl, wherein the phenyl moiety in the phenyl-C1-C4 alkyl is unsubstituted or substituted by 1, 2 or 3 groups R 10 Substitution, where R 10 is as defined above, in particular having one of the above preferred meanings; preferably R 1 , R 3 , R 4 and R 6 Independently selected from C1-C4 alkyl;

[0154] EGW1 and EWG2 are identical and are selected from cyano, CF3, CH(O), C(O)(C1-C4 alkyl), C(O)O-C1-C4 alkyl and CH(COOC1-C4 alkyl)2; preferably cyano; and

[0155] R 7b is hydrogen, cyano, CF3, C1-C4 alkyl, or phenyl, wherein the phenyl group is unsubstituted or substituted by 1, 2 or 3 substituents R 11 Substitution, where R 11 is as defined above, in particular having one of the preferred meanings given above. In particular, each R 11 Independently selected from EWG1, fluorine, chlorine, C1-C 10 Alkyl, C1-C 10 Alkoxy, phenyl, biphenyl, terphenyl or phenyl-C1C 10 More particularly, each R 11is independently selected from fluorine, chlorine, cyano, C1-C4 alkyl, C1-C4 fluoroalkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, phenyl-C1-C4 alkylene, phenyl, biphenyl or terphenyl. Also preferably, R 7b It is 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0156] In another embodiment, the compound of formula (Ib) is a red-emitting compound wherein:

[0157] R 1 , R 3 , R 4 and R 6 independently selected from phenyl, which is unsubstituted or substituted by 1, 2 or 3 substituents R 10 Substitution, where R 10 is as defined above, in particular having one of the above preferred meanings;

[0158] EGW1 and EWG2 are identical and are selected from cyano, CF3, CH(O), C(O)(C1-C4 alkyl), C(O)O-C1-C4 alkyl and CH(COOC1-C4 alkyl)2, preferably cyano; and

[0159] R 7b is hydrogen, cyano, CF3, C1-C4 alkyl, or phenyl, wherein the phenyl group is unsubstituted or substituted by 1, 2 or 3 substituents R 11 Substitution, where R 11 is as defined above, in particular having one of the preferred meanings given above. In particular, each R 11 Independently selected from EWG1, fluorine, chlorine, C1-C 10 Alkyl, C1-C 10 Alkoxy, phenyl, biphenyl, terphenyl or phenyl-C1C 10 More particularly, each R 11 is independently selected from fluorine, chlorine, cyano, C1-C4 alkyl, C1-C4 fluoroalkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, phenyl-C1-C4 alkylene, phenyl, biphenyl or terphenyl. More particularly, each R 11 is independently selected from fluorine, chlorine, cyano, C1-C4 alkyl, C1-C4 fluoroalkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, phenyl-C1-C4 alkylene, phenyl, biphenyl or terphenyl. Also preferably, R 7b It is 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0160] In another embodiment, the compound of formula (Ib) is a red-emitting compound wherein:

[0161] R 1 and R 6 Independently selected from C1-C4 alkyl;

[0162] R 3 and R 4 independently selected from phenyl-C2-C6 alkenyl, wherein the phenyl moiety in the phenyl-C2-C6 alkenyl is unsubstituted or substituted with 1, 2 or 3 substituents R 10 Substitution, where R 10 is as defined above, in particular having one of the above preferred meanings;

[0163] EGW1 and EWG2 are identical and are selected from cyano, CF3, CH(O), C(O)(C1-C4 alkyl), C(O)O-C1-C4 alkyl and CH(COOC1-C4 alkyl)2, preferably cyano; and

[0164] R 7b is hydrogen, cyano, CF3, C1-C4 alkyl, or phenyl, wherein the phenyl group is unsubstituted or substituted by 1, 2 or 3 substituents R 11 Substitution, where R 11 is as defined above, in particular having one of the preferred meanings given above. In particular, each R 11 Independently selected from EWG1, fluorine, chlorine, C1-C 10 Alkyl, C1-C 10 Alkoxy, phenyl, biphenyl, terphenyl or phenyl-C1-C 10 More particularly, each R 11 is independently selected from fluorine, chlorine, cyano, C1-C4 alkyl, C1-C4 fluoroalkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, phenyl-C1-C4 alkylene, phenyl, biphenyl or terphenyl. More particularly, each R 11 is independently selected from fluorine, chlorine, cyano, C1-C4 alkyl, C1-C4 fluoroalkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, phenyl-C1-C4 alkylene, phenyl, biphenyl or terphenyl. Also preferably, R 7b It is 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0165] In another embodiment, the compound of formula (Ic) is a green-emitting compound wherein:

[0166] R 2 , R 3 , R 4 and R 5independently selected from C1-C4 alkyl or phenyl-C1-C4 alkyl, wherein the phenyl moiety in the phenyl-C1-C4 alkyl is unsubstituted or substituted by 1, 2 or 3 groups R 10 Substitution, where R 10 is as defined above, in particular having one of the preferred meanings above; preferably, R 2 , R 3 , R 4 and R 5 Independently selected from C1-C4 alkyl;

[0167] EGW1 and EWG2 are identical and are selected from cyano, CF3, CH(O), C(O)(C1-C4 alkyl), C(O)O-C1-C4 alkyl and CH(COOC1-C4 alkyl)2, preferably cyano; and

[0168] R 7c is hydrogen, cyano, CF3, C1-C4 alkyl, or phenyl, wherein the phenyl group is unsubstituted or substituted by 1, 2 or 3 substituents R 11 Substitution, where R 11 is as defined above, in particular having one of the preferred meanings given above. Also preferably, R 7c It is 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0169] In another embodiment, the compound of formula (Ic) is a red-emitting compound wherein:

[0170] R 2 , R 3 , R 4 and R 5 independently selected from phenyl, which is unsubstituted, partially or fully fluorinated and / or carries 1, 2 or 3 substituents R 10 , where R 10 is as defined above, in particular having one of the above preferred meanings;

[0171] EGW1 and EWG2 are identical and are selected from cyano, CF3, CH(O), C(O)(C1-C4 alkyl), C(O)O-C1-C4 alkyl and CH(COOC1-C4 alkyl)2, preferably cyano; and

[0172] R 7c is hydrogen, cyano, CF3, C1-C4 alkyl, or phenyl, wherein the phenyl group is unsubstituted or substituted by 1, 2 or 3 substituents R 11 Substitution, where R 11 is as defined above, in particular having one of the preferred meanings given above. Also preferably, R 7cIt is 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0173] Preferred examples of green-emitting compounds of formula (Ia), (Ib) and (Ic) are the compounds listed in the following Tables 1 to 21. In addition, the definitions of the symbols in the following tables themselves, independently of the combinations mentioned, are particularly preferred embodiments of the substituents.

[0174] Table 1: Compounds of formula (Ia), wherein EWG1 is cyano, EWG2 is cyano, and R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table A.

[0175] Table 2: Compounds of formula (Ia), wherein EWG1 is CF3, EWG2 is CF3, and R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table A.

[0176] Table 3: Compounds of formula (Ia), wherein EWG1 is CH(O), EWG2 is CH(O), and R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table A.

[0177] Table 4: Compounds of formula (Ia), wherein EWG1 is C(O)CH3, EWG2 is C(O)CH3, and R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table A.

[0178] Table 5: Compounds of formula (Ia), wherein EWG1 is C(O)C2H5, EWG2 is C(O)C2H5, and R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table A.

[0179] Table 6: Compounds of formula (Ia), wherein EWG1 is COOCH3, EWG2 is COOCH3, and R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table A.

[0180] Table 7: Compounds of formula (Ia), wherein EWG1 is COOC2H5, EWG2 is COOC2H5, and R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table A.

[0181] Table 8: Compounds of formula (Ib), wherein EWG1 is cyano, EWG2 is cyano, and R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in table B.

[0182] Table 9: Compounds of formula (Ib), wherein EWG1 is CF3, EWG2 is CF3, and R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in table B.

[0183] Table 10: Compounds of formula (Ib), wherein EWG1 is CH(O), EWG2 is CH(O), and R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in table B.

[0184] Table 11: Compounds of formula (Ib), wherein EWG1 is C(O)CH3, EWG2 is C(O)CH3, and R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in table B.

[0185] Table 12: Compounds of formula (Ib), wherein EWG1 is C(O)C2H5, EWG2 is C(O)C2H5, and R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in table B.

[0186] Table 13: Compounds of formula (Ib), wherein EWG1 is COOCH3, EWG2 is COOCH3, and R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in table B.

[0187] Table 14: Compounds of formula (Ib), wherein EWG1 is COOC2H5, EWG2 is COOC2H5, and R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in table B.

[0188] Table 15: Compounds of formula (Ic), wherein EWG1 is cyano, EWG2 is cyano, and R 1 , R 2 , R 5 and R 6 The combination of corresponds in each case to a row in table C.

[0189] Table 16: Compounds of formula (Ic), wherein EWG1 is CF3, EWG2 is CF3, and R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table C.

[0190] Table 17: Compounds of formula (Ic) wherein EWG1 is CH(O), EWG2 is CH(O), and R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table C.

[0191] Table 18: Compounds of formula (Ic), wherein EWG1 is C(O)CH3, EWG2 is C(O)CH3, and R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table C.

[0192] Table 19: Compounds of formula (Ic), wherein EWG1 is C(O)C2H5, EWG2 is C(O)C2H5, and R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table C.

[0193] Table 20: Compounds of formula (Ic), wherein EWG1 is COOCH3, EWG2 is COOCH3, and R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table C.

[0194] Table 21: Compounds of formula (Ic), wherein EWG1 is COOC2H5, EWG2 is COOC2H5, and R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table C.

[0195] Table A

[0196]

[0197]

[0198] mes= Base = 2,4,6-(CH3)3C6H2

[0199] 4-CH3-C6H4=4-methylphenyl

[0200] Table B

[0201]

[0202]

[0203] mes= Base = 2,4,6-(CH3)3C6H2

[0204] 4-CH3-C6H4=4-methylphenyl

[0205] Table C

[0206]

[0207]

[0208] mes= Base = 2,4,6-(CH3)3C6H2

[0209] 4-CH3-C6H4=4-methylphenyl

[0210] Preferred examples of red-emitting compounds of formula (Ia), (Ib) and (Ic) are the compounds listed in the following Tables 22 to 42. In addition, the definitions of the symbols in the following tables themselves, independently of the combinations mentioned, are particularly preferred embodiments of the substituents.

[0211] Table 22: Compounds of formula (Ia), wherein EWG1 is cyano, EWG2 is cyano, and R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table D.

[0212] Table 23: Compounds of formula (Ia), wherein EWG1 is CF3, EWG2 is CF3, R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table D.

[0213] Table 24: Compounds of formula (Ia), wherein EWG1 is CH(O), EWG2 is CH(O), R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table D.

[0214] Table 25: Compounds of formula (Ia), wherein EWG1 is C(O)CH3, EWG2 is C(O)CH3, R 1 , R 2 , R 5 , R 6and R 7a The combination of corresponds in each case to a row in table D.

[0215] Table 26: Compounds of formula (Ia), wherein EWG1 is C(O)C2H5, EWG2 is C(O)C2H5, R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table D.

[0216] Table 27: Compounds of formula (Ia), wherein EWG1 is COOCH3, EWG2 is COOCH3, with respect to R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table D.

[0217] Table 28: Compounds of formula (Ia), wherein EWG1 is COOC2H5, EWG2 is COOC2H5, R 1 , R 2 , R 5 , R 6 and R 7a The combination of corresponds in each case to a row in table D.

[0218] Table 29: Compounds of formula (Ib), wherein EWG1 is cyano, EWG2 is cyano, and R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in Table E.

[0219] Table 30: Compounds of formula (Ib), wherein EWG1 is CF3, EWG2 is CF3, R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in Table E.

[0220] Table 31: Compounds of formula (Ib), wherein EWG1 is CH(O), EWG2 is CH(O), with respect to R 1 , R 3 , R 4 , R 6 and R 7bThe combination of corresponds in each case to a row in Table E.

[0221] Table 32: Compounds of formula (Ib), wherein EWG1 is C(O)CH3, EWG2 is C(O)CH3, R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in Table E.

[0222] Table 33: Compounds of formula (Ib), wherein EWG1 is C(O)C2H5, EWG2 is C(O)C2H5, R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in Table E.

[0223] Table 34: Compounds of formula (Ib), wherein EWG1 is COOCH3, EWG2 is COOCH3, R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in Table E.

[0224] Table 35: Compounds of formula (Ib), wherein EWG1 is COOC2H5, EWG2 is COOC2H5, R 1 , R 3 , R 4 , R 6 and R 7b The combination of corresponds in each case to a row in Table E.

[0225] Table 36: Compounds of formula (Ic), wherein EWG1 is cyano, EWG2 is cyano, and R 1 , R 2 , R 5 and R 6 The combination of corresponds in each case to a row in table F.

[0226] Table 37: Compounds of formula (Ic), wherein EWG1 is CF3, EWG2 is CF3, R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table F.

[0227] Table 38: Compounds of formula (Ic), wherein EWG1 is CH(O), EWG2 is CH(O), R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table F.

[0228] Table 39: Compounds of formula (Ic), wherein EWG1 is C(O)CH3, EWG2 is C(O)CH3, R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table F.

[0229] Table 40: Compounds of formula (Ic), wherein EWG1 is C(O)C2H5, EWG2 is C(O)C2H5, R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table F.

[0230] Table 41: Compounds of formula (Ic), wherein EWG1 is COOCH3, EWG2 is COOCH3, R of the compounds 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table F.

[0231] Table 42: Compounds of formula (Ic), wherein EWG1 is COOC2H5, EWG2 is COOC2H5, R 2 , R 3 , R 4 , R 5 and R 7c The combination of corresponds in each case to a row in table F.

[0232] Table D

[0233]

[0234]

[0235]

[0236]

[0237] mes: 2,4,6-trimethylphenyl 2,6-Cl2-C6H3: 2,6-dichlorophenyl

[0238] 4-MeO-C6H4: 4-methoxyphenyl 2,6-F2-C6H3: 2,6-difluorophenyl

[0239] 4-EtO-C6H4: 4-ethoxyphenyl C6F5: 2,3,4,5,6-pentafluorophenyl

[0240] 4-CH3-C6H4: 4-methylphenyl C6Cl5: 2,3,4,5,6-pentachlorophenyl

[0241] 2-Cl-C6H4: 2-chlorophenyl 2-F-C6H4: 2-fluorophenyl

[0242] Table E

[0243]

[0244]

[0245]

[0246]

[0247] mes: 2,4,6-trimethylphenyl 2,6-Cl2-C6H3: 2,6-dichlorophenyl

[0248] 4-MeO-C6H4: 4-methoxyphenyl 2,6-F2-C6H3: 2,6-difluorophenyl

[0249] 4-EtO-C6H4: 4-ethoxyphenyl C6F5: 2,3,4,5,6-pentafluorophenyl

[0250] 4-CH3-C6H4: 4-methylphenyl C6Cl5: 2,3,4,5,6-pentachlorophenyl

[0251] 2-Cl-C6H4: 2-chlorophenyl 2-F-C6H4: 2-fluorophenyl

[0252] 4-CN-PV: 2-(4-cyanophenyl)vinyl DIPP: 4-(2,6-diisopropylphenoxy)phenyl

[0253] Table F

[0254]

[0255]

[0256]

[0257]

[0258]

[0259] mes: 2,4,6-trimethylphenyl 2,6-Cl2-C6H3: 2,6-dichlorophenyl

[0260] 4-MeO-C6H4: 4-methoxyphenyl 2,6-F2-C6H3: 2,6-difluorophenyl

[0261] 4-EtO-C6H4: 4-ethoxyphenyl C6F5: 2,3,4,5,6-pentafluorophenyl

[0262] 4-CH3-C6H4: 4-methylphenyl C6Cl5: 2,3,4,5,6-pentachlorophenyl

[0263] 2-Cl-C6H4: 2-chlorophenyl 2-F-C6H4: 2-fluorophenyl

[0264] Among these compounds, particularly preferred are compounds of formula (Ib), especially the green-emitting compounds listed in Tables 8, 9, 10, 11, 12, 13 and 14. Also particularly preferred are the red-emitting compounds of formula (Ib) listed in Tables 30, 31, 32, 33, 34 and 35.

[0265] According to a specific embodiment of the present invention, at least one organic fluorescent dye is a fluorescent dye of formula (Ib), which is selected from the following compounds (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16) (17), (18), (19), (20), (21), (22), (23), (24), (25), (26), (27), (28), (29), (30), (31), (32), (33), (34), (35), (36), (37), (38), (39) or a mixture thereof.

[0266]

[0267]

[0268] mes: 2,4,6-trimethylphenyl 2,6-Cl2-C6H3: 2,6-dichlorophenyl

[0269] 4-MeO-C6H4: 4-methoxyphenyl 2,6-F2-C6H3: 2,6-difluorophenyl

[0270] C6F5: 2,3,4,5,6-pentafluorophenyl C6Cl5: 2,3,4,5,6-pentachlorophenyl

[0271] 2-Cl-C6H4: 2-chlorophenyl 2-F-C6H4: 2-fluorophenyl

[0272] 4-CN-PV: 4-cyanophenylvinyl DIPPP: 4-(2,6-diisopropylphenoxy)phenyl

[0273] Among them, more preferred is the compound of formula (Ib), wherein R 1 , R 3 , R 4 and R 6 Each is a methyl group, and R 7b is phenyl or base.

[0274] Among them, more preferred is the compound of formula (Ib), wherein R 1 and R 6 Each is phenyl, R 3 and R 4 are each 4-methoxyphenyl, and R 7b yes base.

[0275] Among them, more preferred is the compound of formula (Ib), wherein R 1 and R 6 Each is a methyl group, R 3 and R 4 Each is 2-(4-cyanophenyl)vinyl, and R 7b yes base.

[0276] Another aspect of the present invention is novel compounds of formula (Ib), wherein:

[0277] R 1 and R 6 Each is a phenyl group;

[0278] R 3 and R 4 Each is 4-methoxyphenyl or 4-(2,6-diisopropylphenoxy)phenyl;

[0279] EGW1 and EWG2 are each cyano; and

[0280] R 7b is phenyl, which is unsubstituted or substituted by 1, 2, 3, 4 or 5 groups R selected from11 Substitution: EWG1, Fluorine, Chlorine, C1-C 10 Alkyl, C1-C 10 Alkoxy, phenyl, biphenyl, terphenyl or phenyl-C1-C 10 Alkylene.

[0281] Among them, preferred are those compounds (Ib) wherein:

[0282] R 1 and R 6 Each is a phenyl group;

[0283] R 3 and R 4 Each is 4-methoxyphenyl;

[0284] EGW1 and EWG2 are each cyano; and

[0285] R 7b yes phenyl, 2-chlorophenyl, 2-fluorophenyl, 2,6-dichlorophenyl, 2,6-difluorophenyl, 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0286] Among them, also preferred are those compounds (Ib) wherein:

[0287] R 1 and R 6 Each is a phenyl group;

[0288] R 3 and R 4 each is 4-(2,6-diisopropylphenoxy)phenyl;

[0289] EGW1 and EWG2 are each cyano; and

[0290] R 7b yes phenyl, 2-chlorophenyl, 2-fluorophenyl, 2,6-dichlorophenyl, 2,6-difluorophenyl, 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0291] Another aspect of the present invention is novel compounds of formula (Ib), wherein:

[0292] R 1 , R 3 , R 4 and R 6 each is a methyl group;

[0293] EWG1 and EWG2 are each cyano; and

[0294] R 7b yes phenyl, 2-chlorophenyl, 2-fluorophenyl, 2,6-dichlorophenyl, 2,6-difluorophenyl, 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0295] Another aspect of the present invention is novel compounds of formula (Ib), wherein:

[0296] R 1 and R 6 each is a methyl group;

[0297] R 3 and R 4 Each is 4-cyanophenylvinyl;

[0298] EWG1 and EWG2 are each cyano; and

[0299] R 7b yes phenyl, 2-chlorophenyl, 2-fluorophenyl, 2,6-dichlorophenyl, 2,6-difluorophenyl, 2,3,4,5,6-pentafluorophenyl or 2,3,4,5,6-pentachlorophenyl.

[0300] Some compounds of formula (Ia), (Ib) and (Ic) are well known in the art, for example, see US2018 / 0134952, US 2018 / 0208838 and US 2017 / 0247610. The compounds of the present invention and compounds used according to the present invention that are not described in the prior art can be prepared by methods similar to those described in US 2018 / 0134952, US 2018 / 0208838 and US 2017 / 0247610, or by methods similar to those described below and in the experimental part of this specification.

[0301] For example, compounds of formula (Ia), (Ib) and (Ic) can be prepared as follows: wherein, if not explicitly stated, the symbols in the various reaction schemes are as defined above. In addition, those skilled in the art can easily find reaction conditions suitable for the synthesis shown in the reaction schemes by routine experimentation. Other details can also be found in the preparation examples described herein. All reactions are usually carried out in dry glassware in an inert atmosphere, especially in argon.

[0302] The compound of formula (Ib) wherein EWG1 and EWG2 are each cyano can be prepared according to Reaction Scheme 1.

[0303] Reaction 1:

[0304]

[0305] In reaction scheme 1, LG is a leaving group, such as chlorine, bromine or R'-C(=O)-O, wherein R' is a C1-C6 alkyl group. In step (i) of reaction scheme 1, the activated carbonyl compound of formula (IV) is condensed with the pyrrole of formula (II) and then reacted with the pyrrole of formula (III) to obtain the dipyrromethene compound of formula (V). Without wishing to be bound by any theory, it is believed that the reaction of the activated carbonyl compound of formula (IV) with the pyrrole of formula (II) provides a monoacylated pyrrole, which is then reacted with the pyrrole of formula (III). In the case of pyrrole of formula (II), the separation of this monoacylated pyrrole is different from that of pyrrole of formula (III). In step (ii) of reaction scheme 1, the compound of formula (V) can be complexed with a BF3 source, such as a BF3 etherate. Advantageously, the complexation is carried out in the presence of a base. Suitable bases are especially secondary and tertiary amines, especially tertiary amines, such as tri(C1-C 10 alkyl)amine, in particular triethylamine or diisopropylethylamine.

[0306] The compound of formula (II) can be prepared by a condensation reaction between an α-amino ketone of formula (VI) and an α-cyanoketone of formula (VII), as shown in Reaction Scheme 2.

[0307] Reaction 2:

[0308]

[0309] The compound of formula (III) can be prepared in a similar manner to the compound of formula (II).

[0310] The compound of formula (VI) can be prepared from a 2-oxoaldehyde of formula (VIII) as shown in the following reaction scheme 3. The condensation reaction between the 2-oxoaldehyde of formula (VIII) and hydroxylamine provides a 2-oxoaldehyde oxime of formula (IX). Subsequently, the compound of formula (IX) is reduced to an amine of formula (VI).

[0311] Reaction 3:

[0312]

[0313] The compound of formula (VII) can be prepared by treating an ester of formula (X) with acetonitrile in the presence of a base as shown in the following reaction scheme 4.

[0314] Reaction 4:

[0315]

[0316] In Reaction Formula 4, R' is a C1-C6 alkyl group, preferably a C1-C4 alkyl group.

[0317] The compound of formula (Ic) wherein EWG1 and EWG2 are each cyano can be prepared in a manner similar to the compound of formula (Ib), but starting from a 3-cyanopyrrole compound of formula (XI), a 3-cyanopyrrole compound of formula (XII) and a compound of formula (XIII) as shown in the following reaction scheme 5.

[0318] Reaction 5:

[0319]

[0320] In Reaction Formula 5, LG is chlorine, bromine or R'-C(=O)-O, wherein R' is a C1-C6 alkyl group. The condensation reaction in step (i) of Reaction Formula 5 is carried out in a manner similar to step (i) of Reaction Formula 1. The complexation in step (ii) of Reaction Formula 5 is carried out in a manner similar to step (ii) of Reaction Formula 1.

[0321] The compound of formula (XI) can be prepared as shown in reaction formula 6. In step (i) of reaction formula 6, the oxime of formula (XV) is treated with 1,2-dichloroethane in the presence of a base, such as an alkali metal or alkaline earth metal hydroxide, such as KOH, to obtain a pyrrole compound of formula (XVI). The pyrrole of formula (XVI) is N-protected in step (ii) of reaction formula 6 to obtain an N-protected pyrrole of formula (XVII), which can be carried out according to methods known in the art, such as using a silylating agent, such as tert-butyldimethylsilyl chloride, triisopropylsilyl chloride or tert-butyldiphenylsilyl chloride. A bromination reaction is carried out in step (iii) of reaction formula 6, and then a cyanide source is used to nucleophilically replace the bromine in step (iv), and finally deprotected in step (v) of reaction formula 6 to obtain a pyrrole compound of formula (XI). The bromination reaction in step (iii) of reaction formula 6 can be carried out with bromine or N-bromosuccinimide. The bromination can be carried out in the presence of a base. In step (iv) of reaction formula 6, the cyanide source may be copper (I) cyanide. The protecting group PG may be removed in step (v) of reaction formula 6 by methods known in the art, for example, see T. Greene and P. Wuts, "Protective Groups in Organic Synthesis" (3rd edition), John Wiley & Sons, NY (1999). For example, the silyl protecting group may be removed by a deprotecting agent selected from tetrabutylammonium bromide or tetrabutylammonium fluoride in the presence of a solvent.

[0322] Reaction 6:

[0323]

[0324] In Reaction Formula 6, PG represents a protecting group, preferably a silyl protecting group.

[0325] The compound of formula (XII) can be prepared by a method similar to that shown in reaction scheme 6 for the preparation of the compound of formula (XI).

[0326] Alternatively, the compound of formula (Ib) can also be prepared by post-functionalization of a dihalogenated boron dipyrrole of formula (XVIII) as shown in the following reaction formula 7.

[0327] Reaction 7:

[0328]

[0329] In reaction formula 7, Hal is chlorine or bromine, preferably bromine. The cyanation reaction of the compound of formula (XVIII) with the cyanide anion is carried out in the presence of a transition metal catalyst. A suitable cyanide source is zinc cyanide. Suitable transition metal catalysts are particularly palladium catalysts, such as tetrakis(triphenylphosphine)palladium(0); bis[di-(1,2-diphenylphosphino)ethane]palladium(0); bis(dibenzylideneacetone)palladium(0); tris(dibenzylideneacetone)dipalladium(0); bis(triphenylphosphine)palladium(II) chloride; bis(acetonitrile)palladium(II) chloride; [1,1'-bis(diphenylphosphino)ferrocene]-palladium(II) chloride / dichloromethane (1:1) complex; bis(di-(1,2-diphenylphosphino)butane]-palladium(II) chloride; ethyl palladium(II) acetate; palladium(II) chloride; and palladium(II) acetate / tri-o-tolylphosphine complexes, or mixtures of phosphine and Pd salts, or mixtures of phosphine and Pd-complexes, such as dibenzylideneacetone-palladium and tri-tert-butylphosphine (or its tetrafluoroborate); tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphine; palladium acetate and 1,2-bis(diphenylphosphino)ethane in the presence of tetramethylethylenediamine; or Pd-triphenylphosphine catalyst systems bound to polymers, such as tetrakis(triphenylphosphine)palladium on polystyrene.

[0330] The reaction shown is usually carried out in a solvent. Suitable solvents are, for example, polar aprotic solvents such as acetonitrile, nitrogen-containing heterocycles, N,N-disubstituted aliphatic carbonamides (preferably N,N-di(C1-C4 alkyl)(C1-C4)carbonamides), and N-alkyllactams such as dimethylformamide, diethylformamide, dimethylacetamide, dimethylbutyramide and N-methylpyrrolidone (NMP); non-polar solvents such as ethers such as tetrahydrofuran or 1,4-dihydrofuran; Alkanes, or aromatic solvents such as benzene, toluene or xylene.

[0331] The compound of formula (XVIII) wherein each Hal is bromine or each Hal is chlorine can be prepared as shown in the following reaction scheme 8. The bromination of the compound of formula (XIX) can be carried out in a manner similar to step (iii) of reaction scheme 6. The compound of formula (XVIII) wherein each Hal is chlorine can be prepared by treating the compound of formula (XIX) with N-chlorosuccinimide.

[0332] Reaction 8:

[0333]

[0334] The compound of formula (Ia) can be prepared by post-functionalizing a dihalogenated boron dipyrrole of formula (XX) with a cyanating agent such as trimethylsilyl cyanide in the presence of a Lewis acid such as tin tetrachloride as shown in the following reaction formula 9. The cyanation reaction can be carried out in a manner similar to that described in Biorg. Med. Chem. Lett. 18 (2008), 3112-3116.

[0335] Reaction 9:

[0336]

[0337] The compound of formula (XX) can be prepared as shown in the following reaction formula 10. In step (i) of reaction formula 10, the hemiacetal of formula (XXI) reacts with the pyrrole compounds of formula (XXII) and (XXIII) under acidic conditions to obtain a dipyrromethene compound of formula (XXIV). In step (ii) of reaction formula 10, the dipyrromethene of formula (XXIV) is treated with a chlorinating agent such as N-chlorosuccinimide in tetrahydrofuran to obtain dichloropyrromethene, which is then treated with an oxidizing agent such as 5,6-dicyano-1,4-benzoquinone in step (iii) of reaction formula 10 to obtain a dichloropyrromethene compound of formula (XXV). The complexation in step (iv) of reaction formula 10 is carried out in a manner similar to step (ii) of reaction formula 1.

[0338] Reaction 10:

[0339]

[0340] The compounds of formula (Ia), (Ib) and (Ic) wherein the aromatic or heteroaromatic group is connected at the meso position can also be prepared by the acid-catalyzed condensation reaction of a (hetero)aromatic aldehyde with the pyrrole compound to obtain a dipyrromethene compound, as shown in reaction formula 11, wherein the compound of formula (Ib) is used as an example. The dipyrromethene compound is then oxidized, for example using 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) or p-chloranil to obtain a dipyrromethene compound. The complexation is carried out in a manner similar to step (ii) of reaction formula 1. Those skilled in the art will appreciate that the compound of formula (Ic) can be prepared in a similar manner, wherein the substituent in the meso position is an optionally substituted aromatic or heteroaromatic group.

[0341] Reaction 11:

[0342]

[0343] Asymmetric compounds of formula (Ia), (Ib) and (Ic) having an aryl or heteroaryl group in the meso position and EWG1 and EWG2 being cyano groups, can be prepared respectively by condensing the acylated pyrrole with the second pyrrole to give a dipyrromethene compound, which is then subjected to the action of a base and boron trifluoride etherate to give the title compound.

[0344] Alkenyl-substituted BODIPY dyes can be prepared by Pd-catalyzed CC coupling of the corresponding chloro-substituted BODIPYs following the Suzuki, Heck or Sanogashira reactions.

[0345] Styryl-substituted BODIPY dyes can be prepared by a one-step Knoevenagel condensation reaction of a methyl-substituted BODIPY of formula (Ia), (Ib) or (Ic) with an optionally substituted benzaldehyde in the presence of a base, the base being particularly an organic nitrogen base such as piperidine. Typically, the reaction is carried out in the presence of an acid. Suitable acids are acetic acid or p-toluenesulfonic acid. The reaction can advantageously be carried out under microwave irradiation. Molecular sieves can also advantageously be added to remove the resulting reaction water. Compounds of formula (Ia), (Ib) and (Ic) in which EWG1 and EWG2 are each formyl (-CH(O)) can be prepared by Vilsmeier formylation reaction, respectively. Functionalization of BODIPY dyes via formyl groups can be carried out in a manner similar to that described in the literature, for example, see Dyes and Pigments 136 (2017) 852-858; RSC Adv., 2013, 3, 4793-4800. This method is shown in the following reaction formula 12 for the compound of formula (Ib).

[0346] Reaction 12:

[0347]

[0348] Where EWG1 and EWG2 are each C(O)R 13 The compound of formula (Ib) can be prepared from pyrrole, wherein the initial pyrrole carries C(O)R 13 The pyrrole compound can be obtained by Knorr-pyrrole synthesis in a manner similar to that described in Journal of Organic Chemistry, 2008, 73, 2146-2154.

[0349] Where EWG1 and EWG2 are each C(O)OR 14 Compounds of formula (Ib) can be prepared by a method similar to that shown in reaction scheme 1, but using 1H-pyrrole-3-carboxylate (XXV) instead of cyano-substituted pyrroles (II) and (III). Esters can be obtained by condensation reaction between α-aminoketones and esters in the manner of Knorr-pyrrole synthesis.

[0350]

[0351] Some compounds (XXV) are commercially available, for example ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate.

[0352] The color converter of the present invention preferably comprises at least one compound of the formula (Ia), (Ib), (Ic) or a mixture thereof, which emits green light in the wavelength range of 500-560 nm by using excitation light. Such excitation light usually has a central emission wavelength in the wavelength range of 420-480 nm.

[0353] Also preferably, the color converter according to the invention comprises at least one compound of the formula (Ia), (Ib), (Ic) or a mixture thereof, which emits red light in the wavelength range of 595-700 nm, preferably 610-660 nm, by using excitation light. Such excitation light generally has a central emission wavelength in the wavelength range of 420-600 nm.

[0354] The excitation light may be generated by a blue LED, including mini-LEDs and micro-LEDs, and / or by any luminescent material contained in the color converter. The luminescent material emits light in a wavelength range in which at least one compound of formula (Ia), (Ib) and (Ic) can absorb light. The luminescent material may be an organic fluorescent dye, such as a photosensitizer, which absorbs energy in the form of electromagnetic radiation and transfers the energy to the compound of formula (Ia), (Ib) and (Ic) via a resonance energy transfer mechanism; for example via Alternatively, the organic fluorescent dye may be any compound whose emitted photons can be reabsorbed by the compounds of formula (Ia), (Ib) and (Ic). Representative examples of organic fluorescent dyes include coumarin derivatives, cyanine derivatives, fluorescein derivatives, phthalocyanine derivatives, benzyl derivatives, pyrromethene derivatives including compounds of formula (Ia), (Ib) and (Ic), stilbene derivatives, Oxazine derivatives, naphthalimide derivatives, pyrazine derivatives, benzimidazole derivatives, benzo Azole derivatives, benzothiazole derivatives, imidazopyridine derivatives and oxazole derivatives.

[0355] More preferably, the color converter comprises: a first compound of formula (Ia), (Ib), (Ic) or a mixture thereof, which can emit light having a central emission wavelength in the range of 500-560 nm by using an excitation light having a wavelength of 420-480 nm; and a second compound of formula (Ia), (Ib), (Ic) or a mixture thereof, which can emit light having a central emission wavelength in the range of 595-700 nm, preferably 610-660 nm, by using an excitation light having a wavelength of 420 to more than 600 nm. The first compound of formula (Ia), (Ib) and (Ic) generally has an emission spectrum in the range of 500-560 nm, and a FWHM of 60 nm or less. The first compound of formula (Ia), (Ib) or (Ic) preferably has an emission spectrum in the range of 500-560 nm, and a FWHM of 45 nm or less. More preferably, the first compound of formula (Ia), (Ib) or (Ic) preferably has an emission spectrum in the wavelength range of 520-540 nm, and a FWHM of 45 nm or less. The second compound of formula (Ia), (Ib) or (Ic) preferably has an emission spectrum in the wavelength range of 610-660 nm, and a FWHM of 90 nm or less, preferably 70 nm or less, in particular 60 nm or less. More preferably, the second compound of formula (Ia), (Ib) or (Ic) preferably has an emission spectrum in the wavelength range of 610-640 nm, and a FWHM of 60 nm or less.

[0356] According to another embodiment of the invention, the color converter further comprises at least one light scattering agent. By using scattering agents, higher luminosity can be achieved. Suitable light scattering agents are inorganic white pigments, such as titanium dioxide, barium sulfate, lithopone, zinc oxide, zinc sulfide, calcium carbonate, which have an average particle size according to DIN 13320 of 0.01-10 μm, preferably 0.1-1 μm, more preferably 0.15-0.4 μm. The content of these light scattering agents is usually 0.01-5.0% by weight, preferably 0.05-0.5% by weight, more preferably 0.1-0.4% by weight, based on the total polymer content of the polyethylene terephthalate matrix material containing the scatterers.

[0357] Examples of suitable organic light scatterers include those based on: polyacrylates; polyalkyl methacrylates, such as polymethyl methacrylate (PMMA); polytetrafluoroethylene (PTFE); siloxane-based scatterers, such as hydrolyzed poly(alkyltrialkoxysilanes), and mixtures thereof. The size (average diameter - weight average) of these light scatterers is generally in the range of 0.5-50 μm, preferably 1-10 μm. The content of these light scatterers is generally 1-10% by weight, in each case based on the polymer of the layer containing the scatterer. Useful light scatterers are, for example, mixtures of 3-5% by weight of PMMA-based scatterers and 1.5-2% by weight of siloxane-based scatterers.

[0358] Also suitable are light-scattering compositions which contain polymer particles based on vinyl acrylate having a core / shell morphology and also TiO2, see EP-A 634 445.

[0359] According to another embodiment of the present invention, the color converter according to the above embodiments may further comprise one or more inorganic components for fine tuning the optical properties (eg refractive index) of the film, such as micron-sized silica.

[0360] According to another embodiment of the present invention, the color converter according to the above embodiment may further contain other additives, such as flame retardants, antioxidants, light stabilizers, free radical scavengers, singlet oxygen quenchers, antistatic agents. Such stabilizers are well known to those skilled in the art.

[0361] Antioxidants are agents which inhibit oxidation and which are used to prevent degradation of components sensitive to oxidation. Suitable antioxidants or free radical scavengers are, for example, phenols, in particular sterically hindered phenols, such as butylated hydroxyanisole (BHA) or butylated hydroxytoluene (BHT), or sterically hindered amines (HALS). Such stabilizers are available, for example, from BASF under the trade name In some cases, the antioxidants and free radical scavengers may be supplemented by auxiliary stabilizers, such as phosphites or phosphonites, such as those sold by BASF under the trade name Sale.

[0362] In a preferred embodiment of the present invention, the color converter does not contain any antioxidants or free radical scavengers. In another preferred embodiment of the present invention, the color converter does not contain any tertiary amines, catechol derivatives and nickel compounds.

[0363] According to a preferred embodiment, the color converter of the invention does not contain any added solvents.

[0364] The color converter according to the invention comprises or consists of one or more layers which contain a polyethylene terephthalate matrix material and at least one organic fluorescent dye according to the invention.

[0365] Advantageously, the compounds of formula (Ia), (Ib), (Ic) are heat-stable. Therefore, the compounds of formula (Ia), (Ib), (Ic) or mixtures thereof can be introduced into the polyethylene terephthalate matrix material via extrusion, for example in an extrusion line. The extrusion line generally comprises an extruder as a plasticizing device, a sheet die as a forming tool, optionally a polishing assembly / calender as a calibration die, optionally a cooling bed and / or a roller conveyor for post-cooling, optionally a take-up roller and a separating saw. The extrusion line can be a single-layer extrusion line or a multi-layer co-extrusion line. The extruder can be a single screw, a twin screw, a multi-screw extruder or a planetary roller extruder. Alternatively, extrusion force (plunger extrusion) can be applied by a piston or a plunger. Advantageously, extrusion is carried out in the absence of any added solvent.

[0366] The polyethylene terephthalate matrix material is preferably dried at a temperature of 130-180°C for 4-10 hours prior to extrusion.

[0367] According to the present invention, the polyethylene matrix material as defined above, at least one organic fluorescent dye of the present invention, the light scattering agent if present and other additives if present can be combined or metered into the forcing machine separately. It is also possible to meter formula (Ia), (Ib), (Ic) compound or its mixture into via masterbatch technology. The light scattering agent can also be added via masterbatch technology, wherein the light scattering agent is fully dispersed in the solid carrier material. Suitable carrier material is a thermoplastic material, for example polyethylene terephthalate, or other polymers that can be fully compatible with the polyethylene terephthalate matrix material.

[0368] The polyethylene terephthalate matrix material melts or softens in the extruder, i.e. the feed is plasticized. It may be advantageous if the extruder has a plurality of heating zones which can be individually temperature-controlled. The temperature of the melt is preferably in the range of 250-280° C. and can be adjusted substantially by the temperature of the extruder, the length of the heating zones, the residence time of the melt in the extruder, the extruder torque and / or the screw rotation speed.

[0369] The concentration of the at least one compound of the formula (Ia), (Ib), (Ic) or a mixture thereof in the color converter according to the invention depends on various factors, including the absorption intensity of the compounds of the formula (Ia), (Ib) and (Ic) at the excitation wavelength, and the thickness of the layer formed. If the layer is thin, the concentration of the at least one compound of the formula (Ia), (Ib), (Ic) or a mixture thereof is generally higher than in the case of thick layers.

[0370] In the color converters of the invention, the total concentration of the compounds of the formulae (Ia), (Ib) and (Ic) is generally in the range of 0.0005 to 8% by weight, preferably 0.001 to 5% by weight, more preferably 0.001 to 1% by weight, based on the total polymer weight of the polyethylene terephthalate matrix material.

[0371] Preferably, in applications for displays, the color converter comprises a green-emitting compound of the formula (Ia), (Ib), (Ic) or a mixture thereof and a red-emitting compound of the formula (Ia), (Ib), (Ic) or a mixture thereof, wherein the weight ratio between all green-emitting compounds and all red-emitting compounds is from 5:1 to 50:1.

[0372] In particular, in applications for displays, the concentration of the green-emitting compounds of the formula (Ia), (Ib), (Ic) and mixtures thereof in the color converter is generally 0.005-5% by weight, preferably 0.01-4% by weight, more preferably 0.01-1% by weight, most preferably 0.01-0.5% by weight, based on the total polymer weight of the polyethylene terephthalate matrix material. In particular, in applications for displays, the concentration of the red-emitting compounds of the formula (Ia), (Ib), (Ic) and mixtures thereof in the color converter is generally 0.001-2% by weight, preferably 0.001-1% by weight, more preferably 0.002-0.8% by weight, most preferably 0.002-0.5% by weight, based on the total polymer weight of the polyethylene terephthalate matrix material.

[0373] In particular, in applications for conventional lighting, the concentration of the red-emitting compounds of formula (Ia), (Ib), (Ic) and mixtures thereof in the color converter is in the range of 0.0001-0.5% by weight, preferably 0.001-0.1% by weight, based on the total polymer weight of the polyethylene terephthalate matrix material. In particular, in applications for conventional lighting, the concentration of the green-emitting compounds of formula (Ia), (Ib), (Ic) and mixtures thereof in the color converter is usually in the range of 0.001-0.8% by weight, preferably 0.002-0.6% by weight, more preferably 0.003-0.5% by weight, based on the total polymer weight of the polyethylene terephthalate matrix material.

[0374] In a specific embodiment, the color converter has a multilayer structure. In this embodiment, one or more of the layers, but not all layers, or all layers, contain a scatterer, preferably TiO2. Thus, in one embodiment of the invention, the green-emitting compound of the formula (Ia), (Ib), (Ic) or a mixture thereof and the red-emitting compound of the formula (Ia), (Ib), (Ic) or a mixture thereof are present in different layers. In another preferred embodiment, the green-emitting compound of the formula (Ia), (Ib), (Ic) or a mixture thereof and the red-emitting compound of the formula (Ia), (Ib), (Ic) or a mixture thereof are present in the same layer.

[0375] In one embodiment of the present invention, especially when used for display applications, the thickness of each layer is generally 2-1000 micrometers (μm), preferably 5-500 μm, more preferably 10-350 μm. In another embodiment, especially when used for conventional lighting applications, the thickness of each layer containing the fluorescent dye of the present invention is 2 micrometers to 5 millimeters.

[0376] When the color converter consists of one layer or has a layer structure, the layer comprising at least one fluorescent dye according to the invention is preferably continuous, so that the light emitted by the LED must in any case pass through the polyethylene terephthalate matrix comprising at least one compound of the formula (Ia), (Ib), (Ic) or a mixture thereof.

[0377] The color converter may include at least one substrate layer and / or at least one barrier film layer to prevent the color converter from deteriorating. The color converter of the present invention may include at least one barrier layer against oxygen and / or water to prevent the organic fluorescent dye used according to the present invention from deteriorating, see WO 2012 / 152812. Barrier film layers may be provided on both sides of the color converter, or the color converter may be surrounded by at least one barrier layer on all sides. A suitable barrier layer may itself have a multilayer structure. The multilayer structure may be a two-layer structure, a three-layer structure, a four-layer structure, a five-layer structure, or a structure of more than five layers. Suitable materials for the barrier layer are, for example, polyvinyl alcohol, polyacrylonitrile, polyvinylidene chloride (PVDC), liquid crystal polymer (LCP), polystyrene-acrylonitrile (SAN), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyamide, polyoxymethylene, polyimide, polyetherimide, epoxy resin, polymers derived from ethylene-vinyl acetate (EVA), and polymers derived from ethylene-vinyl alcohol (EVOH). An additional adhesive or bonding layer may be provided for adhering the barrier layer to the layer comprising at least one fluorescent dye according to the invention. The barrier layer may also be laminated to the colored layer comprising at least one fluorescent dye according to the invention. In general, the barrier layer has the geometry of the layer with which it is in contact. However, this is not absolutely necessary, as long as it ensures that the barrier layer prevents oxygen from penetrating into the layer comprising at least one fluorescent dye according to the invention. In general, the barrier layer has a thickness of 0.01 μm to 5 mm, preferably 0.1-1000 μm, more preferably 1-100 μm. The glass barrier layer preferably has a thickness of 0.01-5000 μm, more preferably 0.1-1000 μm. These layers can be combined with other layers during extrusion and / or finishing to form a laminate or multilayer sheet.

[0378] In one embodiment of the present invention, the inventive color converter does not comprise any barrier layer.In another embodiment of the present invention, the inventive color converter comprises at least one barrier layer.

[0379] The color converter of the invention for use in lighting devices and backlight units is used in a remote phosphor arrangement. In this case, the color converter is spatially separated from the LED. Different media can be present between the color converter and the LED, such as air, rare gases, nitrogen or other gases, or mixtures thereof.

[0380] When the color converter consists of one layer or has a layer structure, the layer containing at least one organic fluorescent dye of the present invention is generally a self-supporting film, but can also be applied to a substrate layer. In the present invention, a self-supporting film is a film, a portion of which is not in contact with a carrier material such as a substrate. The carrier layer generally imparts mechanical properties to the color converter. The material type of the carrier layer is generally not critical, provided that it is transparent and has the required mechanical strength. Representative substrate layers are plastic films, such as cellulose acetate, polyethylene terephthalate, polyolefins such as polyethylene and polypropylene, polymethyl acrylate, polymethyl methacrylate, aliphatic polyesters, polyamides, aromatic polyamides, polyimides, polyphenylene sulfide, polystyrene, polycarbonate and siloxane. The substrate layer generally has a thickness of 5-3000 μm. In a preferred embodiment, the color converter of the present invention does not include a substrate.

[0381] Similarly, when the color converter consists of one layer or has a layer structure, the layer comprising at least one organic fluorescent dye according to the invention can be applied to a substrate layer, for example glass, metal plates and foils, paper sheets and the like.

[0382] In a further preferred embodiment, the color converter according to the invention comprises neither a substrate layer nor a barrier layer.

[0383] In another embodiment, the color converter of the invention may comprise additional scattering layers, or layers for stability and / or for avoiding inhomogeneities (avoiding fogging on the screen).For example, the color converter of the invention may be produced by coextrusion with polycarbonate on both sides.

[0384] The compounds of formula (Ia), (Ib) and (Ic) are particularly useful in non-emissive displays due to their narrowband emission in the green spectral range of 500-560 nm, in particular 510-540 nm, and a FWHM of 60 nm or less, in particular 45 nm or less. They significantly increase the color gamut of displays with RGB color filters. Similarly, the compounds of formula (Ia), (Ib) and (Ic) are particularly useful in non-emissive displays due to their narrowband emission in the red spectral range of 595-700 nm, in particular 610-660 nm, and a FWHM of 70 nm or less, in particular 60 nm or less. They also significantly increase the color gamut of displays with RGB color filters.

[0385] Therefore, the present invention also relates to a backlight unit comprising:

[0386] (i) a light source for emitting light; and

[0387] (ii) at least one color converter as defined herein.

[0388] The light source in a standard LCD backlight unit (BLU) is typically a plurality of LEDs. Preferably, the LEDs are blue LEDs having a central emission wavelength of 400-480 nm. Suitable blue LEDs are, for example, those based on gallium nitride (GaN) or indium gallium nitride (InGaN). White light emitting diodes currently used for LCD flat panels use a Ce:YAG down-conversion phosphor layer on a plurality of blue emitting LED chips. These WLEDs typically have a correlated color temperature of 6000-12000 K, preferably 6500-11000 K. In particular, the light emitted from the white LEDs contains wavelengths in the range of 400-700 nm.

[0389] The backlight unit can be an edge-lit backlight or a full-array backlight. The difference between an edge-lit backlight and a full-array backlight lies in the arrangement of the light sources. In an edge-lit configuration, the LEDs are assembled at the edge of a rectangular light guide plate, and the light from the LEDs is totally internally reflected on the inner surface of the light guide plate and finally extracted from the top surface of the light guide plate. The color converter faces the top side of the light guide plate. In a full-array backlight, the color converter is arranged above the array of LEDs in a remote phosphor arrangement.

[0390] According to the invention, a backlight unit comprises at least one color converter as defined above.

[0391] The backlight unit may further include a reflector below the light guide, a lower diffuser disposed on the light guide, a brightness improvement film and / or a diffusion film.

[0392] According to an embodiment of the invention, the color converter does not contain any light scattering agent.

[0393] According to a preferred embodiment of the invention, the color converter comprises an inorganic or organic light scattering agent. Suitable inorganic and organic light scattering agents are those mentioned above, especially those mentioned as preferred examples. Light scattering agents in color converters for display applications typically have a diameter of 5-500 nm.

[0394] According to the invention, the color converter is physically separated from the light source, i.e., the color converter is in a remote phosphor arrangement relative to at least one light source. When used in a backlight unit, the distance between the LED light source and the color converter may be 0.01-20 mm, such as 0.01-10 mm, or 0.01-5 mm, or 0.05-3.5 mm. The backlight unit is incorporated into a liquid crystal display module.

[0395] Therefore, the present invention also relates to a liquid crystal display module, comprising:

[0396] (i) a liquid crystal panel comprising a thin film transistor (TFT) array, a liquid crystal layer, and a color filter array, wherein the color filter array comprises red, green, and blue color filters;

[0397] (ii) at least one light source, and

[0398] (iii) at least one converter as defined herein.

[0399] The light source is typically a plurality of LEDs. Suitable light sources are white light emitting diodes or blue light emitting diodes including micro-LEDs and mini-LEDs as defined above.

[0400] In particular, the color converter may comprise a light scattering agent as defined above.

[0401] According to the invention, the color converter is physically separated from the light source, i.e. the color converter is in a remote phosphor arrangement relative to the light source. The distance between the light source and the color converter may be 0.01-20 mm, e.g. 0.01-10 mm, or 0.01-5 mm, or 0.05-3.5 mm. Typically, the color converter is arranged between the light source and the liquid crystal panel, i.e. the color converter and the light source are components of a backlight unit as defined above. The liquid crystal display panel comprises a color filter array, a thin film transistor (TFT) array opposite the color filter substrate, and a liquid crystal layer.

[0402] Regardless of whether the LCD display is constructed with a full array or edge-lit LED light source, light passes through the liquid crystal layer and the color filter array in sequence.

[0403] The color filter array comprises a plurality of red, green and blue color filters, a red color filter for red pixels; a green color filter for green pixels and a blue color filter for blue pixels. Each of the three color filters operates independently and the color of a single pixel is represented by one of the three colors or by a combination of at least two of the three colors. The color filter array typically comprises a light blocking member, which is used to define a matrix of pixel areas. The light blocking member is also referred to as a black matrix. The black matrix blocks light that is outside the display, which would otherwise appear on the visual side of the substrate, thereby reducing the overall contrast. The color filter array may additionally comprise white pixels in the array.

[0404] The liquid crystal layer includes a plurality of liquid crystal molecules. The liquid crystal display device also includes a pair of polarizers.

[0405] The liquid crystal display panel may be a transmissive display panel, a reflective display panel, or a transflective display panel.

[0406] The above-mentioned LCD module is of passive matrix type or active matrix type. Active matrix LCD includes active driving elements, such as thin film transistors (TFT) or diodes in each pixel element.

[0407] Active matrix LCD devices may operate according to twisted nematic (TN), in-plane switching (IPS), vertical alignment (VA), or multi-domain vertical alignment (MVA) technology.

[0408] Advantageously, due to the use of the color converter of the present invention, most of the light is generated in the primary wavelengths. Therefore, less energy is wasted because less light is filtered out compared to prior art LED backlights. The LCD device of the present invention produces concentrated peaks in its green and / or red primary wavelengths, which can be mixed to produce a larger color gamut with more natural and vivid colors.

[0409] Additionally, in some embodiments, a liquid crystal display module may be provided along with a touch-sensitive display element.

[0410] In a further aspect, the invention relates to an apparatus selected from a static visual display device, a dynamic visual display device and a lighting device, comprising a color converter as defined above. Static visual display devices are for example visual display devices of computers, televisions, visual display devices in printers, kitchen appliances and advertising flat panels, lighting and information flat panels. Dynamic visual display devices are for example visual display devices in small phones, laptops, tablet computers, digital cameras, MP-3 players, vehicles and destination displays on buses and trains.

[0411] Another aspect of the invention relates to a television device comprising a display device as defined above.

[0412] Another aspect of the invention relates to a lighting device (lighting arrangement) comprising at least one color converter as defined above.

[0413] In particular, the present invention relates to a lighting device comprising:

[0414] (i) at least one LED selected from a blue LED having a central emission wavelength of 400-480 nm and a white LED having a correlated color temperature of 3000-20000 K; and

[0415] (ii) at least one color converter as defined above;

[0416] The color converter is arranged remotely relative to at least one LED, ie the color converter is spatially separated from the LED.

[0417] In one embodiment, the lighting device of the present invention comprises only one LED. In a preferred embodiment, the lighting device of the present invention comprises a plurality of LEDs. In one embodiment, the lighting device of the present invention comprises a plurality of LEDs, all of which are blue. In another embodiment, the lighting device of the present invention comprises several LEDs, at least one of which is blue, and at least one LED is non-blue but emits light of another color.

[0418] In applications for conventional lighting, the distance between the LED and the color converter is typically greater than 0.1 mm, such as 0.2 mm or greater, and in some embodiments equal to or greater than 0.1-10 cm, such as 0.3-5 cm or 0.5-3 cm.

[0419] In general, the type of LED used is not critical to the lighting device of the present invention. In a preferred embodiment, the power density of the blue LED light contacting the converter surface is typically less than 200 mW / cm 2 , preferably less than 120mW / cm 2 , more preferably less than 80 mW / cm 2 It is also possible to use LEDs with higher power densities, such as 150 or 200 mW / cm 2 .

[0420] The color converter can be arranged around the LED in a concentric manner, for example, or have a planar geometry. It can be in the form of a plate, sheet or film, in the form of a droplet, or in cast form, for example.

[0421] The lighting device of the present invention is suitable for lighting indoors, outdoors, in offices, vehicles, torches, game machines, street lamps, and traffic signs.

[0422] The lighting devices of the present invention show excellent optical properties with high lighting efficiency. They show warm white light at a CCT below 4000K, especially below 3500K, with a high average color imparting index greater than 90, preferably at least 92, especially at least 95; have a high R9 value greater than 60, preferably at least 70, especially at least 75; and have a high lighting efficiency greater than 80 lumens / watt.

[0423] The present invention is described in more detail below by way of examples. Example

[0424] Abbreviations used: conc. means concentration; ex. means example; FQY means fluorescence quantum yield; PC means polycarbonate; PET means polyethylene terephthalate; Rf means retention factor; TLC means thin layer chromatography.

[0425] I. Preparation of compounds of formula (Ib)

[0426] All experiments were performed in dry glassware under argon.

[0427] Example 1: Compound of formula (Ib), wherein EWG1=EWG2=CN; R 1 , R 3 , R 4 and R 6 are each methyl; and R 7b It is ethyl:

[0428]

[0429] 1.1 Preparation

[0430]

[0431] The title compound was prepared as described in Heteroatom Chemistry, Vol. 5, No. 4, 1994 403-407.

[0432] 1.2 Preparation

[0433]

[0434] A mixture of 1.96 g (0.0074 mol) of the above dipyrromethene compound from Example 1.1, 525 mL toluene, 8.4 g (0.065 mol) of N-ethyl-N,N-diisopropylamine and 13.2 g (0.089 mol) of boron trifluoride diethyl etherate was heated to 75° C. for 2 hours. The mixture was then cooled to room temperature. The mixture was washed 4 times with 500 mL of water. The toluene phase was concentrated in vacuo and subjected to column chromatography using dichloromethane as solvent. 589 mg (25%) of the red compound were isolated with an HPLC purity of 99.6%. According to DSC (glass), the starting point of the decomposition was 286° C.

[0435] Example 2: Compound of formula (Ib), wherein EWG1=EWG2=CN; R 1 =R 6 =phenyl; R 3 =R 4 Each is 4-methoxyphenyl; and R 7b It is 2,4,6-trimethylphenyl:

[0436]

[0437] 2.1 Preparation

[0438]

[0439] The reaction is carried out in a similar manner to that described by AR Katritzky, J. Org. Chem. 2000, 65, 8819-8821.

[0440] A mixture of 12.5 g (71 mmol) of 4-methoxythiobenzamide, 10.81 g (71 mmol) of 1-H-benzotriazole-1-methanol, 200 mL of toluene and 68 mg (0.35 mmol) of p-toluenesulfonic acid was heated to reflux for 19 hours. The water formed was stripped off during the reaction. The reaction mixture was cooled to room temperature, 100 mL of cyclohexane was added, and the precipitate was collected by filtration and washed 3 times with 10 mL of cyclohexane. The product was purified by column chromatography on silica using ethyl acetate and dichloromethane as eluents. 12.05 g (57%) of a yellow solid was obtained.

[0441] Rf(CH2Cl2:ethyl acetate, 5:1)=0.53

[0442] 2.2 Preparation

[0443]

[0444] The reaction was carried out in a manner similar to that described in AR Katritzky, J. Org. Chem. 2000, 65, 8819-8821. A mixture of 3.00 g (10.1 mmol) of the compound from 2.1 in 70 mL of THF and 1.57 g (11.1 mmol) of methyl iodide was cooled to 0° C. Then 1.27 g (11 mmol) of potassium tert-butoxide was added to 8 mL of THF over 10 minutes. The yellow solution became a yellow suspension. After stirring for 10 minutes, 1.46 g (11.1 mmol) of trans-cinnamonitrile was added. 3.42 g (30 mmol) of potassium tert-butoxide dissolved in 12 mL of THF was added over 10 minutes. The mixture was stirred at 0° C. for 5 minutes and then heated to reflux for 60 minutes. The reaction mixture was then cooled to room temperature. The solvent was evaporated in vacuo and the residue was absorbed in a mixture of dichloromethane and water. The precipitate is insoluble in dichloromethane and can be filtered, washed with dichloromethane and water. 1.33 g (48%) of a white solid are obtained.

[0445] Rf=0.86(CH2Cl2:ethyl acetate=10:1)

[0446] 2.3 Preparation

[0447]

[0448] 0.65 g (2.4 mmol) of the mixture of the above compounds from 2.2 was dissolved in 30 mL of dichloroethane. Then 0.18 g (1.19 mmol) of The mixture was stirred at reflux for 4 hours. The mixture was cooled to room temperature. 0.36 g (1.54 mmol) of dichlorodicyanobenzoquinone was then added and the mixture was stirred for 5 minutes, turning dark green. The mixture was diluted with dichloromethane, washed with aqueous NaHCO3 solution, hydrochloric acid, water and dried over MgSO4. The solvent was evaporated under reduced pressure. 0.72 g (90%) of a red solid was obtained.

[0449] Rf(CH2Cl2)=0.49

[0450] 2.4 Preparation

[0451]

[0452] To a mixture of 0.79 g (1.2 mmol) of the above compound from 2.3, 0.84 g (6.42 mmol) of N,N-diisopropylethylamine and 1.82 g (12.84 mmol) of boron trifluoride etherate dissolved in 40 mL of dichloroethane were added at room temperature. The mixture was stirred at room temperature for 10 minutes and the reaction mixture was diluted with dichloromethane. The solution was washed with NaHCO3 solution, hydrochloric acid and dried with MgSO4. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography using cyclohexane and ethyl acetate as eluents. 0.67 g (79%) of a red solid was obtained.

[0453] Rf (cyclohexane:ethyl acetate, 2:1) = 0.55.

[0454] Example 3: Compound of formula (Ib), wherein EWG1=EWG2=CN; R 1 =R 3 =R 4 =CH3; and R 7b It is 2,6-dichlorophenyl:

[0455]

[0456] 3.1 Preparation of potassium salt of 3-oxobutane-1-carbonitrile

[0457] A mixture of 4.40 g (50 mmol) of ethyl acetate, 12.46 g (60 mmol) of acetonitrile, 100 mL of THF and 6.73 g (60 mmol) of potassium tert-butoxide was stirred at room temperature for 18 hours. The resulting suspension was used as is.

[0458] 3.2 Preparation of 1-oxime acetone

[0459] A mixture of 9.0 g (40% in H2O, 50 mL) of methylglyoxal and 3.47 g (50 mmol) of hydroxylamine hydrochloride was stirred at room temperature for 18 hours. The resulting solution was used as is.

[0460] 3.3 Preparation of 2,4-dimethyl-1H-pyrrole-3-carbonitrile

[0461] 6.54 g of zinc are activated with 30 g of acetic acid and 10 mL of water. The solutions prepared according to 3.1 and 3.2 above are added simultaneously to the mixture over 2 hours and the mixture is heated to 50° C. for a further 2 hours. The mixture is filtered; THF is evaporated under reduced pressure. The product is isolated by extraction with dichloromethane and purified by column chromatography. 2.13 g (13%) of a white solid are isolated.

[0462] Rf (toluene:ethyl acetate, 10:1) = 0.27.

[0463] 3.4 Preparation

[0464]

[0465] A mixture of 7.56 g (63 mmol) of the pyrrole compound from 3.3 above, 5.25 g (30 mmol) of 2,6-dichlorobenzaldehyde, 600 mL of dichloromethane and 30 mL of trifluoroacetic acid was stirred at room temperature for 20 hours. A compound with Rf (CH2Cl2) = 0.25 was formed. Then 8.88 g (39 mmol) of dichlorodicyanobenzoquinone was added, and the mixture was stirred at room temperature for 2 hours. Water was added and the phases were separated. The aqueous phase was extracted with dichloromethane, the combined organic phases were washed with water, and the solvent was removed under reduced pressure. 13 g (quantitative) of the title compound was isolated and used without further purification.

[0466] Rf(CH2Cl2)=0.55.

[0467] 3.5 Preparation

[0468]

[0469] A mixture of 300 mL of toluene, 1.28 g (3.3 mmol) of the compound from 3.4 above, 6.72 g (56.4 mmol) of ethyl-diisopropylamine (Hünig base) was stirred at room temperature for 10 minutes. Then 7.66 g (51.5 mmol) of boron trifluoride etherate was added and the mixture was heated to 30° C. for 1 hour. The reaction mixture was then washed 3 times with water. The solvent was evaporated and the residue was purified by silica gel column chromatography, wherein dichloromethane was used as eluent. 688 mg (47%) of a red solid were obtained.

[0470] Rf(CH2Cl2)=0.6.

[0471] Example 4: Compound of formula (Ib), wherein EWG1=EWG2=CN; R 1 =R 3 =R 4 =CH3; and R 7b It is phenyl:

[0472]

[0473] The title compound was prepared following a procedure similar to that described in Example 3, except using benzaldehyde in place of 2,6-dichlorobenzaldehyde.

[0474] Rf(dichloromethane)=0.42.

[0475] Example 5: Compound of formula (Ib), wherein EWG1=EWG2=CN; R 1 =R 3 =R 4 =CH3; and R 7b It is 2,4,6-trimethylphenyl

[0476]

[0477] The title compound was prepared in a manner similar to that described in Example 3, except that Aldehyde replaces 2,6-dichlorobenzaldehyde.

[0478] Rf(dichloromethane)=0.62.

[0479] Example 6: Compound of formula (Ib), wherein EWG1=EWG2=CN; R 1 =R 3 =R 4 =phenyl; and R 7b It is 2,4,6-trimethylphenyl ( base)

[0480]

[0481] The title compound was prepared following a procedure similar to that described in Example 2, except using benzylthioamide in step 1 instead of 4-methoxythiobenzamide.

[0482] Rf (cyclohexane:ethyl acetate, 3:1) = 0.44.

[0483] Example 7: Compound of formula (Ib), wherein EWG1=EWG2=CN; R 1 =R 3 =R 4 =phenyl; and R 7b It is 2,3,4,5,6-pentafluorophenyl:

[0484]

[0485] The title compound was prepared in a manner similar to that described in Example 6, except that pentafluorobenzaldehyde was used instead of aldehyde.

[0486] Rf (cyclohexane:ethyl acetate, 2:1) = 0.64.

[0487] Example 8: Compound of formula (Ib), wherein EWG1=EWG2=CN; R 1 =R 3 =R 4 = methyl; and R 7b It is 2-chlorophenyl

[0488]

[0489] The title compound was prepared following a procedure similar to that described in Example 3, except using 2-chlorobenzaldehyde in step 4 instead of 2,6-dichlorobenzaldehyde.

[0490] Rf(CH2Cl2)=0.48.

[0491] Example 9: Compound of formula (Ib), wherein EWG1=EWG2=CN; R 1 =R 6 =CH3; R 3 =R 4 =2-(4-cyanophenyl)vinyl, and R 7b It is 2,4,6-trimethylphenyl:

[0492]

[0493] The compound from Example 5 (200mg, 0.48mmol), 4-cyanobenzaldehyde (161mg, 1.2mmol), piperidine (410mg, 4.8mmol) and p-toluenesulfonic acid hydrate (7mg, 0.04mmol) were stirred under reflux in 15mL toluene for 1.5 hours. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate. The reaction mixture was washed with water and saturated saline solution. The organic phase obtained was dried with MgSO4 and concentrated. The crude title compound was purified by silica gel chromatography (cyclohexane / ethyl acetate gradient) to obtain the title compound (2mg, 0.6%) as a purple solid. TLC (cyclohexane / dichloromethane, 2:1) Rf=0.53.

[0494] Example 10: Compound of formula (Ib), wherein EWG1=EWG2=CN; R 1 =R 6 =phenyl; R 3 =R 4 =2-(4-cyanophenyl)vinyl, and R 7b It is 2,4,6-trimethylphenyl:

[0495]

[0496] 10.1 Preparation of 4-(2,6-diisopropylphenoxy)benzonitrile

[0497]

[0498] 2,6-Diisopropylphenol (10.0 g, 54.4 mmol), 4-fluorobenzonitrile (6.59 g, 54.4 mmol) and K2CO3 (8.27 g, 59.9 mmol) were stirred in 100 mL of dimethylformamide (DMF) at 120°C for 2.5 hours (TLC control). After cooling to room temperature, the reaction mixture was poured into water (900 mL) and extracted with methyl tert-butyl ether (3 x 200 mL). The organic phase was concentrated. The obtained crude product (15.5 g) was purified by silica gel chromatography (cyclohexane / dichloromethane gradient) to give the title compound as a yellow oil (purity: 95%; 8.09 g, yield: 50.6%). TLC (cyclohexane / dichloromethane 2:1) Rf=0.40.

[0499] 10.2 4-(2,6-Diisopropylphenoxy)benzamide

[0500]

[0501] The reaction was carried out in a manner similar to that described by TD Penning et al., J. Med. Chem. 2002, 45, 3482-3490). To a suspension of 4-(2,6-diisopropylphenoxy)benzonitrile (7.60 g, 27 mmol) in tert-butyl alcohol (60 mL) was added 30 mL of dimethyl sulfoxide and powdered KOH (6.61 g, 100 mmol). The mixture was stirred and refluxed for 45 minutes (TLC control), then cooled to room temperature and poured into 350 mL of water. The resulting precipitate was filtered, washed with water (3 x 15 mL) and dried to give the title compound (7.5 g, 93%) as a light yellow solid. TLC (dichloromethane / ethyl acetate 9:1) Rf=0.17.

[0502] 10.3 N-(Benzotriazol-1-ylmethyl)-4-(2,6-diisopropylphenoxy)benzamide

[0503]

[0504] A suspension of 4-(2,6-diisopropylphenoxy)benzamide (4.0 g, 13.5 mmol), 1H-benzotriazole-1-methanol (2.05 g, 13.5 mmol) in toluene (30 mL) with a catalytic amount of p-toluenesulfonic acid (13 mg, 0.1 mmol) was heated under reflux for 4 hours while stirring (TLC control). The water formed was stripped off. After cooling, the resulting precipitate was filtered, washed with toluene (3 x 5 mL) and n-pentane (3 x 10 mL), and dried to give the title compound (5.5 g, 95%) as a white solid.

[0505] TLC (dichloromethane / ethyl acetate 9:1) Rf=0.56.

[0506] 10.4 N-(Benzotriazol-1-ylmethyl)-4-(2,6-diisopropylphenoxy)benzylsulfamide

[0507]

[0508] To a suspension of N-(benzotriazol-1-ylmethyl)-4-(2,6-diisopropylphenoxy)benzamide) in toluene (50 mL) was added Lawesson's reagent (2.32 g, 5.7 mmol). The mixture was stirred at 90°C for 3 hours (TLC control) and then cooled. The resulting precipitate was filtered and the resulting solution was concentrated. The crude product was purified by silica gel chromatography (dichloromethane / ethyl acetate gradient) to give the title compound (3.57 g, 84%) as a yellow solid. TLC (dichloromethane / ethyl acetate 9:1) Rf = 0.79.

[0509] 10.5 2-[4-(2,6-Diisopropylphenoxy)phenyl]-4-phenyl-1H-pyrrole-3-carbonitrile

[0510]

[0511] The reaction was carried out in a similar manner to that described by AR Katritzky et al., J. Org. Chem. 2000, 65, 8819-8821). To a solution of N-(benzotriazol-1-ylmethyl)-4-(2,6-diisopropylphenoxy)benzylsulfamide (3.71 g, 8.3 mmol) and iodomethane (1.3 g, 9.2 mmol) in tetrahydrofuran (40 mL) was added t-BuOK solution (5.6 mL, 20% in tetrahydrofuran, 9.2 mmol) at 0° C. over 5 minutes. The mixture was stirred at 0° C. for a further 10 minutes (TLC control). Then (E)-3-phenylprop-2-enenitrile (1.21 g, 9.2 mmol) and the rest of t-BuOK (15.4 mL, 20% in tetrahydrofuran, 29 mmol) were added at 0° C. over 5 minutes. The reaction mixture was stirred for another 5 minutes at 0°C and then refluxed for 30 minutes (TLC control). The solvent was removed, the residue was taken up in toluene (40 mL), washed with water, dried over MgSO4 and concentrated. The crude product was purified by silica gel chromatography (cyclohexane / dichloromethane, gradient) to give the title compound (1.82 g, 50%) as a light grey solid, TLC (cyclohexane / ethyl acetate 2:1) Rf=0.55, and 5-[4-(2,6-diisopropylphenoxy)phenyl]-4-phenyl-1H-pyrrole-3-carbonitrile (0.93 g, 25%) as a light grey solid, TLC (cyclohexane / ethyl acetate 2:1) Rf=0.35.

[0512] 10.6 Preparation

[0513]

[0514] The apparatus was heated and cooled under argon. 2-[4-(2,6-diisopropylphenoxy)phenyl]-4-phenyl-1H-pyrrole-3-carbonitrile (1.0 g, 2.4 mmol), Aldehyde (0.18g, 1.2mmol), trifluoroacetic acid (1.1mL) and acetic anhydride (0.7mL) in 1,2-dichloroethane (40mL) solution refluxed 30 minutes and stirred (TLC controlled) simultaneously, then cooled.Then, dichlorodicyanobenzoquinone (0.36g, 1.5mmol) was added at room temperature, and the mixture was stirred for 10 minutes (TLC controlled).The reaction mixture was diluted with dichloromethane (50mL), and extracted with water, NaHCO3 saturated aqueous solution and 0.5M HCl (each 1x 40mL), then washed with saturated brine solution, and dried with MgSO4.After concentration, the crude title compound (1.27g 100%) as a purple solid was obtained, with a purity of 91%.

[0515] TLC (cyclohexane / ethyl acetate 2:1) Rf=0.87.

[0516] 10.7 Preparation

[0517]

[0518] The title compound was prepared in a similar manner as described in Example 2.3, but using the compound from 10.6 as starting material. The crude product obtained was purified by silica gel chromatography (cyclohexane / dichloromethane gradient). The obtained fractions were concentrated and taken up in isopropanol (20 mL). The title product was reprecipitated by slowly adding water (10 mL) to give the title compound as a dark purple solid (0.66 g, 55%), TLC (cyclohexane / e 2:1) Rf=0.75.

[0519] II Preparation of Color Converter

[0520] II.1 By extrusion:

[0521] equipment:

[0522] Mixing: Roller table

[0523] Extruder: Twin screw, 16mm / 36D, Dr.Collin GmbH

[0524] Granulator: Granulator, Scheer, Stuttgart

[0525] Foil: Teach-Line extruder + cooling roller, Dr. Collin GmbH

[0526] Experimental procedures:

[0527] Polymer: Polyethylene terephthalate, PET Terez 3200, from TER HELL PLASTIC GMBH

[0528] Pre-drying: 8 hours at 150°C

[0529] Mixing: polymer + dye, 20min Turbula Fuchs

[0530] Extrusion: up to 260°C (cold, 150°C, 250°C, 260°C, 260°C, 260°C and 260°C)

[0531] Drying: 8 hours at 150°C

[0532] Foil: Multi-layer co-extrusion extruder, 20mm / 25D

[0533] Up to 280℃ (cold, 260℃, 275℃, 280℃, 280℃, 280℃ and 280℃) Slit nozzle: 150mm width

[0534] Temperature: 280℃

[0535] Cooling roller:

[0536] Roller temperature 75℃

[0537] The fluorescent dyes used according to the invention are used for producing color converters by extrusion.For this purpose, the compound of Example 1 is introduced into a matrix composed of the abovementioned polyethylene terephthalate (PET Terez 3200 from TER HELL PLASTIC GMBH).

[0538] For comparative purposes, this procedure was repeated, but using compound C1 instead of the compound of Example 1.

[0539]

[0540] Compound C1 degraded / decomposed during extrusion.

[0541] In addition, a color conversion film containing the compound of the present invention and TiO2 was prepared in a similar manner. For each film, the concentration of the compound of the present invention was 0.01% by weight, and the concentration of TiO2 was 0.36% by weight.

[0542] II.2 By solution processing (for comparison purposes):

[0543] Materials used:

[0544] Polymer 1: Polycarbonate (PC, 2808, from Bayer),

[0545] Polymer 2: Methyl methacrylate homopolymer with a Vicat softening temperature of 96° C. according to DIN EN ISO 306 (PMMA, 6N, from Evonik),

[0546] Polymer 3: Styrene homopolymer, density is 1048kg / m 3 , and has a Vicat softening temperature of 98° C. according to DIN EN ISO 306 (PS 168N from Styrolution).

[0547] For comparative purposes, solution-processed membranes were produced. To this end, the compounds according to the invention were incorporated into matrices consisting of the polymers 1, 2 and 3, respectively, as described below.

[0548] About 2.5 g of polymer 1, 2 or 3 and 0.01 wt % of the dye were dissolved in about 5 mL of dichloromethane, and then 0.36 wt % of TiO2 (Kronos 2233) was dispersed therein. The resulting solution / dispersion was applied to the glass surface with a doctor blade so that the wet film thickness was 400 μm. After the solvent had been dried and removed, the film was peeled off from the glass and dried overnight at 50° C. in a vacuum drying kitchen. Two circular film specimens with a diameter of 15 mm were punched out from each film with a thickness of 67 μm and used as analytical samples.

[0549] The fluorescence quantum yield (FQY) of these analyzed samples was detected with a C9920-02 quantum yield measurement system (from Hamamatsu). This was performed by irradiating each sample with 470 nm light in an integrating sphere (Ulbricht sphere). The proportion of unabsorbed excitation light and the proportion of fluorescence emitted by the sample were detected by a CCD spectrometer by comparison with a reference detection in an Ulbricht sphere without sample. The spectral intensity of the unabsorbed excitation light or the spectral intensity of the emitted fluorescence was integrated to obtain the absorption intensity or fluorescence intensity or fluorescence quantum yield of each sample.

[0550] Fluorescence quantum yield (FQY) test results:

[0551] The compound of Example 1:

[0552] Extruded PET-film: emission λmax: 523 nm; emission, FWHM: 33 nm; FQY: 86%;

[0553] Solution processed PC-film: FQY: 89%.

[0554] Comparative Compound C1:

[0555] Extruded PET-film: emission λmax: 527 nm; emission, FWHM: 40 nm; FQY: 30%;

[0556] Solution processed PC-matrix: FQY: 90%.

[0557] Surprisingly, the compound of Example 1 did not degrade or decompose during extrusion. In contrast, comparative compound C1 decomposed / degraded during extrusion, which was manifested by a low fluorescence quantum yield.

[0558] The results for each of the green-emitting compounds of Examples 1, 3, 4, 5 and 8 in PET in a layer with a thickness of 70 μm are summarized in Table I.

[0559] Table I: Concentration of green-emitting compound: 0.01 wt %; TiO2 concentration: 0.36 wt %

[0560]

[0561] For comparison, solution-processed films in PC with a thickness of 67 μm were prepared, containing the compounds of Examples 1, 3, 4, 5 or 8 and TiO 2 , respectively. The results are summarized in Table II.

[0562] Table II: Solution processed films in PC, concentration of green emitting compound: 0.01 wt%; concentration of TiO2: 0.36 wt%

[0563]

[0564] The results for each of the red-emitting compounds of Examples 2, 6, 7 and 10 in PET in a layer with a thickness of 70 μm are summarized in Table III.

[0565] Table III: Concentration of red-emitting compound: 0.01 wt%; TiO2 concentration: 0.36 wt%; λ excitation: 570 nm

[0566]

[0567] For comparison, solution-processed films in PC with a thickness of 67 μm were prepared, containing the compounds of Examples 2, 6, 7 and 10 and TiO2, respectively. The results are summarized in Table IV

[0568] Table IV: Concentration of red-emitting compound: 0.01 wt %; TiO2 concentration: 0.36 wt %; λ excitation: 570 nm

[0569]

[0570] III. Preparation of Display Films Containing the Green-Emitting Compound and the Red-Emitting Compound of the Invention by Extrusion

[0571] Two films were produced using an extrusion line. The film thickness was monitored online by a capacitive sensor. The extruder had a screw diameter of 30 mm and a processing length of 20D. The nozzle width was 300 mm, resulting in a maximum film width of about 250 mm. The extrusion assembly was followed by a coolable / heatable cooling roll / smoothing device with trimming and winding units. The maximum take-up speed was 16 m / mm. Coils with a thickness of 130 μm and 150 μm were obtained.

[0572] The PET pellets containing the compound according to the invention were predried in a circulating air dryer at 150° C. overnight.

[0573] Two display films were produced by extrusion at thicknesses of 130 μm and 150 μm, comprising 0.027 wt % of the compound of Example 4, 0.0041 wt % of the compound of Example 2 and 0.3 wt % TiO2 in PET.

[0574] Extrusion temperature: 260-290℃

[0575] Cooling roller temperature: 75°C

[0576] The resulting film was illuminated with a Fortimo blue LED, wherein the total light irradiance from the LED was measured by an optical detection tool equipped with an optical module in an integrating sphere from Instrument System, see Figure 1 Optical parameters such as color coordinates CIE-x and CIE-y, color coordinates CIE-u' (L*, u*, y*) in CIE 1976, correlated color temperature CCT* (in Kelvin), color point distance (BBL) from the Planck curve were measured in an integrating sphere. The results are listed in Table V.

[0577] Table V: Photometric data of the converter according to the invention for Fortimo blue LEDs

[0578] No. CIE-x CIE-y CIE-u′ CCT[K] Planck distance Fortimo 0.1537 0.0259 0.2048 0 0.00E+00 130μm film 0.2771 0.2698 0.1950 11977 -7.78E-03 150μm film 0.2922 0.2845 0.2005 8943 -9.34E-03

[0579] These films (optical stack + LCD + color filters) were tested in a TV display and gave a DCI coverage of 99%.

[0580] Display films containing green-emitting compounds and red-emitting compounds of the present invention were prepared by extrusion, co-extruded with PC on both sides.

[0581] Three films were produced using an extrusion line. The film thickness was monitored online by a capacitive sensor. The extruder had a screw diameter of 30 mm and a processing length of 20D. The nozzle width was 300 mm, resulting in a maximum film width of about 250 mm. The extrusion assembly was followed by a coolable / heatable cooling roller / smoothing device with trimming and winding units. The maximum take-up speed was 16 m / mm. Coils of PET films with a thickness of 200 μm, 250 μm and 300 μm were obtained. All films were coextruded with PC on both sides, 25 μm on each side.

[0582] The PET pellets containing the compound according to the invention were predried in a circulating air dryer at 150° C. overnight.

[0583] - dyes: compounds of Examples 2 and 5,

[0584] -PET: Shinkong 5015W

[0585] -Siloxane-based scattering agent: HSP200

[0586] -ABA structure for thermal stability and resistance to unevenness,

[0587] - A layer with 0.3% Sylysia 340 (micrometer-sized silica particles) in PC, 25 μm (same on both sides: ABA)

[0588] - Layer B: Compound of Example 5: 0.017 wt %; Compound of Example 2: 0.0026 wt %; 1% Siloxane HSP 200

[0589] -Thickness of B layer: 200μm, 250μm and 300μm

[0590] Extrusion temperature: 260-290℃

[0591] Cooling roller temperature: 75°C

[0592] The resulting film was illuminated with a Fortimo blue LED, where the total light from the LED was measured by an optical detection tool equipped with an optical module in an integrating sphere from Instrument Systems. Optical parameters such as the color coordinates CIE-x and CIE-y, the color coordinates CIE-u' (L*, u*, y*) in CIE 1976 were measured in the integrating sphere. The results are listed in Table VI.

[0593] Table VI: Photometric data of the converter according to the invention for Fortimo blue LEDs

[0594] No. CIE-x CIE-y CIE-u′ Fortimo 0.1537 0.0259 0.2048 200μm film 0.2322 0.1929 0.1914 250μm film 0.2522 0.2177 0.1975 300μm film 0.2643 0.2318 0.2013

[0595] These films were also tested in a TV set using the color converter of the present invention instead of the QDF of a commercial TV (TCL U55X9006). The stack configuration is shown below:

[0596] Blue LED / diffusion film / color converter of the present invention / DBEF (2D-prism) / BEF (reflective polarizer)

[0597] The following color points (CIE 1931) were measured with the Hera Spectro:

[0598] No. CIE-x CIE-y 200μm film 0.2481 0.2074 250μm film 0.2694 0.2272 300μm film 0.2797 0.2385

[0599] III Photostability

[0600] The T80 values ​​of the compound of Example 1 in different polymer matrices were measured. T80 was measured at 100 mW / cm 2 The fluorescence (product abs*QY) decays to a value at which it reaches 80% of its initial value when irradiated with blue light (450 nm). For this purpose, a polyethylene terephthalate (PET) polymer film doped with 0.36 wt. % TiO2 and the compound of Example 1 (0.01 wt. %) was prepared as described above. The results are summarized in Table VII. Film thickness: 70 μm

[0601] Table VII: Lifetime (days) when irradiated (T80)

[0602]

[0603] It was found that the lifetime of the organic fluorescent compound of Example 1 was significantly increased once embedded in the extruded polyethylene terephthalate film compared to polymer matrices such as polystyrene, polymethyl methacrylate and polycarbonate.

[0604] Additionally, the compounds of Examples 2, 4, 5 and 7 were tested in PET and PC under T80 blue illumination (450 nm) and T80 white illumination (DLM Flex). The results are summarized in Tables VIII and IX.

[0605] Table VIII: Lifespan (days) when irradiated (T80)

[0606] Results for compounds emitting red light; λ excitation: 570 nm

[0607] - In 70 μm PET film, dye concentration = 0.01%, TiO2 concentration = 0.36%; and

[0608] - In 67μm PC film, dye concentration = 0.01%, TiO2 concentration = 0.36%

[0609]

[0610] >Indicates that the experiment is still running

[0611] Table IX: Lifespan (days) when irradiated (T80)

[0612] Results for compounds that emit green light;

[0613] - In 70 μm PET film, dye concentration = 0.01%, TiO2 concentration = 0.36%; and

[0614] - In 67μm PC film, dye concentration = 0.01%, TiO2 concentration = 0.36%

[0615]

[0616] In addition, the compound of Example 10 was tested in PET and PC under T95 blue illumination (450 nm) and T95 white illumination (DLM Flex). The results are summarized in Table X.

[0617] Table X: Lifespan under irradiation (days) (T95)

[0618] Results for the compound of Example 10 emitting red light; λ excitation: 570 nm

[0619] - In 70 μm PET film, dye concentration = 0.01%, TiO2 concentration = 0.36%; and

[0620] - In 67μm PC film, dye concentration = 0.01%, TiO2 concentration = 0.36%

[0621]

[0622] > indicates that this experiment is still running.

Claims

1. A color converter, comprising: (a) a polyethylene terephthalate base material; and (b) at least one organic fluorescent dye introduced into the polyethylene terephthalate matrix material by extrusion, which is selected from the compounds of formula (Ib) or mixtures thereof: in EWG1 and EWG2 are independently CN; R 1 , R 3 , R 4 , R 6 are independently selected from hydrogen, fluorine, COOR 14 , CH(COOR 14 ) 2 , C 1 -C 20 Alkyl, C 2 -C 20 Alkenyl, C 2 -C 20 Alkynyl, C 3 -C 20 Cycloalkyl, C 4 -C 20 Cycloalkenyl, C 6 -C 14 aryl, heterocyclic or heteroaryl, Among them C 1 -C 20 Alkyl, C 2 -C 20 Alkenyl and C 2 -C 20 Alkynyl is unsubstituted or substituted by one or more substituents R 8 replace, Among them C 3 -C 20 Cycloalkyl and C 4 -C 20 The cycloalkenyl group is unsubstituted or substituted by one or more substituents R 9 replace, Among them C 6 -C 14 The aryl group is unsubstituted or substituted by one or more substituents R 10 replace, Wherein the heterocyclic group and the heteroaryl group are unsubstituted or substituted by one or more substituents R 10 replace; R 7b is hydrogen, fluorine, cyano, C 1 -C 20 Alkyl, C 2 -C 20 Alkenyl, C 2 -C 20 Alkynyl, C 3 -C 20 Cycloalkyl, C 4 -C 20 Cycloalkenyl, C 6 -C 14 aryl or heteroaryl; Among them C 1 -C 20 Alkyl, C 2 -C 20 Alkenyl and C 2 -C 20 Alkynyl is unsubstituted or substituted by one or more substituents R 8 replace, Among them C 3 -C 20 Cycloalkyl and C 4 -C 20 The cycloalkenyl group is unsubstituted or substituted by one or more substituents R 9 replace, Among them C 6 -C 14 The aryl group is unsubstituted or substituted by one or more substituents R 11 replace; Each R 8 independently selected from fluorine, C 3 -C 20 Cycloalkyl, C 4 -C 20 Cycloalkenyl, C 6 -C 14 Aryl, C 6 -C 14 an aryloxy group or a heteroaryl group, Among them C 3 -C 20 Cycloalkyl and C 4 -C 20 The cycloalkenyl group is unsubstituted or substituted by one or more substituents R 9 Replace, and Among them C 6 -C 14 Aryl and C 6 -C 14 The aryloxy group is unsubstituted or substituted by one or more substituents R 10 replace; Each R 9 are independently selected from cyano, fluoro, C 1 -C 10 Alkyl, C 1 -C 10 Fluoroalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Fluoroalkoxy or tri-(C 1 -C 10 Alkyl)silyl; Each R 10 are independently selected from cyano, fluoro, C 1 -C 10 Alkyl, C 1 -C 10 Fluoroalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Fluoroalkoxy, tri-(C 1 -C 10 alkyl)silyl, heteroaryl, phenyl or phenoxy, wherein the aromatic rings in the last two groups are unsubstituted or substituted by one or more substituents R 12 replace; Each R 11 Independently selected from EWG1, fluorine, chlorine, bromine, C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Fluoroalkoxy, tri-(C 1 -C 10 alkyl)silyl, N(C 1 -C 20 alkyl) 2 ,N(C 6 -C 14 Aryl) 2 , heteroaryl, biphenyl, terphenyl, spirofluorenyl, C 6 -C 14 Aryl, C 6 -C 14 Aryl-C 1 -C 10 Alkylene, C 6 -C 14 Aryl-C 1 -C 10 Alkylene-O-, wherein the last six groups are unsubstituted in the aryl moiety or are substituted by one or more substituents R 12 replace; Each R 12 Independently selected from EWG1, C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Fluoroalkoxy, tri-(C 1 -C 10 alkyl) silyl or C 3 -C 20 Cycloalkyl; R 14 Selected from hydrogen, C 1 -C 10 Alkyl, C 1 -C 10 Fluoroalkyl, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkyl-C 1 -C 10 Alkylene, C 6 -C 14 Aryl or C 6 -C 14 Aryl-C 1 -C 10 Alkylene, Among them C 6 -C 14 Aryl and C 6 -C 14 Aryl-C 1 -C 10 The aryl moiety in the alkylene group is unsubstituted or substituted with one or more substituents R 10 replace.

2. The color converter of claim 1, wherein the polyethylene terephthalate matrix material comprises at least 90 wt. % polyethylene terephthalate, based on the total polymer content of the polyethylene terephthalate matrix material.

3. The color converter according to claim 1, wherein each R 10 are independently selected from cyano, fluoro, C 1 -C 10 Alkyl, C 1 -C 10 Fluoroalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 Fluoroalkoxy, tri-(C 1 -C 10 alkyl)silyl, phenyl, phenoxy or heteroaryl.

4. The color converter according to any one of claims 1 to 3, wherein R 1 , R 3 , R 4 and R 6 Each independently selected from C 1 -C 10 Alkyl, phenyl or phenyl-C 2 -C 6 Alkenyl, wherein in the last two radicals, phenyl and in the phenyl-C 2 -C 6 The phenyl moiety in the alkenyl group is unsubstituted or substituted with 1, 2 or 3 substituents R 10 replace.

5. The color converter according to any one of claims 1 to 3, wherein all R 1 , R 3 , R 4 and R 6 Each independently selected from C 1 -C 10 Alkyl; or all R 1 , R 3 , R 4 and R 6 Each independently selected from phenyl, wherein the phenyl group is unsubstituted or carries 1, 2, 3, 4 or 5 substituents R 10 .

6. The color converter according to any one of claims 1 to 3, wherein R in formula (Ib) 7b It is hydrogen, cyano, CF 3 , C 1 -C 4 alkyl, pyridyl, dibenzofuranyl, or phenyl, wherein the phenyl group is unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents R 11 replace.

7. The color converter according to claim 6, wherein R in formula (Ib) 7b is hydrogen, C 1 -C 4 Alkyl, or phenyl, the phenyl is unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents selected from the following R 11 Substitution: Fluorine, Chlorine, Cyano, C 1 -C 4 Alkyl, C 1 -C 4 Fluoroalkyl, C 1 -C 4 Alkoxy, C 1 -C 4 Fluoroalkoxy, benzyloxy, COO(C 1 -C 4 alkyl), pyridyl, phenyl-C 1 -C 10 alkylene, phenyl, biphenyl, terphenyl, 9,9-dimethylfluorenyl, wherein the aromatic moieties in the last five groups are unsubstituted or substituted by 1, 2 or 3 groups selected from CN, C 1 -C 4 Alkyl, C(O)C 1 -C 4 Alkyl or COO(C 1 -C 4 Alkyl) group R 12 replace.

8. A color converter according to any one of claims 1 to 3, comprising at least a first compound of formula (Ib) or a mixture thereof which emits light with a central emission wavelength in the range of 500-560 nm, and at least a second compound of formula (Ib) or a mixture thereof which emits light with a central emission wavelength in the range of 595-700 nm.

9. The color converter according to any of claims 1 to 3, wherein the at least one organic fluorescent dye is a fluorescent dye of formula (Ib) selected from compounds (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21), (22), (23), (24), (25), (26), (27), (28), (29), (30), (31), (32), (33), (34), (35), (36), (37), (38), (39) or mixtures thereof: 4-CN-PV: 2-(4-cyanophenyl)vinyl DIPPP: 4-(2,6-diisopropylphenoxy)phenyl.

10. The color converter according to any one of claims 1 to 3, further comprising at least one light scattering agent.

11. A backlight unit, comprising: (i) a light source for emitting light; and (ii) A color converter according to any one of claims 1 to 10, At least one of the color converters is remotely disposed relative to the light source.

12. A liquid crystal display module, comprising: (i) a liquid crystal panel comprising a thin film transistor (TFT) array, a liquid crystal layer and a color filter array, wherein the color filter array comprises red, green and blue color filters; (ii) at least one light source; and (iii) At least one color converter according to any one of claims 1 to 10.

13. A light emitting device comprising: (i) at least one LED selected from a blue LED having a central emission wavelength of 400-480 nm or a cool white LED having a correlated color temperature of 3,000-20,000 K; and (ii) at least one color converter according to any one of claims 1 to 10; At least one color converter is remotely located relative to at least one LED.

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